US20040195552A1 - Method for preparing light-absorbing polymeric compositions - Google Patents

Method for preparing light-absorbing polymeric compositions Download PDF

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US20040195552A1
US20040195552A1 US10/817,271 US81727104A US2004195552A1 US 20040195552 A1 US20040195552 A1 US 20040195552A1 US 81727104 A US81727104 A US 81727104A US 2004195552 A1 US2004195552 A1 US 2004195552A1
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Max Weaver
James Krutak
Brian Maxwell
Gerry Rhodes
Samuel Hilbert
Jean Fleischer
William Parham
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/56—Mercapto-anthraquinones
    • C09B1/58—Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals
    • C09B1/585—Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals substituted by aryl radicals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/56—Mercapto-anthraquinones
    • C09B1/62—Mercapto-anthraquinones with mercapto groups substituted by a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/14—Benz-azabenzanthrones (anthrapyridones)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • This invention relates to an improved method for preparing light-absorbing polymeric compositions, which are useful as powders or pellets for incorporation into a variety of thermoplastic resins such as cellulose esters, polyesters, polyolefins, polycarbonates, polyamides, etc. by conventional melt or solution blending techniques.
  • thermoplastic resins such as cellulose esters, polyesters, polyolefins, polycarbonates, polyamides, etc.
  • the colored thermoplastic resins thus produced have good clarity, good color development, excellent fastness to light and are useful for a variety of end uses where nonhazardous, nonmigrating, or nonextractable colorants are needed.
  • thermoplastic polymers may be colored by adding pigments or solvent dyes (e.g., see Thomas G. Weber, Editor, Coloring of Plastics, John Wiley & Sons, New York, 1979).
  • pigments e.g., see Thomas G. Weber, Editor, Coloring of Plastics, John Wiley & Sons, New York, 1979.
  • solvent dyes K. Venkataraman, Editor, The Chemistry of Synthetic Dyes, Vol. 8, Academic Press, New York, 1978, pp.
  • Plastics, paints, printing inks, rubber, cosmetics, and similar materials are typically colored by organic pigments when superior brilliance and tinctorial strength are important. Toxicity considerations have presented chronic problems relative to the use of organic pigments since some have been shown to be potential carcinogens and to cause contact dermatitis.
  • Plastics are also colored by using color concentrates consisting of physical admixtures of polymers and colorants (usually solvent dyes).
  • color concentrates consisting of physical admixtures of polymers and colorants (usually solvent dyes).
  • color polymeric materials such as polyester, e.g., poly(ethylene terephthalate) and blends thereof, present a number of problems, including:
  • Colorants may not mix well, for example, when using two or more color cencentrates to obtain a particular shade.
  • Colorants may diffuse or exude during storage and use of the colored polymeric material.
  • the colored polymeric compositions which are prepared by the process of this invention eliminate or minimize the aforementioned problems associated with the use of conventional dyes and pigments.
  • colored polyester compositions have been prepared by copolymerizing relatively low amounts of monomeric colorants during the polymer preparation (U.S. Pat. Nos. 5,194,571; 5,106,942; 5,102,980; 5,032,670; 4,892,922; 4,740,581; 4,403,092; 4,359,570; 4,267,306 and W092/07913).
  • the preparation of these colored polymers require dyes having outstanding thermal stability since the colorants are exposed to very high temperatures for prolonged periods of time necessary for polyester formation, thus severely circumscribing the selection of efficacious colorants.
  • only the nonazo type colorants have been shown to have the adequate thermal stability for copolymerization into polyesters, since azo type compounds do not have the resquite thermal stability for copolymerization.
  • polyurethanes have been prepared by reacting dyes bearing two hydroxyalkyl group with aliphatic and aromatic isocyanates (U.S. Pat. No. 5,194,463).
  • the organic isocyanates themselves are extremely toxic and present difficult handling problems. They also are reactive with water and thus the reaction requires specially dried monomeric dyes.
  • the colored polyurethanes as a class do not have excellent thermal stability.
  • Light-absorbing polymeric compositions have also been produced by free radical polymerization of vinyl functionalized light-absorbing monomers (U.S. Pat. Nos. 5,310,837; 5,334,710; 5,359,008; 5,434,231 and 5,461,131).
  • This invention relates to a method for preparing a light absorbing linear polymeric having Formula I
  • A comprises the residue of a diacidic monomer comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1200 nm and wherein the remaining portion of A comprises the residue of a non-light absorbing monomer which does not absorb significantly at wavelengths above 300 nm or has a light absorption maximum below 300 nm and wherein B is a divalent organic radical selected from C 2 -C 12 alkylene, C 3 -C 8 cycloalkylene, C 1 -C 4 alkylene- C 3 -C 8 -cycloalkylene- C 1 -C 4 alkylene, C 1 -C 4 alkylene-arylene- C 1 -C 4 alkylene, C 2 -C 4 alkylene-O— C 2 -C 4 alkylene, and C 2 -C 4 -alkylene-L-arylene- C 2 -C 4 alkylene and C 2 -C 4 alkylene and C 2
  • the process comprises reacting said diacidic monomer with an organic compound of Formula II
  • B is as defined above and X and X 1 reactive groups and are independently selected from bromine, iodine and R—SO 2 O; wherein R is selected from C 1 -C 6 alkyl; C 1 -C 6 alkyl substituted with chlorine, fluorine, C 1 -C 6 alkoxy, aryl, aryloxy, arylthio or C 3 -C 8 cycloalkyl; C 3 -C 8 cycloalkyl or aryl, with said reaction being carried out in a solvent in the presence of a base; wherein the useful diacid light-absorbing monomers have Formula III
  • H represents an acidic hydrogen atom
  • Y is a divalent light-absorbing moiety selected from a variety of chromophoric classes including azo, disazo, bis-azo, methine, arylidene, polymethine, azo-methine, azamethine, anthraquinone, anthrapyridone (3H-dibenz[f,ij]isoquinoline- 2,7-dione, nitroarylamines anthrapyridine (7H-dibenz[f,ij]isoquinoline-7-one, phthaloylphenothiazine (14H-naphth[2,3-a] phenothiazine-8,13-dione, benzanthrone(7H (de) anthracene-7-one), anthrapyrimidine(7H-benzo[e] perimidine-7-one), anthrapyrazole, anthraisothiazole, triphenodio
  • H represents an acidic hydrogen atom
  • Y 1 is a divalent moiety, selected from-O 2 C—R 1 —CO 2 — and-O—R 2 —O-and-O 2 C—R 3 —O—, wherein R 1 is selected from C 2 -C 12 alkylene, 1-4-cyclohexylene, arylene, arylene-O-arylene, arylene-S 2 -arylene, arylene-S-arylene, and C 1 -C 4 alkylene-O—C 1 -C 4 alkylene; wherein R 2 is selected from arylene, arylene-O-arylene, arylene-S-arylene, arylene-SO 2 -arylene, phenylene-phenylene, and phenylene-C(R 4 ) 2 -phenylene; wherein R 4 is selected from hydrogen and C 1 -C 4 alkyl; wherein R 3 is selected from arylene.
  • the hydrogen atoms are preferably attached to an oxygen, a sulfur or a nitrogen atom which in combination provides two acidic functional group which can produce the corresponding anions under basic conditions by removal of the protons.
  • the acidic functional groups usually have an acid dissociation constant of about 10 ⁇ 15 to about 10 ⁇ 12 (pK a of from about 1.5 to about 12).
  • pK a of from about 1.5 to about 12
  • both protons may be attached to a single nitrogen which is attached to a sulfonyl moiety thus providing two acidic hydrogens on a single functional group.
  • Typical, acidic groups which provide one acidic hydrogen include-CO 2 H, —SH, —OH attached to an aromatic ring, —CONHCO—, —SO 2 —NH—CO—, —SO 2 —NH—SO 2 —, 1(H)-1,2,4-triazol-3-yl-, imidazolyl, benzimidazolyl, pyrazolyl, —SO 2 H attached to aromatic ring, —NHSO 2 R 5 and-SO 2 NHR 5 , wherein R 5 is selected from C 1 -C 6 alkyl; C 1 -C 6 alkyl substituted with at least one group selected from C 1 -C 6 alkoxy, aryl, aryloxy, arylthio or C 3 -C 8 cycloalkyl; C 3 -C 8 cycloalkyl; aryl.
  • An example of an acidic functional group providing two acidic hydrogen attached to nitrogen is the sulfamoyl group (—SO 2 NH 2 ).
  • the preferred method for producing light absorbing polymeric compositions utilizes the monomers of Formula III, wherein the protons are a part of the-CO 2 H, OH attached to aromatic ring, —CO—NH—CO— or 1(H,)-1,2,4-triazol-3-yl functional groups.
  • the carboxy groups are normally attached to an aromatic ring carbon or aliphatic carbon which is a part of Y.
  • the hydroxy groups are normally attached to an unsubstituted or substituted phenyl or naphthyl radical which is a part of Y.
  • the —CO—NHCO— groups are usually attached to an aromatic ring to provide an imide such as phthalimide or naphthalimide which are a part of Y.
  • the 1(H)-1,2,4-triazol-3-yl group has the following Formula V, wherein R 5 ′ is
  • triazole selected from hydrogen, C 1 -C 6 alkyl or aryl. It should be observed that the triazole may exist in isomeric form as follows:
  • the 1(H)-1,2,4-triazol-3-yl group is preferably attached to a sulfur atom which is attached to the remainder of Y.
  • the method of the invention in the broadest sense involves the preparation of light absorbing polymeric compositions by reacting a diacidic monomer comprising at least 1 mole % of at least one diacidic light absorbing monomer represented by H-A-H with an organic compound containing two reactive groups represented by X—B—X 1 , where B, X and X 1 are as defined above.
  • a diacidic monomer comprising at least 1 mole % of at least one diacidic light absorbing monomer represented by H-A-H
  • the diacidic monomer H-A-H must be acidic enough to form two nucleophiles in the presence of base under convenient reaction conditions for the most advantageous process. This usually requires that diacidic monomers have pK a values of about 12 or below.
  • n represents the number of repeating units.
  • the number of repeating units must be at least 2, but usually ranges between about 2 and about 25, with the preferred number being between about 3 and about 15.
  • composition produced by the method of the invention comprises, as stated above, a polymer having the general formula ⁇ A-B ⁇ n .
  • the composition also comprises one or more cyclic compounds having the general formula
  • m may be 1, 2, 3, or 4, e.g., the cyclic compounds having the general structures:
  • the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X 1 , and the conditions used to facilitate the reaction to produce the composition.
  • the cyclic compounds may constitute up to about 35 weight percent, typically about 0.5 up to 30 weight percent, of the total weight of the composition produced by the method of the invention.
  • Suitable bases include alkali metal carbonates; alkali metal bicarbonates; tertiary amines such as triethylamine, tri-n-butylamine, N-methylpiperidine, N,N′-dimethylpiperazine, N-methylmorpholine, N,N,N′,N′-tetramethylenediamine, etc.; aromatic nitrogen bases such as pyridines, picolines, quinolines, isoquinolines, N-alkylpyrroles, N-alkylimidazoles, etc.; bicyclic nitrogen containing bases having non-hindered electron pairs, such as 1,8-diazabicyclo[4,3,0]undec-7-ene (DBU), 1,5-diazabicylco[4,3,0]non-5-ene (DBN) and 1,4-diazadicyclo[2,2,2]octane (DABCO®).
  • DBU 1,8-diazabicyclo[4,3,0]undec-7-
  • Typical solvents useful in the polymerization reaction include aprotic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-methyl-N-phenyl formamide, dimethyl sulfoxide, aliphatic nitriles, sulfolane, hexamethyl phosphoramide, etc. and mixtures thereof.
  • aprotic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-methyl-N-phenyl formamide, dimethyl sulfoxide, aliphatic nitriles, sulfolane, hexamethyl phosphoramide, etc. and mixtures thereof.
  • Water, alcohols, ketones pyridine and ether-alcohols, such as the Cellosolves also are sometimes useful.
  • One requirement is that the solvent not form a stronger nu
  • the new improved process of the invention allows the preparation of near ultraviolet (UV-A, UV-B and UV-C), visible and near infrared light absorbing linear polymeric compositions at relatively low temperatures, usually at from about 75° C. to about 125° C., without prolonged heating times. Furthermore, the method is adaptable to batch-process production which is advantageous for expensive products such as colorants, near infrared absorbers and near ultraviolet absorbers. The method is adaptable to a wide range of chromophoric classes since the polymer preparative reaction is carried out at relatively low temperature, which for example, allows colored polymeric compositions to be readily prepared from the very important azo class of colorants.
  • X and X 1 are both a sulfonate ester of the formula-OSO 2 R, wherein R is selected from C 1 -C 4 alkyl, phenyl or p-methylphenyl and wherein B is selected from C 2 -C 6 alkylene, —CH 2 -1,4-cyclohexylene-CH 2 —, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 1,4-cyclohexylene, —CH 2 CH 2 (OCH 2 CH 2 ) 2-3 and —CH 2 CH 2 O-1,4-phenylene-O—CH 2 CH 2 —.
  • preferred reactants of Formula II are those where B is selected from-CH 2 CH 2 —, —CH 2 CH(CH 3 )CH 2 —, —CH 2 C(CH 3 ) 2 CH 2 —, —(CH 2 ) 4 —, —(CH 2 ) 6 —, —CH 2 CH 2 (OCH 2 CH 2 ⁇ 1-4 and-CH 2 -1,4-cyclohexylene-CH 2 —.
  • Typical reactants of Formula II are as follows:
  • the invention also relates to a light absorbing linear polymeric composition having Formula Ia:
  • a 1 comprises the residue of at least one diacidic monomer having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and wherein B is defined above and which has been prepared by reacting a diacid light-absorbing monomer of Formula III (H—Y—H) as defined above with an organic compound having Formula II (X—B—X 1 ) as defined above, with the polymer producing reaction having been carried out in a solvent in the presence of base.
  • the above-described light absorbing composition of formula Ia also contains or comprises one or more cyclic compounds having the formula
  • a 1 and B are defined above and m may be 1, 2, 3, or 4.
  • m may be 1, 2, 3, or 4.
  • the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X 1 , and the conditions used to facilitate the reaction to produce the composition.
  • the cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
  • the invention also relates to a light absorbing linear polymeric composition having Formula Ib
  • a 2 comprises the residue of at least one diacidic monomer, having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and which comprises at least about 50% by weight of the total of the composition of Formula Ib and wherein the remainder of A 2 comprises the residue of at least one non-light absorbing monomer of Formula IV above, and wherein said polymeric composition has been prepared by reacting diacidic monomers of Formula III and Formula IV with an organic compound having Formula II above, with the polymer producing reaction having been carried out in a solvent in the presence of base.
  • the light absorbing composition of formula Ib also contains or comprises one or more cyclic compounds having the formula
  • a 2 and B are defined above and m may be 1, 2, 3, or 4.
  • m may be 1, 2, 3, or 4.
  • the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X 1 , and the conditions used to facilitate the reaction to produce the composition.
  • the cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
  • polydyes The polymer compositions of Formula I, Ia, and Ib and the cyclic compositions of formulas I-A, I-B and I-C are referred to as “polydyes” herein when they absorb visible light thus rendering them strongly colored.
  • the invention further relates to a thermoplastic polymeric composition which comprises a thermoplastic polymer blended with at least one light absorbing linear polymeric composition of Formula I, Ia or Ib above which, as noted above, contain or comprise one or more cyclic compounds having the general formula I-A.
  • the thermoplastic polymeric composition is usually selected from polyesters, polyolefins, polyamides, polyimides, polyvinyl chloride, polyurethanes, polycarbonates, cellulose esters, polyacrylates, polyvinylesters, polyester-amides, polystyrene, polyacrylonitrile- butadiene- styrene and polystyrene-acrylonitrile.
  • the preferred thermoplastic polymeric composition comprises the light-absorbing polymeric compositions of Formula Ia.
  • the invention also relates to some of the diacidic light absorbing monomers used to prepare the light absorbing polymeric composition of Formula I, Ia, or Ib.
  • R 6 is the residue of an aromatic or heteroaromatic amine which has been dizaotized and coupled with a coupling component H-Z and is preferably derived from the aromatic and heteroaromatic amine classes of aniline, 1-aminonaphthalene, 1-aminoanthraquinone, 4-aminoazobenzene, 2-aminothiazole, 2-aminobenzothiazole, 3-amino-2,1-benzisothiazole, 2-aminothieno[2,3-d]thiazole, 5-aminoisothiazole, 5-aminopyrazole, 4-aminopyrazoloisothiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,4-thiadiazole, 5-amino-1,2,3-triazole, 2-amino-1,3,4-triazole, 2(5) aminoimidazole, 3-aminopyridine, 2(3) aminothiophene, 2(3) aminobenzo[b
  • Z is the residue of an electron rich coupling component selected from the classes of anilines, 1-aminonaphthalenes, 1,2-dihydroquinolines,1,2,3,4-teterahydroquinolines, benzmorpholines (3,4-dihydro-2H-1,4-benzoxazine), pyrazolones, pyrazoles, 3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles, 4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-bithiazoles, julolidines (2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizines), 1-oxajulolidines, 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolines, 2,6-diamino-3 cyanopyridines, 2-aminothiazoles, 2-aminothiophenes,
  • Preferred disazo compounds correspond to Formula VII
  • R 6 and Z are as defined above and R 7 is a divalent aromatic or heteroaromatic radical selected from the classes 1,4-phenylene, naphthalene-1,4-diyl, thiazol-2,5-diyl and thiophene-2,5-diyl:
  • R 8 is selected from hydrogen or 1-2 groups selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, cyano, halogen, —NHCO C 1 -C 6 alkyl, —NHCO 2 C 1 -C 6 alkyl, —NHCO aryl, —NHCONH aryl or NHCONH C 1 -C 6 alkyl;
  • R 9 is selected from hydrogen, C 1 -C 6 alkyl, halogen, aryl, heteroaryl;
  • R 10 is selected from hydrogen, C 1 -C 6 alkoxycarbonyl, cyano, carbamoyl, aryl, arylsulfonyl, aroyl, —CONH C 1 -C 6 alkyl, or C 1 -C 6 alkylsulfonyl; with the provision that two acidic functional groups containing one acidic hydrogen each or one functional group containing two acidic hydrogens are present on compounds of Formula VII.
  • the preferred methine, arylidene, polymethine, azamethine, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxopyrroline and aryl isoindoline compounds correspond to Formula VIII, VIIIa, VIIIb, IX, X, XI and XII, respectively:
  • R 11 is the residue of an aniline, 1-naphthylamine, 1,2-dihydroquinoline, 1,2,3,4-tetrahydroquinoline, 1,3,3-trimethyl-2-methyleneindole, 1,3-dihydro-2-methylene-1,1,3-trimethyl-2H-benz[e]indole, imidazo [2,1-b] thiazole, benzomorpholine (3,4-dihydro-2H-1,4,benzoxazine), indole, 2,3-dihydroindole, 2-aminothiazole, julolidine (2,3,6,7-tetrahydro-1H, 5H-benz [ij] quinolizine, 1-oxajulolidine, 4H-pyrrolo [3,2,1-ij]-quinoline, phenol, naphthol, thiophenol, pyrrole, pyrazole, furan, thiophene, carbazole, pheno
  • the bis-azo compound corresponds to Formula VIIa
  • R 6 is as defined above and Y 1 is the residue of a bis coupling component selected from the classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazines), 3-cyano-6-hydroxy-2-pyridones, 2,6-diaminopyridines, 2,3-dihydroindoles, naphthylamines, 2-aminothiazoles, or a combination of these; with the provision the compounds of Formula VIIa contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl group (—SO 2 NH 2 ) which contains two acidic hydrogens.
  • a bis coupling component selected from the classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazines), 3-cyan
  • anthraquinone, anthrapyridone and anthrapyrimidine compounds correspond to the light absorbing compounds of Formulae XIV-XIXf
  • R 14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C 1 -C 10 alkylamino, C 3 -C 8 alkenylamino, C 3 -C 8 alkynylamino, C 3 -C 8 cycloalkylamino, arylamino, halogen, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, aryl, aroyl, C 1 -C 6 alkanoyl, C 1 -C 6 alkanoyloxy, NHCO C 1 -C 6 alkyl, NHCOaryl, NHCO 2 C 1 -C 6 alkyl, NHSO 2 C 1 -C 6 alkyl, NHSO 2 aryl, C 1 -C 6 alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO 2 C 1 -C 6
  • Q and Q′ are independently selected from-O—, —N(COR 10 )—, —N(SO 2 R 10 )—, —N(R 10 )—, —S—, —SO 2 —, —CO 2 —, —CON(R 10 )—, SO 2 N (R 10 )—, wherein R 10 is selected from hydrogen, aryl, C 3 -C 8 cycloalkyl, or C 1 -C 10 alkyl; R 15 is selected from hydrogen, cyano, C 1 -C 6 alkylamino, C 1 -C 6 alkoxy, halogen, arylthio, aryl, heteroaryl, heteroarylthio, C 1 -C 6 alkoxycarbonyl, aroyl or arylsulfonyl; R 16 is selected from hydrogen, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl and aryl; R 16 ′ is selected from
  • Typical coupler residues which are represented by Z above in Formulae VI, VII, XIII for the classes of azo, disazo and azo-methine compounds, respectively include:
  • R 17 is selected f rom the group consisting of hydrogen, 1-2 groups selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, —O—C 2 -C 6 alkylene-OH, O—C 2 -C 6 alkylene-C 1 -C 6 alkanoyloxy, C 1 -C 6 alkylene-OH, C 1 -C 6 alkylene-C 1 -C 6 alkanoyloxy, halogen, carboxy, C 1 -C 6 alkoxycarbonyl, trifluoromethyl, NHCOR 24 , NHCO 2 R 24 , NHCON(R 24 )R 25 , and NHSO 2 R 25 , wherein R 24 is selected from hydrogen, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl or aryl, R 25 is selected from C 1 -C 10 alkyl, C 3 -C 8 cycloal
  • R 5 ′, R 16 ′ and Q are as defined above;
  • R 18 and R 19 are independently selected from hydrogen, unsubstituted C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl and aryl or R 18 and R 19 may be combined with another element to which they are attached to form a radical Z having the formula
  • Q 2 is selected from a covalent bond, —O—, —S—, —SO 2 —, —CO—, —CO 2 —, —N—(C 1 -C 6 alkyl)-, —N(CO C 1 -C 6 alkyl)-, —N(SO 2 C 1 -C 6 alkyl)-, —N(CO aryl)-, or-N(SO 2 aryl);
  • R 20 , R 21 and R 22 are independently selected from the group consisting of or C 1 -C 6 alkyl;
  • R 23 is selected from hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, heteroaryl or aryl.
  • Typical electron, rich aromatic residues which are represented by R 11 in Formulae VIII-XII include:
  • R 26 is selected from the group consisting of hydrogen, a group selected from C 1 -C 6 alkoxycarbonyl, CO 2 H, C 1 -C 6 alkyl or C 1 -C 6 alkoxy; wherein R 17 -R 23 are as defined previously.
  • Typical coupler residues which are represented by Y 1 in Formula VIIa above include those of the formula (Z 1 -L 1 -Z 2 ) wherein Z 1 and Z 2 are independently selected from
  • L 1 is bonded to the nitrogen atom of Z 1 and Z 2 ; wherein L 1 is selected from C 2 -C 12 alkylene, C 3 -C 8 cycloalkylene, arylene, C 1 -C 4 alkylene-C 3 -C 8 cycloalkylene-C 1 -C 4 alkylene, C 1 -C 4 alkylene-arylene-C 1 -C 4 alkylene, C 2 -C 4 alkylene-O-arylene-O—C 2 -C 4 alkylene, —C 2 -C 4 alkylene O 1-3 —C 2 -C 4 alkylene, C 2 -C 4 alkylene-S—C 2 -C 4 alkylene, C 2 -C 4 alkylene-SO 2 —C 2 -C 4 alkylene, C 2 -C 4 alkylene-N(SO 2 C 1 -C 6 alkyl) —C 2 -C 4 alkylene, C 2 -C 4
  • C 1 -C 6 alkyl C 1 -C 6 alkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkanoyl, —CONH C 1 -C 6 alkyl, —SO 2 NH C 1 -C 6 alkyl, —CON(C 1 -C 6 alkyl) 2 , —SO 2 N(C 1 -C 6 alkyl) 2 , —NHSO 2 C 1 -C 6 alkyl, —N(C 1 -C 6 alkyl) SO 2 C 1 -C 6 alkyl, etc.
  • the C 1 -C 6 alkyl portion of the group refers to a straight or branched chain alkyl group containing one to six carbon atoms and these substituted with one or more groups selected from carboxy, cyano, —SO 2 NH 2 , SO 2 NH C 1 -C 6 alkyl, cyano, fluorine, chlorine, C 1 -C 6 alkoxy, aryloxy, aryl, heteroaryl, arylthio, heteroarylthio, C 3 - C 8 -cycloalkyl, —O 2 C C 1 -C 6 alkyl or-CO 2 C 1 -C 6 alkyl.
  • C 1 -C 4 alkylene, C 2 -C 4 alkylene, C 1 -C 6 alkylene, C 2 -C 6 alkylene, and C 2 -C 12 alkylene are used to refer to divalent aliphatic hydrocarbon radicals containing one to four carbon atoms, two to four carbon atoms one to six carbon atoms, two to six carbon atoms, or two to twelve carbon atoms, respectively, and these optionally substituted with one or more groups selected from C 1 -C 6 alkoxy, hydroxy, —O 2 C C 1 -C 6 alkyl, carboxy, CO 2 C 1 -C 6 alkyl, chlorine, fluorine, aryl or aryloxy.
  • C 3 -C 8 cycloalkyl and C 3 -C 8 cycloalkylene are used to refer to fully saturated monovalent and divalent cycloaliphatic radicals, respectively, and these substituted by one or more C 1 -C 6 alkyl groups.
  • C 3 -C 8 alkenyl and C 3 -C 8 alkynyl are used to refer to straight or branced hydrocarbon radicals containing at least one double bond or at least one triple bond, respectively.
  • aryl NH aryl, aryloxy, aroyl, arylthio, arylsulfonyl, aryloxysulfonyl, —N(SO 2 aryl)-, —N(CO aryl)-, NHCO aryl, —NH CONH aryl, NHSO 2 , aryl, etc.
  • the aryl portion of the group represents phenyl and naphthyl and these substituted with one or more groups selected from-CO 2 H, C 1 -C 6 alkyl, CO 2 C 1 -C 6 alkyl, SO 2 NH 2 , SO 2 NH C 1 -C 6 alkyl, hydroxy, O C 1 -C 6 alkyl, S C 1 -C 6 alkyl, phenyl, O-arylene-CO 2 H, —S-arylene-CO 2 H, SO 2 arylene-CO 2 H, halogen, NHSO 2 C 1 -C
  • arylene is used to represent 1,2-, 1,3-, and 1,4-phenylene and these optionally substituted with one or more groups mentioned above as possible substituents on the aryl radical.
  • heteroaryl is used to describe a 5 or 6 membered heterocyclic aromatic ring containing one oxygen atom, and/or one sulfur atom, and/or up to three nitrogen atoms, said heterocyclic aryl ring optionally fused to one or two phenyl rings or another 5 or 6-membered heteroaryl ring.
  • ring systems include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, thiatriazolyl, oxatriazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazinyl, oxazinyl, triazinyl, thiadiazinyl, oxadiazinyl, dithiazinyl, dioxazinyl, oxathiazinyl, tetrazynyl, thiatriazinyl, oxatriazinyl, dithiadiazinyl, imidazolinyl, dihydropyrimidyl, tetrahydro
  • halogen is used to refer to fluorine, chlorine, bromine and iodine.
  • the unsubstituted and substituted C 1 -C 10 alkyl groups or portion of groups mentioned refer to fully saturated hydrocarbon radicals containing one to ten carbon atoms, either straight or branched chain, and such alkyl radicals substituted with one or more of the following: C 3 -C 8 cycloalkyl, aryl, hydroxy, cyano, —O—C 2 -C 4 alkylene OH, —O—C 2 -C 4 alkylene O 2 C—C 1 -C 6 alkyl, —S—C 2 -C 4 alkylene-OH, chlorine, fluorine, —O—C 1 -C 6 alkyl, —O-aryl, —SO 2 aryl, —SO 2 —C 1 -C 6 alkyl, 2-pyrrolidino, phthalimidino, phthalimido, succinimido, glutarimido, o-benzoic sulfimide, vinyl
  • Y 2 is selected from 1,2-phenylene; 1,2 pheylene substituted with C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, —CO 2 H, —CO 2 C 1 -C 5 alkyl or nitro; C 2 -C 4 alkylene, vinylene, —O CH 2 —, —SCH 2 —, —CH 2 OCH 2 —, —OCH 2 CH 2 —, —CH 2 SCH 2 —, —NHCH 2 —, —NHCH 2 CH 2 , —N(C 1 -C 6 alkyl)CH 2 —, NHC(C 1 -C 6 alkyl) 2 , —N(C 1 -C 6 alkyl) CH 2 CH 2 or-NHC (aryl) 2 -; groups of the formulae:
  • R 26 is selected from hydrogen, C 1 -C 10 alkyl, C 2 -C 4 alkylene-OH, C 2 -C 4 alkylene-CO 2 H, C 2 -C 4 alkylene-CO 2 C 1 -C 6 alkyl, chloro, C 1 -C 6 alkoxy, C 1 -C 4 alkylene-arylene-CO 2 H, C 2 -C 4 alkylene-O-arylene-CO 2 H or C 2 -C 4 alkylene-S-arylene-CO 2 H and R 5 ′ R 17 , R 25 and Q are as defined previously:
  • light absorbing is used to indicate the property of absorbing near ultra violet, visible or near infrared light, more particularly absorbing light between the wavelengths of 300-1200 nm, preferably between about 325 nm and 1100 nm, and most preferably between about 325 nm and 1000 nm.
  • Typical aromatic amines which are useful as the coupling components to prepare compounds of Formulae VI, VII and VIII and as intermediates for preparing the compounds of Formula VIII, VIIIa, IX, X, XI and XII are as follows:
  • Typical diazotizable amines (R 6 NH 2 ) useful in the preparation of azo, disazo and bis-azo compounds of Formulae VI, VII, and VIIa, respectively, are adequately disclosed in the literature, e.g.:
  • Typical coupling components H-Z useful in preparing azo compounds, disazo and azo-methine compounds of Formula VI, VII and XIII, respectively, are disclosed in the literature, e.g: H. R. Schwander, Dyes and Pigments, 3(1982) 133-160; L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107-63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.; U.S. Pat. Nos.
  • Typical active methylene compounds useful in the preparation of methine, arylidene, polymethine, azamethine and azo-methine compounds corresponding to Formulae VIII, VIIIa, VIIIb, IX and XIII, respectively, are disclosed in the literature, e.g. U.S. Pat. Nos. 4,338,247; 4,617,373; 4,617,374; 4,707,537; 4,749,774; 4,826,903; 4,845,187; 4,950,732; 4,981,516 and 5,283,326.
  • the light-absorbing polymeric and cyclic compositions are incorporated into a wide variety of thermoplastic polymers using conventional techniques, e.g. solution or melt blending, such as those employed to incorporate other additives in such polymers (see R. Gumbleter and H. Müeller, Editors: Plastics Additives Handbook, Hansu Publishers, New York, 1985, pp. 507-533; 729-741).
  • the light absorbing polymeric and cyclic compositions may be dry blended in the form of pellets or powders with or without adhesion promoters or dispersing agents. This premix can be subsequently processed on extruders or injection molding machines.
  • Other conventional additives such as plasticizers, nucleating agents, flame retardants, lubricants, etc. may also be present in the final thermoplastic composition.
  • thermoplastic polymers useful for blending with the light absorbing polymeric and cyclic compositions include the homopolymers, copolymers and blends of polyesters, e.g., poly(ethylene terephthalate); polyolefins, e.g., polypropylene, polyethylene, linear low density polyethylene, polybutylene, and copolymers made from ethylene, propylene and/or butylene; copolymers from acrylonitrile, butadiene, and styrene; copolymers from styrene and acrylonitrile; polyamides, e.g., Nylon 6 and Nylon 66; polyvinyl chloride; polyurethanes; polyvinylidene chloride; polycarbonates; cellulose esters, e.g., cellulose acetate, propionate, butyrate, or mixed esters; polyacrylates, e.g., poly(methyl methacrylate);
  • polyesters e.g., poly(ethylene
  • a multiplicity of colors may be obtained by combining individual colors, e.g., subtractive colors such as yellow, magenta and cyan according to known color technology (see N. Ohta, Photographic Science and Engineering. Volume 15, No. 5, September-October 1971, pp. 395-415).
  • the actual amount of the light absorbing polymers used in combination with thermoplastic polymer will depend upon the inherent tinctorial strength of the chromophore used to prepare the light absorbing polymer, the mole % of the light absorbing monomer used to prepare the light absorbing polymer and the required level of light absorption necessary to achieve a certain property.
  • the amount of light-absorbing polymer added to the thermoplastic polymer is such that the total amount of light-absorbing polymer in the final thermoplastic blend is from about 0.001% by weight to about 20% by weight, preferably from about 0.01% by weight to about 10% by weight.
  • the final thermoplastic polymer blends thus provided are useful as a variety of molded and extruded articles, including thick and thin plastic films, plastic sheeting, molded plastic articles, containers and fibers, and the like.
  • the light-absorbing polymeric compositions absorb visible light they may be used to impart light or heavy shades of a variety of colors to thermoplastics. Certain compounds which possess unique visible light-absorbing properties are useful also as toners in imparting a desirable neutral to slightly blue hue to polyesters having a yellow appearance as described in U.S. Pat. No. 5,384,377, which discloses the copolymerization of certain thermally stable colorants for this purpose during polyester manufacture. Some of the infra-red absorbing polymeric and cyclic compositions are useful in imparting invisible markings to thermoplastics as described in U.S. Pat. No.
  • the ultra violet absorbing polymeric and cyclic compositions may be used to impart ultra violet (UV) light screening properties to the thermoplastics; to serve as optical brighteners for the thermoplastics or to serve as UV stabilizers for the polymers themselves or for other light absorbers such as colorants.
  • UV ultra violet
  • the weight average molecular weights (Mw) and the number average molecular weights (Mn) of the polymeric compositions were determined using gel permeation chromatography (GPC) analysis.
  • the methanol-wet filter cake was slurried in 1.0 L of water, the mixture acidified by the addition of acetic acid and the yellow product was collected by filtration, washed with hot water and dried in air (yield- 21.16 g).
  • GPC gel permeation chromatography
  • the methanol-wet filter cake was added to water (600 mL) and the mixture was acidified with acetic acid, and then the polymeric product was collected by filtration, washed with water and dried in air (yield 18.18 g).
  • the blue polymer had a molecular weight average of 3,038, a number average molecular weight of 1,814 and a polydispersity of 1.67.
  • the blue solid was precipitated by acidification with acetic acid with stirring.
  • the mixture was heated to about 60° C. with occasional stirring and the solid was collected by filtration, washed with hot water and dried in air. Further purification was accomplished by reslurrying the product in hot methanol (300 mL), allowing to cool to room temperature, collecting by filtration, washing with methanol and air drying to yield the starting material (31.5 g) for Example 2.
  • Eastar® PETG copolyester 6763 a poly(ethylene-1,4-cyclohexanedimethylene) terephthalate, (Eastman Chemical Co.) (400 g. of previously dried pellets) was dry blended with the yellow anthraquinone polymeric composition (0.12 g) of Example 1. The blend was extruded with a C. W. Brabender 3 ⁇ 4 in. extruder, equipped with a mixing screw, at 250° C. into a water bath and the extrudate pelletized.
  • the pellets were redried at 70° C. for about 17 hrs. at a pressure of about 1-5 torr. A portion of the dried pellets (1.40 g) was pressed into a 18-20 mil film at 250° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4 inch ram). A transparent yellow film was produced with excellent color development, which contained about 300 ppm by weight of the yellow polymeric composition.
  • Example 4 was repeated using 0.12 g of the blue anthraquinone polymeric composition of Example 2 to give a bright blue transparent copolyester film with good color development.
  • Example 4 was repeated using 0.12 g of the red azo polymeric composition of Example 3 to produce a bright red transparent film having good color development.
  • the polydye has a weight average molecular weight (Mw) of 3,769, a number average molecular weight (Mn) of 2,119 and a polydispersity of 1.78.
  • 1,2-ethanediol, dimethanesulfonate (0.73 g, 0.0033 mole), potassium carbonate (0.5 g) and DMF (30.0 mL) was heated at about 95° C. for 3.0 hours.
  • the reaction mixture was drowned into methanol (150 mL) with stirring and the blue polydye product was collected by filtration and washed with methanol.
  • The. methanol-wet cake was reslurried in water (200 mL) and the mixture acidified with acetic acid.
  • the methanol-wet cake was reslurried in 100 mL water and acidified by adding acetic acid with stirring. After heating to about 50° C., the product was collected by filtration, washed with hot water and dried in air (yield—1.2 g).
  • the blue polydye had a weight average molecular weight (Mw) of 2,764, a number average molecular weight (Mn) of 1,607 and a polydispersity of 1.72.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the visible light absorption maxima were at 586,630 nm.
  • the dipotassium salt of the diacidic anthraquinone compound was dissolved by adding to water (500 mL) and stirring.
  • the blue product which was precipitated by acidification with acetic acid was collected by filtration, washed with hot water and then dried in air (yield—21.5 g).
  • FDMS indicated the structure to be consistent with that given above in Example 10 for the starting diacidic anthraquinone compound.
  • the potassium salt of thiosalicyclic acid (4.75 g, 0.03 mole) was made by addition to DMF (75 mL) and heating in the presence of potassium carbonate (8.70 g, 0.06 mole) for 2.0 hours at about 95° C.
  • the cooled mixture was added to a solution of 1,8-dichloro-4,5-dinitroanthraquinone (5.51 g, 0.015 mole) dissolved in DMF (150 mL) at about 0-5° C. with stirring.
  • the reaction mixture was allowed to warm to about 25° C. with stirring continued for 2.0 hours and then poured into water.
  • the product was obtained in essentially quantitatively yield by slowly acidifying with 10% hydrochloric acid and was then collected by filtration, washed with water and dried in air.
  • FDMS indicated the product to be mostly the starting anthraquinone compound used in Example 11a.
  • GPC analysis indicated a weight average molecular weight of 5,252, a number average molecular weight of 2,179 and a polydispersity of 2.41. Absorption maxima at 583 nm and 628 nm were observed in the visible light absorption spectrum in DMF.
  • the methanol-wet cake was reslurried in water (500 mL) and acidified and the polydye then collected by filtration, washed with water and dried in air (yield—4.25 g).
  • GPC analysis indicated the polydye to have a weight average molecular weight of 1,901, a number average molecular weight of 1,588 and a polydispersity of 1.20.
  • An absorption maximum at 461 nm was observed in the visible light absorption spectrum in DMF.
  • the reaction mixture was drowned into methanol (100 mL) and the green polydye was washed with methanol, water containing acetic acid, hot water and then dried in air (yield—1.30 g).
  • GPC analysis indicated a weight average molecular weight of 1,839, a number average molecular weight of 1,040 and a polydispersity of 1.77. Absorption maxima were observed in the visible light absorption spectrum in DMF at 448, 603, and 645 nm.
  • Example 23 was repeated except that the disulfonate used was 1,3-propanediol, 2,2-dimethyl, dimethanesulfonate (0.65 g, 0.0025 mole) to give the yellow polydye (yield—0.76 g) which had a weight average molecular weight-of 1,056, a number average molecular weight of 979 and a polydispersity of 1.08 by GPC analysis.
  • the disulfonate used was 1,3-propanediol, 2,2-dimethyl, dimethanesulfonate (0.65 g, 0.0025 mole) to give the yellow polydye (yield—0.76 g) which had a weight average molecular weight-of 1,056, a number average molecular weight of 979 and a polydispersity of 1.08 by GPC analysis.
  • Example 23 was repeated except that 1,6-hexanediol, dimethanesulfonate (0.68 g, 0.0025 mole) was used as the disulfonate to give the yellow polydye (yield—1.16 g) which had a weight average molecular weight of 1,827, a number average molecular weight of 961 and a polydispersity of 1.90 by GPC analysis.
  • Example 23 was repeated except that 1,2-ethanediol, bis(4-methylbenzenesulfonate (0.82 g, 0.0025 mole) was used as the disulfonate to yield the yellow polydye (yield—0.41 g) which had a weight average molecular weight of 2,442, a number average molecular weight of 1,885 and a polydispersity of 1.29 by GPC analysis.
  • Example 33 was repeated using 1,5-bis(2-carboxyphenylthio) anthraquinone (1.02 g, 0.002 mole) and terephthalic acid (0.33 g, 0.002 mole), 1,2-ethanediol, dimethanesulfonate (0.87 g, 0.004 mole) and potassium carbonate (0.87 g) to yield the yellow polydye (0.90 g).
  • GPC analysis indicated a weight average molecular weight of 875, a number average molecular weight of 811, and a polydispersity of 1.08.
  • Colored EASTAR® copolyester 6763 film was produced by melt blending the polydyes of Examples 7-36 and extruding according to the following procedure to produce Examples 37-66 (Table 1).
  • EASTAR® PETG polyester 6763 a poly(ethylene-1,4-cyclohexanedimethylene) terephthalate (Eastman Chemical Company) (300 g of previously dried pellets) was dry blended with the anthraquinone polydye composition (0.12 g). The blend was extruded with a C. W. Brabender 3 ⁇ 4 in extruder, equipped with a mixing screw, at 250° C. into a water bath and the extrudate pelletized.
  • the pellets were redried at 70° C. for 17 hrs. at a pressure of about 1-5 torr. A portion (1.40 g) of the dried pellets was pressed into a 18-20 mil film at 250° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4 inch ram).
  • the transparent films contained about 300 ppm of the polydyes and each showed excellent color development to produce the colors indicated in Table 1.
  • the reaction mixture was drowned into methanol (500 mL) and the black polydye was collected by filtration, washed with water containing acetic acid, hot water and dried in air (yield—9.5 g).
  • GPC analysis indicated a weight average molecular weight of 7,512, a number average molecular weight of 1,700 and a polydispersity of 4.42.
  • EASTAR® PETG copolyester 6763 (291 g of previously dried pellets) was dry blended with the black polydye of Example 67 (9.0 g) and the blend extruded and a portion of the resulting pellets was pressed into a black film containing approximately 3.0% by weight of polydye by using the procedure described in Example 4.
  • 1,2-ethanedioli dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.5 g) and DMF (20 mL) was heated at about 95° C. with occasional stirring for 5.0 hours.
  • the reaction mixture was drowned into methanol.
  • Acetic acid (1.0 mL) was added and the polydye was collected by filtration and washed with water and dried in air.
  • GPC analysis indicated a Mw of 9,876, a Mn of 3,917 and a polydispersity of 2.52. An absorption maximum at 506. nm was observed in the visible light absorption spectrum in DMF.
  • the crude dye was reslurried in hot methanol and the mixture allowed to cool.
  • the final dye was collected by filtration, washed with methanol and dried in air. An absorption maximum was observed at 431 nm in DMF.
  • the diacid dye was used as the starting material in Example 86.
  • Colored EASTAR® PETG 6763 film was produced by melt blending the polydyes of Examples 69-93 and extruding according to the following procedures to produce Examples 94-118 (Table 2).
  • EASTAR® PETG polyester 6763 a poly(ethylene-cyclohexanedimethylene) terephthalate, (Eastman Chemical Company) (300 g of previously dried pellets) was dry blended with the azo dye composition (0.12 g) and the blend extruded and finally a 18-20 mil thick film prepare as described above for Examples 37-66.
  • Colored polyester film was produced by melt blending and extruding EASTAR® PETG polyester 6763 (Eastman Chemical Company) (300 g previously dried pellets) which had dry blended with the polydyes of Examples 119, 120, 121 to produce Examples 122-124, respectively, according to the procedure used to produce Examples 37-66.
  • the film of Example 122 was violet and those of Examples 123 and 124 were bright yellow.
  • a benzylidene type UV light fluorescent compound (1.0 g, 0.0028 mole) having the structure
  • EASTAPAK® PET 7352 a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of previously dried pellets) was dry blended with the polymeric UV light fluorescent material of Example 126 (0.16 g). The blend was extruded with a C. W. Brabender 3 ⁇ 4 inch extruder, equipped with a mixing screw, at 285° C. into a water bath and the extrudate pelletized. The pellets which contained about 400 ppm of the UV light absorber showed a strong blue white fluorescence under UV light.
  • Example 127 was repeated except that 8 mg of the UV light fluorescent material of Example 126 was added to the EASTAPAK® PET 7352. The resulting pellets showed a strong blue-white fluorescence under UV light and appeared very white in sunlight.
  • EASTAPAK® PET 7352 a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of previously dried pellets) was dry blended with the polymeric phthalocyanine compound of Example 129 (0.12 g). The blend was extruded with a C. W. Brabender 3 ⁇ 4 inch extruder, equipped with a mixing screw, at 2850 into a water bath and the extrudate pelletized. The cyan pellets were redried at 70° C. for about 17 hrs at a pressure of about 1-5 torr. A portion of the dried pellets (1.40 g) was pressed into a film at 285° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4-inch ram). A transparent cyan film was produced by quenching in water and had an absorption maximum at 684 nm in the light absorption spectrum.
  • Example 130 was repeated except that 4 mg of the polymeric phthalocyanine compound of Example 129 was added to the PET.
  • the final film contained-about 10 ppm and had a light absorption maximum at 685 nm.
  • EASTAPAK® PET 7352 a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of dried pellets) was dry blended with the polydye of Example 18 (0.6 g). The blend was extruded with a C. W. Brabender 3 ⁇ 4 inch extruder, equipped with a mixing screw, at 285° C. into a water bath and the extrudate pelletized. Good color production resulted with no evidence of color loss by sublimation to give dark red pellets containing about 0.15% by weight of the polydye.
  • Example 132 was repeated using 0.6 g of the polydye of Example 75 as the colorant to give yellow pellets having about 0.15% by weight of the polydye. No loss of color by sublimation was observed.
  • miscellaneous diacidic compounds of Table 21 are reacted with essentially equimolar amounts of the disulfonate compounds of Table 21 in DMF in the presence of potassium carbonate to yield the polydyes of Examples 466-505 in Table 21.
  • Example 540 diethylene glycol, dimethanedisulfonate
  • Example 542 1,4-cyclohexanedimethanol, dimethanedisulfonate

Abstract

The present invention recites a method comprising reacting in a solvent in the presence of a base
a) at least one diacidic monomer comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1200 nm and 99-0 mole % of a non-light absorbing monomer which does not absorb significant light at wavelengths above 300 nm or has a light absorption maximum below 300 nm, with
b) an organic compound of Formula II
X—B—X1
wherein B is a divalent organic radical to form a light absorbing composition comprising a mixture of a polymer having the formula
Figure US20040195552A1-20041007-C00001
and a cyclic compound having the general formula
Figure US20040195552A1-20041007-C00002
wherein B is as defined above; n is at least 2, m is 1, 2, 3 or 4 and A comprises the residue of a diacidic monomer comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1000 nm and wherein the remaining portion of A comprises the residue of a non-light absorbing monomer which does not absorb significant light at wavelengths above 300 nm or has a light absorption maximum below 300 nm.

Description

    RELATED APPLICATION
  • This application is a continuation-in-part of our application Ser. No. 08/976,206 filed Nov. 21, 1997, which is based upon and claims the priority of provisional application 60/031,478 filed Nov. 27, 1996.[0001]
    • BACKGROUND OF THE INVENTION
  • This invention relates to an improved method for preparing light-absorbing polymeric compositions, which are useful as powders or pellets for incorporation into a variety of thermoplastic resins such as cellulose esters, polyesters, polyolefins, polycarbonates, polyamides, etc. by conventional melt or solution blending techniques. The colored thermoplastic resins thus produced have good clarity, good color development, excellent fastness to light and are useful for a variety of end uses where nonhazardous, nonmigrating, or nonextractable colorants are needed. [0002]
  • It is well-known that thermoplastic polymers may be colored by adding pigments or solvent dyes (e.g., see Thomas G. Weber, Editor, [0003] Coloring of Plastics, John Wiley & Sons, New York, 1979). The use of pigments, however, is accompanied by undesirable properties such as opacity, dullness of color, low tintorial strength, etc. Also, difficulties in uniformly blending the in soluble pigments with the thermoplastic resin are often encountered. Also useful for coloring thermoplastic polymers are the solvent dyes (K. Venkataraman, Editor, The Chemistry of Synthetic Dyes, Vol. 8, Academic Press, New York, 1978, pp. 81-131), which provide compositions having improved clarity, brightness in hue and high tinctorial strength, but which may lead to dye migration, extraction, etc. from the colored thermoplastic polymer. These problems are of particular concern when solvent dyes are used to color flexible polymers such as polyvinyl chloride, polyethylene and polypropylene which have low glass transition temperatures.
  • Plastics, paints, printing inks, rubber, cosmetics, and similar materials are typically colored by organic pigments when superior brilliance and tinctorial strength are important. Toxicity considerations have presented chronic problems relative to the use of organic pigments since some have been shown to be potential carcinogens and to cause contact dermatitis. [0004]
  • Plastics are also colored by using color concentrates consisting of physical admixtures of polymers and colorants (usually solvent dyes). However, the use of such physical admixtures to color polymeric materials such as polyester, e.g., poly(ethylene terephthalate) and blends thereof, present a number of problems, including: [0005]
  • Colorant migration during drying of the colored polyester pellets. [0006]
  • Colorant migration during extrusion and colorant accumulation on dies which can cause shutdowns for clean-up. Such colorant migration and accumulation result in time consuming and difficult clean-up, particularly when a polymer of another color is subsequently processed on the same equipment. [0007]
  • Colorants may not mix well, for example, when using two or more color cencentrates to obtain a particular shade. [0008]
  • Colorants may diffuse or exude during storage and use of the colored polymeric material. [0009]
  • The colored polymeric compositions which are prepared by the process of this invention eliminate or minimize the aforementioned problems associated with the use of conventional dyes and pigments. [0010]
    • PRIOR ART
  • To attempt to overcome some of the problems mentioned above, particularly as relates to coloring polyesters, colored polyester compositions have been prepared by copolymerizing relatively low amounts of monomeric colorants during the polymer preparation (U.S. Pat. Nos. 5,194,571; 5,106,942; 5,102,980; 5,032,670; 4,892,922; 4,740,581; 4,403,092; 4,359,570; 4,267,306 and W092/07913). However, the preparation of these colored polymers require dyes having outstanding thermal stability since the colorants are exposed to very high temperatures for prolonged periods of time necessary for polyester formation, thus severely circumscribing the selection of efficacious colorants. For example, only the nonazo type colorants have been shown to have the adequate thermal stability for copolymerization into polyesters, since azo type compounds do not have the resquite thermal stability for copolymerization. [0011]
  • Furthermore, it is known to prepare polymeric dyes by reacting dyes containing reactive hydroxy and amino groups with organic di-acid chlorides in solvents (U.S. Pat. Nos. 2,994,693; 3,403,200; 4,619,990; 4,778,742; 5,401,612). Although this method of polymer preparation allows the use of a wide range of chromophoric classes, including azo compounds, as colorant monomers, the polymerization reaction in each case involves the use of very reactive organic di-acid chlorides which are toxic and involve difficult to handle inorganic halogen compounds in their preparation and have accompanying problems of hydrolysis in the presence of water which causes serious handling and storage problems. The hydrolysis product (HCl) is particularly corrosive and makes storage of these compounds difficult. Furthermore, since the di-acid chlorides will react with water, the monomeric dyes must be specially dried to avoid side reactions in the polymer preparation. [0012]
  • In a similar attempt to prepare polymeric dyes using relatively low temperatures, polyurethanes have been prepared by reacting dyes bearing two hydroxyalkyl group with aliphatic and aromatic isocyanates (U.S. Pat. No. 5,194,463). However, the organic isocyanates themselves are extremely toxic and present difficult handling problems. They also are reactive with water and thus the reaction requires specially dried monomeric dyes. Also, the colored polyurethanes as a class do not have excellent thermal stability. [0013]
  • It is further known to prepare colored condensation polymers by reacting a polymerizable lactone or a hydroxyalkanoic acid with a dye containing reactive hydroxy group (U.S. Pat. No. 4,933,426). The procedure again requires relatively high reaction temperatures and prolonged times and use a large excess of the lactone reactant. The method is further hindered by the fact that some lactones are suspected carcinogens. [0014]
  • Light-absorbing polymeric compositions have also been produced by free radical polymerization of vinyl functionalized light-absorbing monomers (U.S. Pat. Nos. 5,310,837; 5,334,710; 5,359,008; 5,434,231 and 5,461,131). [0015]
  • Finally, it is known that one may color plastics, in particular polyolefins, with low melting, cross-linked colored polyester compositions containing residues of terephthalic acid, isophthalic acid, or both, a low-molecular weight trimethylol alkane, i.e., 1,1,1-trimethylol propane and a copolymerizable colorant, said colorant being present at a level of 0.1-25% by weight (U.S. Pat. No. 4,116,923). Difficulties are encountered, however, in preparing these highly cross-linked colored polymers as extreme care with regard to the temperature, amount of vacuum, the level of colorant present, and the reaction time, is necessary in order to attempt to reproduce the same quality of cross-linked colored polyester composition. Further, these colored polyester compositions are brittle or low melting and may cause deterioration in physical properties of themoplastic polymers when added in quantities sufficient to produce a high level of coloration. [0016]
  • Practice of the Invention [0017]
  • This invention relates to a method for preparing a light absorbing linear polymeric having Formula I [0018]
    Figure US20040195552A1-20041007-C00003
  • wherein A comprises the residue of a diacidic monomer comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1200 nm and wherein the remaining portion of A comprises the residue of a non-light absorbing monomer which does not absorb significantly at wavelengths above 300 nm or has a light absorption maximum below 300 nm and wherein B is a divalent organic radical selected from C[0019] 2-C12 alkylene, C3-C8 cycloalkylene, C1-C4 alkylene- C3-C8-cycloalkylene- C1-C4 alkylene, C1-C4 alkylene-arylene- C1-C4 alkylene, C2-C4 alkylene-O— C2-C4 alkylene, and C2-C4-alkylene-L-arylene- C2-C4 alkylene and C2-C4 alkylene- (L-C2-C4 alkylene)1-4, wherein L is a linking group selected from-O—, —S—, —SO2—, —NH—, —N(C1-C6alkyl)-, —N(aryl)-, —N(SO2 C1-C6 alkyl)-, —N(SO2aryl)-, —SO2N(C1-C6 alkyl)- and combinations thereof; wherein n is at least 2.
  • The process comprises reacting said diacidic monomer with an organic compound of Formula II [0020]
  • X—B—X1   II
  • wherein B is as defined above and X and X[0021] 1 reactive groups and are independently selected from bromine, iodine and R—SO2O; wherein R is selected from C1-C6 alkyl; C1-C6 alkyl substituted with chlorine, fluorine, C1-C6 alkoxy, aryl, aryloxy, arylthio or C3-C8 cycloalkyl; C3-C8 cycloalkyl or aryl, with said reaction being carried out in a solvent in the presence of a base; wherein the useful diacid light-absorbing monomers have Formula III
  • H—Y—H   III
  • wherein H represents an acidic hydrogen atom; Y is a divalent light-absorbing moiety selected from a variety of chromophoric classes including azo, disazo, bis-azo, methine, arylidene, polymethine, azo-methine, azamethine, anthraquinone, anthrapyridone (3H-dibenz[f,ij]isoquinoline- 2,7-dione, nitroarylamines anthrapyridine (7H-dibenz[f,ij]isoquinoline-7-one, phthaloylphenothiazine (14H-naphth[2,3-a] phenothiazine-8,13-dione, benzanthrone(7H (de) anthracene-7-one), anthrapyrimidine(7H-benzo[e] perimidine-7-one), anthrapyrazole, anthraisothiazole, triphenodioxazine, thiaxanthene-9-one, fluorindine (5,12-dihydroquinoxaline[2,3-b]phenazine, quinophthalone, phthalocyanine, metal phthalocyanine, naphthalocyanine, metal naphthalocyanine, nickel dithiolenes, squarylium compounds, croconium compounds, coumarin (2H-1-benzopyran-2-one), coumarin imine (2H-1-benzopyran-2-imine), perinone, benzodifuran, phthaloylacridone, phthaloylphenoxazine (14H-naphtho[2,3-a]phenoxazine-8,13-done, phthaloylacridone (13H-naphtho[2,3-c]acridine-5,8,14-trione), anthraquinonethioxanthane (8H-naphtho[2,3-c]thioxanthene-5,8,13-trione, anthrapyridazone, pyrrolo[3,4-c]pyrrole, indigo, thioindigo, quinoline, xanthene, acridine, azine, cyanine, oxazine, 1,4 and 1,5-naphthoquinones, 2,5-diarylaminoterephthalic acids and esters, pyromellitic acid dimide, naphthalene-1,4,5,8-tetracarboxylic acid diimide, 3,4,9,10-perylene-tetracarboxylic acid diimide, 3-aryl- 2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxopyrroline, arylisoindoline, hydroxybenzophenone, benoztriazole, naphthotriazole, diminoisoindoline, naphthopyran (3H-naphtho[2,1-6]pyran-3-one and 3-imine, phthalimides, 2-arylbenzazoles, carbostyryls, 1,2-diarylethenes, 2,5-diarylthiophenes, 2,5-diaryl-1,3,4-oxadiazoles, triazines, 2,5-diarylfurans, 2,5-diaryl-1,3,4-thiadiazoles, thiophenes, 1,3-diphenyl-2-pyrazolines, 2-arylbenzofurans, 2,6-diphenylbenzofurans, quinolines, quinoxalines, 3,4-diarylfuanones, distyrylarenes, benzanthrones, polyarenes and naphthalimides; wherein the hydrogen atoms of Formula III are independently bonded to an oxygen, sulfur, or nitrogen atom which is a part of the light absorbing moiety Y; wherein the useful non light-absorbing monomers have Formula IV, [0022]
  • H—Y1—H   IV
  • wherein H represents an acidic hydrogen atom; Y[0023] 1 is a divalent moiety, selected from-O2C—R1—CO2— and-O—R2—O-and-O2C—R3—O—, wherein R1 is selected from C2-C12 alkylene, 1-4-cyclohexylene, arylene, arylene-O-arylene, arylene-S2-arylene, arylene-S-arylene, and C1-C4 alkylene-O—C1-C4 alkylene; wherein R2 is selected from arylene, arylene-O-arylene, arylene-S-arylene, arylene-SO2-arylene, phenylene-phenylene, and phenylene-C(R4)2-phenylene; wherein R4 is selected from hydrogen and C1-C4 alkyl; wherein R3 is selected from arylene.
  • In diacid light absorbing monomers having Formula III, the hydrogen atoms are preferably attached to an oxygen, a sulfur or a nitrogen atom which in combination provides two acidic functional group which can produce the corresponding anions under basic conditions by removal of the protons. The acidic functional groups usually have an acid dissociation constant of about 10[0024] −15 to about 10−12 (pKa of from about 1.5 to about 12). In the case of nitrogen, both protons may be attached to a single nitrogen which is attached to a sulfonyl moiety thus providing two acidic hydrogens on a single functional group.
  • Typical, acidic groups which provide one acidic hydrogen include-CO[0025] 2H, —SH, —OH attached to an aromatic ring, —CONHCO—, —SO2—NH—CO—, —SO2—NH—SO2—, 1(H)-1,2,4-triazol-3-yl-, imidazolyl, benzimidazolyl, pyrazolyl, —SO2H attached to aromatic ring, —NHSO2R5 and-SO2NHR5, wherein R5 is selected from C1-C6 alkyl; C1-C6 alkyl substituted with at least one group selected from C1-C6 alkoxy, aryl, aryloxy, arylthio or C3-C8 cycloalkyl; C3-C8 cycloalkyl; aryl.
  • An example of an acidic functional group providing two acidic hydrogen attached to nitrogen is the sulfamoyl group (—SO[0026] 2NH2).
  • The preferred method for producing light absorbing polymeric compositions utilizes the monomers of Formula III, wherein the protons are a part of the-CO[0027] 2H, OH attached to aromatic ring, —CO—NH—CO— or 1(H,)-1,2,4-triazol-3-yl functional groups. The carboxy groups are normally attached to an aromatic ring carbon or aliphatic carbon which is a part of Y. The hydroxy groups are normally attached to an unsubstituted or substituted phenyl or naphthyl radical which is a part of Y. The —CO—NHCO— groups are usually attached to an aromatic ring to provide an imide such as phthalimide or naphthalimide which are a part of Y. The 1(H)-1,2,4-triazol-3-yl group has the following Formula V, wherein R5′ is
    Figure US20040195552A1-20041007-C00004
  • selected from hydrogen, C[0028] 1-C6 alkyl or aryl. It should be observed that the triazole may exist in isomeric form as follows:
    Figure US20040195552A1-20041007-C00005
  • The 1(H)-1,2,4-triazol-3-yl group is preferably attached to a sulfur atom which is attached to the remainder of Y. [0029]
  • The method of the invention in the broadest sense involves the preparation of light absorbing polymeric compositions by reacting a diacidic monomer comprising at least 1 mole % of at least one diacidic light absorbing monomer represented by H-A-H with an organic compound containing two reactive groups represented by X—B—X[0030] 1, where B, X and X1 are as defined above. Thus, the method may be summarized as:
    Figure US20040195552A1-20041007-C00006
  • The diacidic monomer H-A-H must be acidic enough to form two nucleophiles in the presence of base under convenient reaction conditions for the most advantageous process. This usually requires that diacidic monomers have pK[0031] a values of about 12 or below.
  • The dinucleophilic monomer, formed by the removal of the two hydrogen atoms by the base, attacks the electrophilic compound II, thus displacing anions X[0032] − and X1 −, with head-to-tail combination with covalent bonding to produce a linear polymer A-Bn, wherein n represents the number of repeating units. The number of repeating units must be at least 2, but usually ranges between about 2 and about 25, with the preferred number being between about 3 and about 15.
  • The composition produced by the method of the invention comprises, as stated above, a polymer having the general formula A-B[0033] n. The composition also comprises one or more cyclic compounds having the general formula
    Figure US20040195552A1-20041007-C00007
  • wherein m may be 1, 2, 3, or 4, e.g., the cyclic compounds having the general structures: [0034]
    Figure US20040195552A1-20041007-C00008
  • The number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X[0035] 1, and the conditions used to facilitate the reaction to produce the composition. The cyclic compounds may constitute up to about 35 weight percent, typically about 0.5 up to 30 weight percent, of the total weight of the composition produced by the method of the invention.
  • Suitable bases include alkali metal carbonates; alkali metal bicarbonates; tertiary amines such as triethylamine, tri-n-butylamine, N-methylpiperidine, N,N′-dimethylpiperazine, N-methylmorpholine, N,N,N′,N′-tetramethylenediamine, etc.; aromatic nitrogen bases such as pyridines, picolines, quinolines, isoquinolines, N-alkylpyrroles, N-alkylimidazoles, etc.; bicyclic nitrogen containing bases having non-hindered electron pairs, such as 1,8-diazabicyclo[4,3,0]undec-7-ene (DBU), 1,5-diazabicylco[4,3,0]non-5-ene (DBN) and 1,4-diazadicyclo[2,2,2]octane (DABCO®). [0036]
  • Typical solvents useful in the polymerization reaction include aprotic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-methyl-N-phenyl formamide, dimethyl sulfoxide, aliphatic nitriles, sulfolane, hexamethyl phosphoramide, etc. and mixtures thereof. Water, alcohols, ketones pyridine and ether-alcohols, such as the Cellosolves, also are sometimes useful. One requirement is that the solvent not form a stronger nucleophile in the presence of the base than that obtained from the diacidic monomer H-A-H. [0037]
  • The new improved process of the invention allows the preparation of near ultraviolet (UV-A, UV-B and UV-C), visible and near infrared light absorbing linear polymeric compositions at relatively low temperatures, usually at from about 75° C. to about 125° C., without prolonged heating times. Furthermore, the method is adaptable to batch-process production which is advantageous for expensive products such as colorants, near infrared absorbers and near ultraviolet absorbers. The method is adaptable to a wide range of chromophoric classes since the polymer preparative reaction is carried out at relatively low temperature, which for example, allows colored polymeric compositions to be readily prepared from the very important azo class of colorants. [0038]
  • The preferred reactants of Formula II [0039]
  • X—B—X1
  • are the disulfonate compounds where X and X[0040] 1 are both a sulfonate ester of the formula-OSO2R, wherein R is selected from C1-C4 alkyl, phenyl or p-methylphenyl and wherein B is selected from C2-C6 alkylene, —CH2-1,4-cyclohexylene-CH2—, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 1,4-cyclohexylene, —CH2CH2(OCH2CH2)2-3 and —CH2CH2O-1,4-phenylene-O—CH2CH2—. Particularly, preferred reactants of Formula II are those where B is selected from-CH2CH2—, —CH2CH(CH3)CH2—, —CH2C(CH3)2CH2—, —(CH2)4—, —(CH2)6—, —CH2CH2(OCH2CH21-4 and-CH2-1,4-cyclohexylene-CH2—.
  • Typical reactants of Formula II are as follows: [0041]
    Figure US20040195552A1-20041007-C00009
  • The invention also relates to a light absorbing linear polymeric composition having Formula Ia: [0042]
    Figure US20040195552A1-20041007-C00010
  • wherein A[0043] 1 comprises the residue of at least one diacidic monomer having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and wherein B is defined above and which has been prepared by reacting a diacid light-absorbing monomer of Formula III (H—Y—H) as defined above with an organic compound having Formula II (X—B—X1) as defined above, with the polymer producing reaction having been carried out in a solvent in the presence of base. The above-described light absorbing composition of formula Ia also contains or comprises one or more cyclic compounds having the formula
    Figure US20040195552A1-20041007-C00011
  • wherein A[0044] 1 and B are defined above and m may be 1, 2, 3, or 4. As stated hereinabove, the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X1, and the conditions used to facilitate the reaction to produce the composition. The cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
  • The invention also relates to a light absorbing linear polymeric composition having Formula Ib [0045]
    Figure US20040195552A1-20041007-C00012
  • wherein A[0046] 2 comprises the residue of at least one diacidic monomer, having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and which comprises at least about 50% by weight of the total of the composition of Formula Ib and wherein the remainder of A2 comprises the residue of at least one non-light absorbing monomer of Formula IV above, and wherein said polymeric composition has been prepared by reacting diacidic monomers of Formula III and Formula IV with an organic compound having Formula II above, with the polymer producing reaction having been carried out in a solvent in the presence of base. The light absorbing composition of formula Ib also contains or comprises one or more cyclic compounds having the formula
    Figure US20040195552A1-20041007-C00013
  • wherein A[0047] 2 and B are defined above and m may be 1, 2, 3, or 4. Again, the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid H-A-H, the structure of the organic compound X—B—X1, and the conditions used to facilitate the reaction to produce the composition. The cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
  • The polymer compositions of Formula I, Ia, and Ib and the cyclic compositions of formulas I-A, I-B and I-C are referred to as “polydyes” herein when they absorb visible light thus rendering them strongly colored. [0048]
  • The invention further relates to a thermoplastic polymeric composition which comprises a thermoplastic polymer blended with at least one light absorbing linear polymeric composition of Formula I, Ia or Ib above which, as noted above, contain or comprise one or more cyclic compounds having the general formula I-A. The thermoplastic polymeric composition is usually selected from polyesters, polyolefins, polyamides, polyimides, polyvinyl chloride, polyurethanes, polycarbonates, cellulose esters, polyacrylates, polyvinylesters, polyester-amides, polystyrene, polyacrylonitrile- butadiene- styrene and polystyrene-acrylonitrile. The preferred thermoplastic polymeric composition comprises the light-absorbing polymeric compositions of Formula Ia. [0049]
  • The invention also relates to some of the diacidic light absorbing monomers used to prepare the light absorbing polymeric composition of Formula I, Ia, or Ib. [0050]
  • Preferred azo compounds useful in the practice of the invention correspond to Formula VI [0051]
  • R6—N═N-Z   VI
  • wherein R[0052] 6 is the residue of an aromatic or heteroaromatic amine which has been dizaotized and coupled with a coupling component H-Z and is preferably derived from the aromatic and heteroaromatic amine classes of aniline, 1-aminonaphthalene, 1-aminoanthraquinone, 4-aminoazobenzene, 2-aminothiazole, 2-aminobenzothiazole, 3-amino-2,1-benzisothiazole, 2-aminothieno[2,3-d]thiazole, 5-aminoisothiazole, 5-aminopyrazole, 4-aminopyrazoloisothiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,4-thiadiazole, 5-amino-1,2,3-triazole, 2-amino-1,3,4-triazole, 2(5) aminoimidazole, 3-aminopyridine, 2(3) aminothiophene, 2(3) aminobenzo[b]thiophene, 2-aminothieno[3,2-bithiophene, 3-aminothieno[2,3-c]isothiazole, 3-amino-7-benz- 2,1-isothiazole, 3-aminobenzothienoisothiazole, 3-aminoisothiazole[3,4-d]pyrimidine, 5-amino- 1,2,3-triazole, 3(4) aminophthalimide and 5(6) amino-1,2-benzisothiazolon-1,1-dioxide with said aromatic and heteroaromatic ring systems being unsubstituted or substituted with one or more groups selected from C1-C10 alkyl, C1-C6 alkoxy, C3-C8 cycloalkyl, carboxy, halogen, C1-C6 alkoxycarbonyl, formyl, C1-C6 alkanoyl, C1-C6 alkanoyloxy, dicyanovinyl, C3-C8-cycloalkanoyl, thiocyano, trifluroacetyl, cyano, carbamoyl, —CONH C1-C6 alkyl, CONHaryl, CON(C1-C6 alkyl)2, sulfamoyl, SO2NH C1-C6 alkyl, SO2N(C1-C6 alkyl)2, SO2NHaryl, SO2NH C3-C8 cycloalkyl, CONH C3-C8 cycloalkyl, aryl, aroyl, —NHSO2 C1-C6 alkyl, —N(C1-C6 alkyl)SO2 C1-C6 alkyl, —NHSO2 aryl, NHCO C1-C6 alkyl, NHCO C3-C8 cycloalkyl, NHCOaryl, NHCO2 C1-C6 alkyl, NHCONH C1-C6 alkyl, NHCONHaryl, N(C1-C6 alkyl)aryl, arylazo, heteroaryl, aryloxy, arylthio, C3-C8 cycloalkoxy, heteroarylazo, heteroarylthio, arylsulfonyl, tricyanovinyl, aryloxysulfonyl, C1-C6 alkylsulfonyl, trifluoromethyl, fluorosulfonyl, trifluoromethylsulfonyl, thiocyano, hydroxy, nitro or CH=D, wherein D is the residue of an active methylene compound as defined below.
  • Z is the residue of an electron rich coupling component selected from the classes of anilines, 1-aminonaphthalenes, 1,2-dihydroquinolines,1,2,3,4-teterahydroquinolines, benzmorpholines (3,4-dihydro-2H-1,4-benzoxazine), pyrazolones, pyrazoles, 3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles, 4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-bithiazoles, julolidines (2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizines), 1-oxajulolidines, 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolines, 2,6-diamino-3 cyanopyridines, 2-aminothiazoles, 2-aminothiophenes, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), phenols, naphthols, 2,4-pentanediones or acetoacetarylides; with the proviso that the compounds of Formula VI contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl group (—SO[0053] 2NH2) which contains two acidic hydrogens.
  • Preferred disazo compounds correspond to Formula VII [0054]
  • R6—N═N—R7N═N-Z   VII
  • wherein R[0055] 6 and Z are as defined above and R7 is a divalent aromatic or heteroaromatic radical selected from the classes 1,4-phenylene, naphthalene-1,4-diyl, thiazol-2,5-diyl and thiophene-2,5-diyl:
    Figure US20040195552A1-20041007-C00014
  • wherein R[0056] 8 is selected from hydrogen or 1-2 groups selected from C1-C6 alkyl, C1-C6 alkoxy, cyano, halogen, —NHCO C1-C6 alkyl, —NHCO2 C1-C6 alkyl, —NHCO aryl, —NHCONH aryl or NHCONH C1-C6 alkyl; R9 is selected from hydrogen, C1-C6 alkyl, halogen, aryl, heteroaryl; R10 is selected from hydrogen, C1-C6 alkoxycarbonyl, cyano, carbamoyl, aryl, arylsulfonyl, aroyl, —CONH C1-C6 alkyl, or C1-C6 alkylsulfonyl; with the provision that two acidic functional groups containing one acidic hydrogen each or one functional group containing two acidic hydrogens are present on compounds of Formula VII.
  • The preferred methine, arylidene, polymethine, azamethine, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxopyrroline and aryl isoindoline compounds correspond to Formula VIII, VIIIa, VIIIb, IX, X, XI and XII, respectively: [0057]
    Figure US20040195552A1-20041007-C00015
  • wherein R[0058] 11 is the residue of an aniline, 1-naphthylamine, 1,2-dihydroquinoline, 1,2,3,4-tetrahydroquinoline, 1,3,3-trimethyl-2-methyleneindole, 1,3-dihydro-2-methylene-1,1,3-trimethyl-2H-benz[e]indole, imidazo [2,1-b] thiazole, benzomorpholine (3,4-dihydro-2H-1,4,benzoxazine), indole, 2,3-dihydroindole, 2-aminothiazole, julolidine (2,3,6,7-tetrahydro-1H, 5H-benz [ij] quinolizine, 1-oxajulolidine, 4H-pyrrolo [3,2,1-ij]-quinoline, phenol, naphthol, thiophenol, pyrrole, pyrazole, furan, thiophene, carbazole, phenothiazine or phenoxazine compound; R12 is selected from hydrogen, C1-C10 alkyl, C3-C8 alkenyl, C3-C8-alkynyl, C3-C8 cycloalkyl, aryl, CH2CH2O1-3 R13 and C1-C4 alkylene- C3-C8 cycloalkylene, wherein the C1-C6 alkyl groups may be substituted by at least one group selected from carboxy, C1-C6 carbalkoxy, C1-C6 alkanoyloxy, cyano, hydroxy, chlorine, fluorine, C1-C6 alkoxy, C3-C8 cycloalkyl or aryl; R13 is selected from hydrogen, C1-C6 alkoxy or C1-C6 alkanoyloxy; wherein D is the residue of an active methylene compound selected from malononitrile, -cyanoacetic acid esters, malonic acid esters, -cyanacetic acid amides, —C1-C6 alkylsulfonylacetonitriles, -arylsulfonylacetonitriles, —C1-C6 alkanoylacetonitriles, -aroylacetonitriles, -heteroarylacetonitriles, bis(heteroaryl)methanes, 1,3-indanediones, 2-furanones, benzo-2-furanones, naphtho-2-furanones, 2-indolones. 3-cyano-1,6-dihydro-4-methyl-2,6-dioxy (2H)-pyridines, benzo (b) thieno-3-ylidene propane dinitrile-5,5-dioxides, 1,3-bis (dicyanomethylene) indanes, barbituric acid, 5-pyrazolones, dimedone, 3-oxo-2,3-dihydro-1-benzothiophene-1,1-dioxides or aryl-C(CH3)C═C(CN)2, with the proviso that two acidic functional groups containing one acidic hydrogen each, or a functional group containing two acidic hydrogens are present in compounds of Formula VIII, VIIIa, VIIIb, IX, X, XI, and XII.
  • Preferred azo-methine compounds corresond to Formula XIII [0059]
  • D=HC—R7—N═N-Z   XIII
  • wherein D, R[0060] 7 and Z are as defined previously.
  • The bis-azo compound corresponds to Formula VIIa [0061]
  • R6—N═N—Y1N═N—R6   VIIa
  • wherein R[0062] 6 is as defined above and Y1 is the residue of a bis coupling component selected from the classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines (3,4-dihydro-2H-1,4-benzoxazines), 3-cyano-6-hydroxy-2-pyridones, 2,6-diaminopyridines, 2,3-dihydroindoles, naphthylamines, 2-aminothiazoles, or a combination of these; with the provision the compounds of Formula VIIa contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl group (—SO2NH2) which contains two acidic hydrogens.
  • Several diacid monomers which are described in U.S. Pat. Nos. 4,804,719 and 3,689,501 are useful in the practice of the invention, including various anthraquinones, anthrapyridones, anthraisothiazoles, anthrapyrimidines, anthrapyrimidones, phthaloylacridones, etc. [0063]
  • Some of the preferred anthraquinone, anthrapyridone and anthrapyrimidine compounds correspond to the light absorbing compounds of Formulae XIV-XIXf [0064]
    Figure US20040195552A1-20041007-C00016
    Figure US20040195552A1-20041007-C00017
    Figure US20040195552A1-20041007-C00018
  • wherein R[0065] 14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylamino, halogen, C1-C6 alkoxy, C1-C6 alkylthio, aryl, aroyl, C1-C6 alkanoyl, C1-C6 alkanoyloxy, NHCO C1-C6 alkyl, NHCOaryl, NHCO2 C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl, C1-C6 alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO2C1-C6 alkyl, SO2 aryl, —SO2NH C1-C6 alkyl, —SO2N(C1-C6 alkyl)2, —SO2N(C1-C6 alkyl) aryl, CONH C1-C6 alkyl, CON(C1-C6 alkyl)2, CON(C1-C6 alkyl) aryl, C1-C6 alkyl, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino,
    Figure US20040195552A1-20041007-C00019
  • or hydroxy; Q and Q′ are independently selected from-O—, —N(COR[0066] 10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; R15 is selected from hydrogen, cyano, C1-C6 alkylamino, C1-C6 alkoxy, halogen, arylthio, aryl, heteroaryl, heteroarylthio, C1-C6 alkoxycarbonyl, aroyl or arylsulfonyl; R16 is selected from hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl and aryl; R16′ is selected from the group consisting of hydrogen, one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy; wherein each C1-C6 alkyl group and C1-C6 alkyl group which is a portion of another group may contain at least one substituent selected from hydroxy, cyano, chlorine, fluorine, C1-C6 alkoxy, C3-C8 cycloalkoxy, C1-C6 alkylcyclohexyl, hydroxmethyl cyclohexyl, aryl and heteroaryl; with the provision that two acidic groups containing one acidic proton each or one acidic group containing two acidic hydrogens be present in the compounds of Formula XIV-XIXf.
  • Typical coupler residues which are represented by Z above in Formulae VI, VII, XIII for the classes of azo, disazo and azo-methine compounds, respectively include: [0067]
    Figure US20040195552A1-20041007-C00020
    Figure US20040195552A1-20041007-C00021
  • wherein R[0068] 17 is selected f rom the group consisting of hydrogen, 1-2 groups selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, —O—C2-C6 alkylene-OH, O—C2-C6 alkylene-C1-C6 alkanoyloxy, C1-C6 alkylene-OH, C1-C6 alkylene-C1-C6 alkanoyloxy, halogen, carboxy, C1-C6 alkoxycarbonyl, trifluoromethyl, NHCOR24, NHCO2R24, NHCON(R24)R25, and NHSO2R25, wherein R24 is selected from hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl or aryl, R25 is selected from C1-C10 alkyl, C3-C8 cycloalkyl or aryl wherein each C1-C10 alkyl group in R24 and R25 may be further substituted with one or more groups selected from C3-C8 cycloalkyl, aryl, aryloxy, arylthio, CO2H, CO2 C1-C6 alkyl, cyano, hydroxy, succinimido, C1-C6 alkoxy,
    Figure US20040195552A1-20041007-C00022
  • wherein R[0069] 5′, R16′ and Q are as defined above; R18 and R19 are independently selected from hydrogen, unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl and aryl or R18 and R19 may be combined with another element to which they are attached to form a radical Z having the formula
    Figure US20040195552A1-20041007-C00023
  • wherein Q[0070] 2 is selected from a covalent bond, —O—, —S—, —SO2—, —CO—, —CO2—, —N—(C1-C6 alkyl)-, —N(CO C1-C6 alkyl)-, —N(SO2 C1-C6 alkyl)-, —N(CO aryl)-, or-N(SO2 aryl); R20, R21 and R22 are independently selected from the group consisting of or C1-C6 alkyl; R23 is selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, heteroaryl or aryl.
  • Typical electron, rich aromatic residues which are represented by R[0071] 11 in Formulae VIII-XII include:
    Figure US20040195552A1-20041007-C00024
  • wherein R[0072] 26 is selected from the group consisting of hydrogen, a group selected from C1-C6 alkoxycarbonyl, CO2H, C1-C6 alkyl or C1-C6 alkoxy; wherein R17-R23 are as defined previously.
  • Preferred coumarin compounds useful in the practice of the invention correspond to the following formulae: [0073]
    Figure US20040195552A1-20041007-C00025
  • wherein Z[0074] 3 is selected from cyano, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, arylsulfonyl, aryl, heteroaryl, formyl, aroyl, C1-C6 alkanoyl or-CH=D, wherein D, R17, R18 and R19 are as defined previously with the provision that the coumarin compounds contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl (—SO2NH2) group which contains two acidic hydrogens.
  • Typical coupler residues which are represented by Y[0075] 1 in Formula VIIa above include those of the formula (Z1-L1-Z2) wherein Z1 and Z2 are independently selected from
    Figure US20040195552A1-20041007-C00026
  • wherein L[0076] 1 is bonded to the nitrogen atom of Z1 and Z2; wherein L1 is selected from C2-C12 alkylene, C3-C8 cycloalkylene, arylene, C1-C4 alkylene-C3-C8 cycloalkylene-C1-C4 alkylene, C1-C4 alkylene-arylene-C1-C4 alkylene, C2-C4 alkylene-O-arylene-O—C2-C4 alkylene, —C2-C4 alkylene O1-3—C2-C4 alkylene, C2-C4 alkylene-S—C2-C4 alkylene, C2-C4 alkylene-SO2—C2-C4 alkylene, C2-C4 alkylene-N(SO2 C1-C6 alkyl) —C2-C4 alkylene, C2-C4 alkylene-N(SO2 aryl) —C2-C4 alkylene, C2-C4 alkylene-OCO2—C2-C4 alkylene, C2-C4 alkylene-O2C-arylene-CO2—C2-C4 alkylene, C2-C4 alkylene-O2C—C1-C12 alkylene-CO2—C2-C4 alkylene, C2-C4 alkylene-O2C—C3-C8 cycloalkylene-CO2—C2-C4 alkylene, C2-C4 alkylene-NHCO—C2-C4 alkylene and C2-C4 alkylene-NHSO2—C2-C4 alkylene; wherein R17, R18, R20, R21, R22, and R23 are as defined previously.
  • In the above definitions it is intended that in the terms C[0077] 1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkanoyl, —CONH C1-C6 alkyl, —SO2NH C1-C6 alkyl, —CON(C1-C6 alkyl)2, —SO2N(C1-C6 alkyl)2, —NHSO2 C1-C6 alkyl, —N(C1-C6 alkyl) SO2 C1-C6 alkyl, etc. unless otherwise stated that the C1-C6 alkyl portion of the group refers to a straight or branched chain alkyl group containing one to six carbon atoms and these substituted with one or more groups selected from carboxy, cyano, —SO2NH2, SO2NH C1-C6 alkyl, cyano, fluorine, chlorine, C1-C6 alkoxy, aryloxy, aryl, heteroaryl, arylthio, heteroarylthio, C3- C8-cycloalkyl, —O2C C1-C6 alkyl or-CO2 C1-C6 alkyl.
  • The terms C[0078] 1-C4 alkylene, C2-C4 alkylene, C1-C6 alkylene, C2-C6 alkylene, and C2-C12 alkylene are used to refer to divalent aliphatic hydrocarbon radicals containing one to four carbon atoms, two to four carbon atoms one to six carbon atoms, two to six carbon atoms, or two to twelve carbon atoms, respectively, and these optionally substituted with one or more groups selected from C1-C6 alkoxy, hydroxy, —O2C C1-C6 alkyl, carboxy, CO2 C1-C6 alkyl, chlorine, fluorine, aryl or aryloxy.
  • The terms C[0079] 3-C8 cycloalkyl and C3-C8 cycloalkylene are used to refer to fully saturated monovalent and divalent cycloaliphatic radicals, respectively, and these substituted by one or more C1-C6 alkyl groups.
  • The terms C[0080] 3-C8 alkenyl and C3-C8 alkynyl are used to refer to straight or branced hydrocarbon radicals containing at least one double bond or at least one triple bond, respectively.
  • In the terms aryl, NH aryl, aryloxy, aroyl, arylthio, arylsulfonyl, aryloxysulfonyl, —N(SO[0081] 2 aryl)-, —N(CO aryl)-, NHCO aryl, —NH CONH aryl, NHSO2, aryl, etc., the aryl portion of the group represents phenyl and naphthyl and these substituted with one or more groups selected from-CO2H, C1-C6 alkyl, CO2 C1-C6 alkyl, SO2NH2, SO2NH C1-C6 alkyl, hydroxy, O C1-C6 alkyl, S C1-C6 alkyl, phenyl, O-arylene-CO2H, —S-arylene-CO2H, SO2 arylene-CO2H, halogen, NHSO2 C1-C6 alkyl, trifluoromethyl, NH CO C1-C6 alkyl, cyano, or 1(H)-1,2,4-triazol-3-ylthio.
  • The term arylene is used to represent 1,2-, 1,3-, and 1,4-phenylene and these optionally substituted with one or more groups mentioned above as possible substituents on the aryl radical. [0082]
  • The term “heteroaryl” is used to describe a 5 or 6 membered heterocyclic aromatic ring containing one oxygen atom, and/or one sulfur atom, and/or up to three nitrogen atoms, said heterocyclic aryl ring optionally fused to one or two phenyl rings or another 5 or 6-membered heteroaryl ring. Examples of such ring systems include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, thiatriazolyl, oxatriazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazinyl, oxazinyl, triazinyl, thiadiazinyl, oxadiazinyl, dithiazinyl, dioxazinyl, oxathiazinyl, tetrazynyl, thiatriazinyl, oxatriazinyl, dithiadiazinyl, imidazolinyl, dihydropyrimidyl, tetrahydropyrimidyl, tetrazolo [1,5-b]-pyridazinyl and purinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and the like and those rings substituted with one or more substituents listed above in the definition of the term “aryl”. [0083]
  • The term halogen is used to refer to fluorine, chlorine, bromine and iodine. [0084]
  • In the above definitions the unsubstituted and substituted C[0085] 1-C10 alkyl groups or portion of groups mentioned refer to fully saturated hydrocarbon radicals containing one to ten carbon atoms, either straight or branched chain, and such alkyl radicals substituted with one or more of the following: C3-C8 cycloalkyl, aryl, hydroxy, cyano, —O—C2-C4 alkylene OH, —O—C2-C4 alkylene O2 C—C1-C6 alkyl, —S—C2-C4 alkylene-OH, chlorine, fluorine, —O—C1-C6 alkyl, —O-aryl, —SO2 aryl, —SO2—C1-C6 alkyl, 2-pyrrolidino, phthalimidino, phthalimido, succinimido, glutarimido, o-benzoic sulfimide, vinyl sulfonyl, —NHCO C1-C6 alkyl, NHCOH, —NHSO2-C1-C6 alkyl, NHSO2 aryl, —NHCO aryl, —NH—CO2—C1-C6 alkyl, —SO2NH2, —SO2—NH—C1-C6 alkyl, —SO2N—(C1-C6 alkyl)2, —CO2—C1-C6 alkyl, CONH2, —CONH—C1-C6 alkyl, —CO2-aryl, —CON(C1-C6 alkyl)2, —CCONH aryl, —CONH(C1-C6 alkyl) aryl, —SO2N(C1-C6 alkyl) aryl, —SO2—NH—C3-C8 cycloalkyl, —CONH—C3-C8 cycloalkyl, —OCO2—C1-C6 alkyl, —O C2-C4 alkylene CN; groups of the formulae:
    Figure US20040195552A1-20041007-C00027
  • wherein Y[0086] 2 is selected from 1,2-phenylene; 1,2 pheylene substituted with C1-C6 alkyl, C1-C6 alkoxy, halogen, —CO2H, —CO2 C1-C5 alkyl or nitro; C2-C4 alkylene, vinylene, —O CH2—, —SCH2—, —CH2OCH2—, —OCH2CH2—, —CH2SCH2—, —NHCH2—, —NHCH2CH2, —N(C1-C6 alkyl)CH2—, NHC(C1-C6 alkyl)2, —N(C1-C6 alkyl) CH2CH2 or-NHC (aryl)2-; groups of the formulae:
  • —SR25, —SO2CH2CH2SR25, —OCH2CH2SR25,
    Figure US20040195552A1-20041007-C00028
  • wherein R[0087] 26 is selected from hydrogen, C1-C10 alkyl, C2-C4 alkylene-OH, C2-C4 alkylene-CO2H, C2-C4 alkylene-CO2 C1-C6 alkyl, chloro, C1-C6 alkoxy, C1-C4 alkylene-arylene-CO2H, C2-C4 alkylene-O-arylene-CO2H or C2-C4 alkylene-S-arylene-CO2H and R5′ R17, R25 and Q are as defined previously:
  • The term “light absorbing” is used to indicate the property of absorbing near ultra violet, visible or near infrared light, more particularly absorbing light between the wavelengths of 300-1200 nm, preferably between about 325 nm and 1100 nm, and most preferably between about 325 nm and 1000 nm. [0088]
  • Typical aromatic amines which are useful as the coupling components to prepare compounds of Formulae VI, VII and VIII and as intermediates for preparing the compounds of Formula VIII, VIIIa, IX, X, XI and XII are as follows: [0089]
    Figure US20040195552A1-20041007-C00029
    Figure US20040195552A1-20041007-C00030
    Figure US20040195552A1-20041007-C00031
    Figure US20040195552A1-20041007-C00032
  • wherein Q, R[0090] 5′, R17, R18, R19, R20, R21, R22 and R23 are as defined previously.
  • Typical diazotizable amines (R[0091] 6 NH2) useful in the preparation of azo, disazo and bis-azo compounds of Formulae VI, VII, and VIIa, respectively, are adequately disclosed in the literature, e.g.:
  • M. Weaver and L. Shuttleworth, Dyes and Pigments, 3 (1982) 81-121; [0092]
  • L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107-63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.; [0093]
  • U.S. Pat. Nos. 3,438,961; 3,573,273; 3,639,384; 3,707,532; 3,790,557; 3,816,388; 3,816,392; 3,878,189; 3,980,634; 4,012,372; 4,039,522; 4,049,643; 4,083,684; 4,083,844; 4,097,475; 4,105,655; 4,119,621; 4,140,683; 4,180,503; 4,189,428; 4,207,233; 4,211,696; 4,264,495; 4,283,332; 4,400,318; 4,431,585; 4,456,551; 4,487,719; 4,542,207; 4,564,673; 4,619,991; 4,621,136; 4,650,861; 4,668,775; 4,734,490; 4,751,288; 4,760,133; 4,764,600; 4,837,269; 4,841,036; 4,843,153; 4,888,432; 4,960,874; 5,037,966; 5,132,411; 5,144,015; 5,283,326; 5,296,325; 5,352,774. [0094]
  • Typical coupling components H-Z useful in preparing azo compounds, disazo and azo-methine compounds of Formula VI, VII and XIII, respectively, are disclosed in the literature, e.g: H. R. Schwander, Dyes and Pigments, 3(1982) 133-160; L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107-63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.; U.S. Pat. Nos. 3,639,384; 3,639,385; 3,657,215; 3,673,169; 3,816,388; 3,829,410; 3,919,188; 3,950,130; 3,980,634; 4,041,025; 4,097,475; 4,119,621; 4,179,435; 4,234,482; 4,283,332; 4,341,700; 4,400,318; 4,431,585; 4,396,547; 4,619,992; 4,642,339; 4,650,861; 4,668,775; 4,764,600; 4,837,269; 4,843,153; 5,235,047; 5,283,326; 5,352,774. [0095]
  • Typical active methylene compounds useful in the preparation of methine, arylidene, polymethine, azamethine and azo-methine compounds corresponding to Formulae VIII, VIIIa, VIIIb, IX and XIII, respectively, are disclosed in the literature, e.g. U.S. Pat. Nos. 4,338,247; 4,617,373; 4,617,374; 4,707,537; 4,749,774; 4,826,903; 4,845,187; 4,950,732; 4,981,516 and 5,283,326. [0096]
  • According to the present invention the light-absorbing polymeric and cyclic compositions are incorporated into a wide variety of thermoplastic polymers using conventional techniques, e.g. solution or melt blending, such as those employed to incorporate other additives in such polymers (see R. Gächter and H. Müeller, Editors: Plastics Additives Handbook, Hansu Publishers, New York, 1985, pp. 507-533; 729-741). For example, the light absorbing polymeric and cyclic compositions may be dry blended in the form of pellets or powders with or without adhesion promoters or dispersing agents. This premix can be subsequently processed on extruders or injection molding machines. Other conventional additives such as plasticizers, nucleating agents, flame retardants, lubricants, etc. may also be present in the final thermoplastic composition. [0097]
  • A wide range of thermoplastic polymers useful for blending with the light absorbing polymeric and cyclic compositions are known in the art and includes the homopolymers, copolymers and blends of polyesters, e.g., poly(ethylene terephthalate); polyolefins, e.g., polypropylene, polyethylene, linear low density polyethylene, polybutylene, and copolymers made from ethylene, propylene and/or butylene; copolymers from acrylonitrile, butadiene, and styrene; copolymers from styrene and acrylonitrile; polyamides, e.g., Nylon 6 and Nylon 66; polyvinyl chloride; polyurethanes; polyvinylidene chloride; polycarbonates; cellulose esters, e.g., cellulose acetate, propionate, butyrate, or mixed esters; polyacrylates, e.g., poly(methyl methacrylate); polyimides; polyester-amides; polystyrene; and mixtures or blends thereof etc. [0098]
  • It should also be appreciated that a multiplicity of colors may be obtained by combining individual colors, e.g., subtractive colors such as yellow, magenta and cyan according to known color technology (see N. Ohta, [0099] Photographic Science and Engineering. Volume 15, No. 5, September-October 1971, pp. 395-415).
  • The particular chromophore groups present will, of course, determine the color (hue+value+chroma) of the colored polymer composition and finally the color (hue+value+chroma) of the thermoplastic polymer blends of the present invention. A large gamut of colors may be obtained, as noted above. [0100]
  • The actual amount of the light absorbing polymers used in combination with thermoplastic polymer will depend upon the inherent tinctorial strength of the chromophore used to prepare the light absorbing polymer, the mole % of the light absorbing monomer used to prepare the light absorbing polymer and the required level of light absorption necessary to achieve a certain property. Typically, the amount of light-absorbing polymer added to the thermoplastic polymer is such that the total amount of light-absorbing polymer in the final thermoplastic blend is from about 0.001% by weight to about 20% by weight, preferably from about 0.01% by weight to about 10% by weight. The final thermoplastic polymer blends thus provided are useful as a variety of molded and extruded articles, including thick and thin plastic films, plastic sheeting, molded plastic articles, containers and fibers, and the like. [0101]
  • When the light-absorbing polymeric compositions absorb visible light they may be used to impart light or heavy shades of a variety of colors to thermoplastics. Certain compounds which possess unique visible light-absorbing properties are useful also as toners in imparting a desirable neutral to slightly blue hue to polyesters having a yellow appearance as described in U.S. Pat. No. 5,384,377, which discloses the copolymerization of certain thermally stable colorants for this purpose during polyester manufacture. Some of the infra-red absorbing polymeric and cyclic compositions are useful in imparting invisible markings to thermoplastics as described in U.S. Pat. No. 5,461,136, wherein the infrared absorbing compounds are fluorescent in the near infrared and are copolymerized into the thermoplastic condensation polymer during manufacture. The ultra violet absorbing polymeric and cyclic compositions may be used to impart ultra violet (UV) light screening properties to the thermoplastics; to serve as optical brighteners for the thermoplastics or to serve as UV stabilizers for the polymers themselves or for other light absorbers such as colorants. [0102]
  • The weight average molecular weights (Mw) and the number average molecular weights (Mn) of the polymeric compositions were determined using gel permeation chromatography (GPC) analysis. [0103]
  • The following examples illustrate further the practice of the invention.[0104]
    • EXAMPLE 1
  • A mixture of 1,5-bis(2-carboxyphenylthio) anthraquinone (25.60 g, 0.05 mole), 1,2-ethanediol, dimethanesulfonate (10.90 g, 0.05 mole), potassium carbonate (13.82 g, 0.10 mole) and N-methyl-2-pyrrolidinone (NMP) (400 mL) was heated with stirring at 125° C. for 1.0 hr. The reaction mixture was poured into methanol (600 mL) with stirring. The yellow polymeric product was collected by filtration and washed with methanol until filtrate was essentially clear. The methanol-wet filter cake was slurried in 1.0 L of water, the mixture acidified by the addition of acetic acid and the yellow product was collected by filtration, washed with hot water and dried in air (yield- 21.16 g). By gel permeation chromatography (GPC) the polymeric product has a weight average molecular weight of 6,083, and number average molecular weight of 3,000 and a polydispersity value of 2.03. [0105]
    • EXAMPLE 2
  • A mixture of a blue anthraquinone compound (19.65 g 0.03 mole) containing two carboxy groups and having the following structure: [0106]
    Figure US20040195552A1-20041007-C00033
  • 1,2-ethanediol, dimethanesulfonate (6.54 g, 0.03 m),potassium carbonate (8.28 g, 0.06 mole) and N,N-dimethylformamide (DMF) (100 mL) was heated with stirring at about 95° C. for 1.5 hr. The reaction mixture became too thick to stir effectively and additional DMF (50 mL) was added to facilitate stirring. Stirred about 15 min. longer at about 95° C., and then added methanol (100 mL) with good stirring to the slightly cooled reaction mixture. The blue polymeric product was collected by filtration and washed with methanol. The methanol-wet filter cake was added to water (600 mL) and the mixture was acidified with acetic acid, and then the polymeric product was collected by filtration, washed with water and dried in air (yield 18.18 g). By GPC analysis the blue polymer had a molecular weight average of 3,038, a number average molecular weight of 1,814 and a polydispersity of 1.67. [0107]
    • EXAMPLE 2a
  • A mixture of 1,5-bis (isobutylamino)-4,8-dibromoanthraquinone (25.3 g, 0.05 mole), thiosalicylic acid (23.1 g, 0.15 mole), anhydrous K[0108] 2CO3 (20.7 g, 0.15 mole), cupric chloride dihydrate (1.2 g) and DMF (250 mL) was heated at 90-95° C. with stirring for 2.0 hours. Thin layer chromatography (TLC) using 1:1 tetrahydrofuran (THF):cyclohexane showed complete conversion of the red starting material to the desired blue polar product. The reaction mixture was allowed to cool and then was drowned into water (800 mL). The blue solid was precipitated by acidification with acetic acid with stirring. The mixture was heated to about 60° C. with occasional stirring and the solid was collected by filtration, washed with hot water and dried in air. Further purification was accomplished by reslurrying the product in hot methanol (300 mL), allowing to cool to room temperature, collecting by filtration, washing with methanol and air drying to yield the starting material (31.5 g) for Example 2.
    • EXAMPLE 2b
  • 1,5-Bis(isobutylamino)anthraquinone (28.0 g, 0.08 mole) was added to DMF (300 mL) and the mixture stirred at room temperature. A solution of 1,3-dibromo-5,5-dimethylhydantoin (23.0 g, 0.08 m) dissolved in DMF (75.0 mL) was added dropwise to the reaction mixture while warming to about 50° C. After complete addition of the brominating agent, the reaction mixture was heated at 50-60° C. for 1.5 hours, allowed to cool and then drowned by gradual addition to water (500 mL) with stirring. The red product was collected by filtration, washed with water and dried in air. The yield of product was 39.6 g and field desorption mass spectrum analysis (FDMS) showed the product to be 1,5-bis(isobutylamino)-4,8-dibromoanthraquinone used as the intermediate in Example 2a. [0109]
    • EXAMPLE 2c
  • A mixture of 1,5-dichloroanthraquinone (69.5 g, 0.25 mole), isobutylamine (100 g, 1.4 mole) and 2-ethoxyethanol (400 mL) was heated at reflux for 36.0 hours and allowed to cool. Methanol (400 mL) was added to make the mixture containing the crystallized product more stirrable. The dark red product was collected by filtration, washed with methanol, reslurried in hot methanol and allowed to cool, collected by filtration, washed with methanol and dried in air (yield—67.7 g). FDMS showed the product to be the 1,5-bis(isobutylamino)anthraquinone in high purity which was used as the starting material for Example 2b. [0110]
    • EXAMPLE 3
  • A mixture of an azo compound (2.93 g, 0.005 m) containing two 1(H)-1,2,4-triazol-3-thio groups and having the following structure: [0111]
    Figure US20040195552A1-20041007-C00034
  • 1,2-ethanediol, dimethanesulfonate (1.08 g, 0.005 mole), potassium carbonate (1.50 g) and DMF (25.0 mL) was heated at about 95° C. with stirring for 2.5 hrs. The reaction mixture was drowned into methanol (150 mL) and the red polymeric product was collected by filtration, washed with. water containing a little acetic acid and then washed with hot water and dried in air (yield—2.35 g). The polymer by GPC analysis had a weight average molecular weight of 5,396, a number average molecular weight of 3,044 and a polydispersity value of 1.77. [0112]
    • EXAMPLE 4
  • Eastar® PETG copolyester 6763, a poly(ethylene-1,4-cyclohexanedimethylene) terephthalate, (Eastman Chemical Co.) (400 g. of previously dried pellets) was dry blended with the yellow anthraquinone polymeric composition (0.12 g) of Example 1. The blend was extruded with a C. W. Brabender ¾ in. extruder, equipped with a mixing screw, at 250° C. into a water bath and the extrudate pelletized. [0113]
  • The pellets were redried at 70° C. for about 17 hrs. at a pressure of about 1-5 torr. A portion of the dried pellets (1.40 g) was pressed into a 18-20 mil film at 250° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4 inch ram). A transparent yellow film was produced with excellent color development, which contained about 300 ppm by weight of the yellow polymeric composition. [0114]
    • EXAMPLE 5
  • Example 4 was repeated using 0.12 g of the blue anthraquinone polymeric composition of Example 2 to give a bright blue transparent copolyester film with good color development. [0115]
    • EXAMPLE 6
  • Example 4 was repeated using 0.12 g of the red azo polymeric composition of Example 3 to produce a bright red transparent film having good color development. [0116]
    • EXAMPLE 7
  • A mixture of a blue anthraquinone compound (3.46 g, 0.005 mole) containing two acidic 1(H)-1,2,4-triazol-3-ylthio groups and having the following structure [0117]
    Figure US20040195552A1-20041007-C00035
  • 1,2-ethanediol, dimethanesulfonate (1.09 g, 0.005 mole) DMF (30 mL) and potassium carbonate (1.5 g) was heated with stirring at about 95° C. for 2.0 hours and then drowned into methanol (100 mL). The blue polydye was collected by filtration and washed with methanol. The methanol-wet cake was reslurried in water (400 mL) and the stirred mixture was acidified by addition of acetic acid and heated to about 60° C. The final polymeric product was collected by filtration, washed with water and dried in air (yield—1.5 g). Absorption maxima were observed at 594,636 nm in a solution of DMF in the visible light absorption spectrum. By GPC, the polydye has a weight average molecular weight (Mw) of 3,769, a number average molecular weight (Mn) of 2,119 and a polydispersity of 1.78. [0118]
    • EXAMPLE 7a
  • A mixture of 1,5-bis[(3-acetoxy-2,2-dimethylpropyl)amino-4,8-dibromoanthraquinone (6.50 g, 0.01 mole) (product of Example 2—Invention Report Docket No. 70524), 3-mercapto-1(H)-1,2,4-triazole (3.03 g, 0.03 mole), potassium carbonate (4.15 g, 0.03 mole), cupric chloride dihydrate (0.65 g) and DMF (100 mL) was heated 14 hours at about 100-105° C. The reaction mixture was drowned into a mixture of water (400 mL) and 10% aqueous solution of hydrochloric acid (200 mL). The blue product was collected by filtration, washed with hot water and dried in air (yield—6.58 g). FDMS supported the desired structure of the starting anthraquinone compound for Example 7. [0119]
    • EXAMPLE 8
  • A mixture of blue anthraquinone compound (2.48.g, 0.0033 mole) having the following structure [0120]
    Figure US20040195552A1-20041007-C00036
  • 1,2-ethanediol, dimethanesulfonate (0.73 g, 0.0033 mole), potassium carbonate (0.5 g) and DMF (30.0 mL) was heated at about 95° C. for 3.0 hours. The reaction mixture was drowned into methanol (150 mL) with stirring and the blue polydye product was collected by filtration and washed with methanol. The. methanol-wet cake was reslurried in water (200 mL) and the mixture acidified with acetic acid. Collecting the blue solid by filtration, washing with hot water and air drying gave 1.21 g of polydye product, which has absorption maxima at 606,652 nm in DMF in the visible absorption spectrum, a weight average molecular weight of 4,453, a number average molecular weight of 2,721 and a polydispersity of 1.6. [0121]
    • EXAMPLE 8a
  • A mixture of 1,5-bis[(3-acetoxy-2,2-dimethylpropyl)amino]-4,8-dibromoanthraquinone (19.56 g, 0.03 mole), p-hydroxybenzenethiol (17.64 g, 0.14 mole), potassium carbonate (19.32 g, 0.14 mole), cupric chloride dihydrate (1.0 g) and DMF (150 mL) was heated and stirred at 90-95° C. for 7.0 hours and then at 120° C. for about 2.0 additional hours. TLC (50:50 THF:cyclohexane) showed mostly the desired blue product, but still a small amount of violet half-reacted product was present. The reaction mixture was drowned into methanol (500 mL) and the mixture allowed to cool. After crystallization, the blue solid was collected by filtration, washed with methanol, washed with hot water and then dried in air (yield—17.6 g). FDMS supported the desired structure of the starting anthraquinone compound for Example 8. In the visible light absorption spectrum in DMF, a maximum absorbance (λmax) was observed at 652 nm (extinction coefficient ε of 24,638). [0122]
    • EXAMPLE 9
  • A mixture of 1,4-bis-(2,6-dimethyl-4-hydroxyanilino)anthraquinone (4.78 g, 0.01 mole) (Synthesis Example 1 of U.S. Pat. No. 3,918,976), 1,2-ethanediol, dimethanesulfonate (2.18 g, 0.01 mole), potassium carbonate. (3.0 g) and DMF (60 mL) was heated at 90-95° C. with stirring for 4.0 hours. After drowning the reaction mixture into methanol (300 mL), the product was collected by filtration and washed with methanol until filtrate was essentially colorless. The methanol-wet cake was reslurried in 100 mL water and acidified by adding acetic acid with stirring. After heating to about 50° C., the product was collected by filtration, washed with hot water and dried in air (yield—1.2 g). By GPC, the blue polydye had a weight average molecular weight (Mw) of 2,764, a number average molecular weight (Mn) of 1,607 and a polydispersity of 1.72. In DMF, the visible light absorption maxima were at 586,630 nm. [0123]
    • EXAMPLE 10
  • A mixture of an anthraquinone diacidic compound (1.52 g, 0.002 mole) having the following structure [0124]
    Figure US20040195552A1-20041007-C00037
  • 1,2-ethanediol, dimethanesulfonate (0.44 g, 0.002 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated at about 95° C. with occasional stirring for 20 hours. The reaction mixture was downed into methanol (50 mL) and the product was collected by filtration, washed with methanol, water plus acetic acid, hot water and then dried in air (yield—1.05 g). The blue polydye had a weight average molecular weight (Mw) of 3,586, a number average molecular weight (Mn) of 1,867 and a polydispersity value of 1.92. In the visible light absorption spectrum, maxima of absorbance occurred at wavelengths of 605 and 647 nm in DMF. [0125]
    • EXAMPLE 10a
  • A mixture of 1,5-bis-(4-methylcyclohexanemethylamino)-4,8-dibromoanthraquinone (20.0 g, 0.0324 mole), thiosalicyclic acid (11.55 g, 0.075 mole), potassium carbonate (10.35 g, 0.075 m), cupric chloride dihydrate (1.0 g) and DMF (175 mL) was heated at about 95° C. for 4.0 hours and then drowned into acetone (400 mL). The solid which crystallized was collected by filtration, washed with acetone until the filtrate was no longer red. The dipotassium salt of the diacidic anthraquinone compound was dissolved by adding to water (500 mL) and stirring. The blue product which was precipitated by acidification with acetic acid was collected by filtration, washed with hot water and then dried in air (yield—21.5 g). FDMS indicated the structure to be consistent with that given above in Example 10 for the starting diacidic anthraquinone compound. [0126]
    • EXAMPLE 10b
  • A solution of 1,5-bis-(4-methylcyclohexanemethylamino)anthraquinone (65.0 g, 0.142 mole) dissolved in DMF (1.0 L) by stirring at about 55° C. was treated with a solution of N-bromosuccinimide (50.5 g, 0.284 mole) in DMF (200 mL). After addition was completed, the bromination reaction was completed by heating at 55-60° C. for 2.0 hours. Water (1.0 L) was added. to precipitate the red product which was collected by filtration, washed with water and dried in air. After being reslurried in hot methanol and cooling, the product was collected by filtration, washed with a little methanol and air dried (yield—84.0 g). FDMS indicated the structure to be that of the starting, dibrominated anthraquinone compound of Example 10a. [0127]
    • EXAMPLE 10c
  • A mixture of 1,5-dichloroanthraquinone (48.0 g, 0.17 mole), 4-methyl-1-aminomethylcyclohexane (88.9 g, 0.70 mole), 2-ethoxyethanol (400 mL) was stirred and heated at reflux for 35.0 hours and the reaction mixture allowed to cool. The red product was precipitated by the addition of methanol and was the collected by filtration, washed with methanol and dried in air (yield—66.0 g). FDMS indicated the product to be the starting anthraquinone compound for Example 10b. [0128]
    • EXAMPLE 11
  • A mixture of diacidic anthraquinone compound (0.69 g, 0.001 m) having the following structure [0129]
    Figure US20040195552A1-20041007-C00038
  • 1,6-hexanediol, dimethanesulfonate (0.27 g, 0.001 mole), potassium carbonate (0.3 g) and DMF (5.0 mL), was heated with occasional stirring for 2.5 hours at about 95° C. The reaction mixture was drowned into methanol (100 mL) and the product collected by filtration, washed with methanol, water containing a little acetic acid and then finally with hot water and air dried (yield—0.45 g). The blue polydye had an absorption maximum at 610 nm in DMF, a weight average molecular weight of 3,311 a number average molecular weight of 1,272 and a polydispersity value of 2.63. [0130]
    • EXAMPLE 11a
  • A mixture of 1,8-di-(2-carboxyphenylthio)-4,5,-dinitroanthraquinone (4.00 g, 0.0066 mole), aniline (2.5 g) and nitrobenzene (30.0 mL) was heated at reflux with stirring for 5.0 hours. The reaction mixture was drowned into hexane and the hexane decanted. The product was washed again by adding hexane, stirring and decanting. The crude product was slurried in acetone and heated to reflux and the blue product collected by filtration, washed with water and air dried (yield—0.75 g). FDMS indicated the product to be mostly 1,8-dianilino-4,5-di-(2-carboxyphenylthio)anthraquinone, the starting diacidic, anthraquinone compound for Example 11. [0131]
    • EXAMPLE 11b
  • The potassium salt of thiosalicyclic acid (4.75 g, 0.03 mole) was made by addition to DMF (75 mL) and heating in the presence of potassium carbonate (8.70 g, 0.06 mole) for 2.0 hours at about 95° C. The cooled mixture was added to a solution of 1,8-dichloro-4,5-dinitroanthraquinone (5.51 g, 0.015 mole) dissolved in DMF (150 mL) at about 0-5° C. with stirring. The reaction mixture was allowed to warm to about 25° C. with stirring continued for 2.0 hours and then poured into water. The product was obtained in essentially quantitatively yield by slowly acidifying with 10% hydrochloric acid and was then collected by filtration, washed with water and dried in air. FDMS indicated the product to be mostly the starting anthraquinone compound used in Example 11a. [0132]
    • EXAMPLE 12
  • A mixture of the diacidic anthraquinone compound (0.85 g. 0.0015 m) having the following structure [0133]
    Figure US20040195552A1-20041007-C00039
  • 1,6-hexanediol, dimethanesulfonate (0.41 g, 0.0015 m), potassium carbonate (0.5 g) and DMF (5.0 mL) was heated at about 95° C. for 2.0 hours with occasional stirring. The reaction mixture was drowned into methanol (100 mL) and the blue polydye was collected by filtration, washed with methanol, water containing a little acetic acid and finally hot water and then dried in air (yield—0.62 g). GPC analysis indicated a weight average molecular weight of 20,020, a number average molecular weight of 2,313 and a polydispersity of 8.66. An absorption maximum was observed at 591 nm in the visible light absorption spectrum in DMF. [0134]
    • EXAMPLE 12a
  • The anthraquinone diester compound (4.00 g) having the following structure [0135]
    Figure US20040195552A1-20041007-C00040
  • 50% aqueous sodium hydroxide (2.40 g) and 2-ethoxyethanol (60 mL) were combined and heated with stirring at about 95° C. for 0.5 hour. Hydrolysis of ester groups appeared to be complete by TLC (50:50 THF:cyclohexane). The reaction mixture was drowned into water (600 mL) and the blue solution acidified using acetic acid. The blue solid was collected by filtration washed with water and dried in air (yield—3.80 g). FDMS indicated the structure to be mostly that of the starting diacidic anthraquinone compound in Example 12 plus a small amount of a violet compound probably produced by displacement of the bromine atom with the 2-(ethoxy)ethoxy group. [0136]
    • EXAMPLE 12b
  • A mixture of 1-amino-2,4-dibromoanthrquinone (7.62 g, 0.02 mole), dimethyl 5(4-aminophenoxy)isophthalate (9.03 g, 0.03 mole), 1-pentanol (100 mL), potassium acetate 4.0 g), and cupric acetate (0.2 g) was heated at reflux for 4.0 hours and until all of the starting material had been used up as indicated by TLC analysis (20:80 THF:cyclohexane). Several blue components presumed to be a mixture of ester products produced by transesterification were observed. The reaction mixture was drowned into methanol (100 mL) and the product was collected by filtration, washed thoroughly with methanol to remove a red by-product and then washed with water and dried in air (yield—7.81 g). FDMS indicated ions corresponding to the dimethylester, monopentyl ester and dipentylester of the product—the structure of the starting material for Example 12a. [0137]
    • EXAMPLE 12c
  • A mixture of dimethyl 5-(4-nitrophenoxy)isophthalate (30.0 g, 0.09 mole), isopropanol alcohol (350 mL) and ethanol wet Raney nickel catalyst (5.0 g) was hydrogenated at 90° C. for 4.0 hours at 1500 psi hydrogen pressure in an autoclave. Isopropanol (100 mL) was added to the reaction mixture from the autoclave and the solid product dissolved by heating. The Raney nickel was removed by hot filtration and the filtrate allowed to cool. The off-white solid was collected by filtration and dried in air (yield—17.8 g). FDMS indicated the product to be dimethyl 5-(4-aminophenoxy)isophthalate used in Example 12b. [0138]
    • EXAMPLE 12d
  • A mixture of 1-chloro-4-nitrobenzene (47.1 g, 0.30 mole), dimethyl 5-hydroxyisophthalate (63.0 g, 0.30 mole), anhydrous potassium carbonate (41.4 g), potassium iodide (0.2 g) and DMF (200 mL) was heated at 120-125° C. for 1.5 hours, under a slow nitrogen sweep allowing some distillate to be removed (about 75 mL) via a Dean-Stark trap. Additional DMF (50 mL) was added back to the reaction mixture and heating continued for an additional 1.5 hours while an additional amount of distillate (25 mL) was allowed to collect in the Dean-Stark trap. The reaction mixture was allowed to cool to about 45° C. A heavy slurry of pale yellow product resulted which was diluted further by the addition of an ice-water mixture (350 g) with good stirring. Filtration followed by washing with water and drying in air gave the pale yellow dimethyl 5-(4-nitrophenoxy)isophthalate (90.7 g) (structure supported by FDMS) which was used in Example 12c. [0139]
    • EXAMPLE 13
  • A mixture of the diacidic anthraquinone compound (1.26 g, 0.002 mole) having the following structure [0140]
    Figure US20040195552A1-20041007-C00041
  • 1,6-hexandiol, dimethanesulfonate (0.58 g, 0.002 mole), potassium carbonate (0.5 g) and DMF (6.0 mL) was heated at 90-95° C. for 2.0 hours with occasional stirring. The reaction mixture was drowned into methanol (100 mL) and the dark blue-green polydye was collected by filtration, washed with methanol, water containing a little acetic acid and finally with water and then dried in air (yield 1.13 g). GPC analysis indicated a weight average, molecular weight of 14,776, a number average molecular. weight of 2,514 and a polydispersity of 5.88. An absorption maximum was observed at 620 nm in the visible light absorption spectrum in DMF. [0141]
    • EXAMPLE 13a
  • A portion (1.72 g, 0.003 mole) of the bromoanthraquinone product of Example 12a, benzenesulfinic acid, Na salt (0.98 g, 0.006 mole), potassium carbonate (1.38 g) and DMF (25 mL) were mixed and the reaction mixture heated with stirring at 90-95° C. for 1.0 hour. A bathochromic shift in color was observed as the 2-bromo substituent was replaced by the 2-phenylsulfonyl group on the anthraquinone nucleus. The greenish-blue solution was drowned into acetone (100 mL) and the solid material was collected by filtration and washed with acetone until the filtrate was pale blue. The acetone-wet solid was added with stirring to water (200 mL) and the mixture acidified with acetic acid. After being heated to about 75° C., the reaction mixture was filtered and the dark blue solid was washed with hot water and dried in air (yield—1.50 g). FDMS indicated the structure to be that of the starting diacidic anthraquinone compound used in Example 13. [0142]
    • EXAMPLE 14
  • A mixture of the diacidic anthraquinone compound (1.45 g, 0.003 mole) having the structure [0143]
    Figure US20040195552A1-20041007-C00042
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated at about 95° C. for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the blue polydye was collected by filtration and washed with methanol, water containing a little acetic acid and finally hot water and dried in air (yield—1.10 g). GPC analysis indicated a weight average molecular weight of 3,727, a number average weight of 1,031 and a polydispersity of 3.61. Absorption maxima were observed at 623 nm and 585 nm in the visible light absorption spectrum in DMF. [0144]
    • EXAMPLE 15
  • A mixture of the diacidic anthraquinone compound (1.50 g, 0.003 mole) having the following structure [0145]
    Figure US20040195552A1-20041007-C00043
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated with occasional stirring at about 95° C. for 2.0 hours. The reaction mixture was then drowned into methanol (100 mL) and the blue polydye was collected by filtration, washed with methanol, water containing a little acetic acid, and hot water and then dried in air (yield—0.90 g). An absorption maximum at 591 nm was observed in the visible light absorption spectrum in DMF. [0146]
    • EXAMPLE 15a
  • To DMF (40 mL) was added 1-amino-2-Br-4-(5-chlorosulfonyl-2-methoxyanilino) anthraquinone (4.0 g) with stirring. When solution appeared to be complete, conc. ammonium hydroxide (4.0 g) was added and stirring was continued at ambient temperature for 30 minutes. TLC using 50:50 THF:cyclohexane indicated complete reaction of the sulfonyl chloride compound to produce the desired sulfonamide. The reaction mixture was drowned into water and the blue product was collected by filtration, washed with water and air dried (yield—3.8 g). FDMS indicated the structure to be that of the starting compound for Example 15. [0147]
    • EXAMPLE 15b
  • To chlorosulfonic acid (100 mL) was added 1-amino-4-o-anisidino-2-bromoanthraquinone (10.0 g, 0.0236 mole) portionwise with good stirring at 25-30° C. After addition was completed, the reaction mixture was stirred at room temperature for 1.0 hour. The reaction mixture was added in a fine stream to cold isopropanol (800 mL) with stirring. The blue product was collected by vacuum filtration on a sintered glass funnel, washed with isopropanol and dried in air (yield—10.3 g) and used without further purification in Example 15a. [0148]
    • EXAMPLE 16
  • A mixture of the diacidic anthraquinone compound (0.58 g, 0.001 m) having the following structure [0149]
    Figure US20040195552A1-20041007-C00044
  • 1,2-ethanediol, dimethanesulfonate (0.22 g, 0.001 m), potassium carbonate (0.3 g) and DMF (5.0 mL) was heated at 95° C. for 2.5 hours. The reaction mixture was drowned into methanol (100 mL) and the greenish-blue polydye was collected by filtration, washed with methanol, water containing a little acetic acid and water and then air dried (yield—0.33 g). GPC analysis indicated a weight average molecular weight of 4,144 a number average molecular weight of 1,643 and a polydispersity of 2.52. An absorption maximum at 629 nm was observed in the visible light absorption spectrum in DMF. [0150]
    • EXAMPLE 16a
  • A mixture of 1,8-diamino-2,7-dibromo-4,5-dihydroxyanthraquinone (2.19 g, 0.005 mole), thiosalicyclic acid (1.60 g, 0.104 mole), potassium carbonate (1.5 g) and DMF (25.0 mL) was heated at 95-100° C. for 6.0 hours. A bathochromic shift in color occurred as the two bromine atoms were replaced by the 2-carboxyphenylthio groups. The reaction mixture was drowned into methanol and the solid product was collected by filtration and washed with methanol. The product was dissolved in water (100 mL) and the diacidic anthraquinone which precipitated by addition of acetic acid was collected by filtration, washed with water and dried in air (yield—0.86 g). FDMS indicated the product to be that used as starting material for Example 16. [0151]
    • EXAMPLE 17
  • The anthraquinone disulfonyl chloride compound (3.50 g, 0.005 mole) having the following structure [0152]
    Figure US20040195552A1-20041007-C00045
  • (prepared according to the procedure of U.S. Pat. No. 5,453,482, Example 2), m-aminobenzoic acid (1.37 g, 0.10 mole), potassium carbonate (2.80 g) and DMF (30 mL) were mixed and the reaction mixture heated at 90-95° C. for 30 minutes. TLC (50:50 THF:cyclohexane) indicated complete reaction of the disulfonyl chloride to produce the disulfonamide derivative. To the reaction mixture were added 1,6-hexanediol, dimethanesulfonate (1.38 g, 0.005 m), potassium carbonate (1.38 g) and heating and stirring were continued for 2.0 hours at 90-95° C. The reaction mixture was drowned into water and acidified with acetic acid. The bright blue polydye was collected by filtration, washed with water and then air dried (yield—2.07 g) and is believed to have the following repeat unit: [0153]
    Figure US20040195552A1-20041007-C00046
  • GPC analysis indicated a weight average molecular weight of 5,252, a number average molecular weight of 2,179 and a polydispersity of 2.41. Absorption maxima at 583 nm and 628 nm were observed in the visible light absorption spectrum in DMF. [0154]
    • EXAMPLE 18
  • A mixture of the diacidic anthraquinone compound (4.21 g, 0.01 mole) having the following structure [0155]
    Figure US20040195552A1-20041007-C00047
  • 1,2-ethanediol, dimethanesulfonate (2.18 g, 0.01 mole), potassium carbonate (2.68 g, 0.02 mole) and DMF (50 mL) was heated and stirred at 90-95° C. for 1.5 hours. The reaction mixture was drowned into water (400 mL) and acidified with stirring and by adding acetic acid. After being heated to about 50° C., the mixture was filtered and the red polydye washed well with water and dried in air (yield—4.47 g). GPC analysis showed the polydye to have a weight average molecular weight of 1,603, a number average molecular weight of 922 and a polydispersity of 1.74. An absorption maximum at 524 nm was observed in the visible light absorption spectrum in DMF. [0156]
    • EXAMPLE 18a
  • A mixture of 1-amino-2,4-dibromoanthraquinone (11.43 g, 0.03 mole), 3-mercapto-1(H)-1,2,4-triazole (9.09 g, 0.09. mole), potassium carbonate (11.52 g, 0.09 mole) and DMF (150 mL) was heated at about 95° C. with stirring for 1.0 hour. The reaction mixture was drowned into water (500 mL) with stirring and acidified with acetic acid and the red product collected by filtration, washed with water and dried in air (yield—12.64 g). FDMS indicated the product to be the diacidic anthraquinone compound used in Example 18. [0157]
    • EXAMPLE 19
  • A mixture of 1,5-bis-(4-hydroxyphenylthio)anthraquinone (4.56 g, 0.01 mole), 1,2-ethanediol, dimethanesulfonate (2.18 g, 0.01 mole), potassium carbonate (3.0 g) and DMF (50 mL) was heated and stirred at about 95° C. for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the yellow polydye was collected by filtration and washed with methanol. The methanol-wet cake was reslurried in water (500 mL) and acidified and the polydye then collected by filtration, washed with water and dried in air (yield—4.25 g). GPC analysis indicated the polydye to have a weight average molecular weight of 1,901, a number average molecular weight of 1,588 and a polydispersity of 1.20. An absorption maximum at 461 nm was observed in the visible light absorption spectrum in DMF. [0158]
    • EXAMPLE 19a
  • A mixture of 1,5-dichloroanthraquinone (5.54 g, 0.02 mole), 4-hydroxybenzenethiol (6.30 g, 0.05 mole), potassium carbonate. (6.90 g, 0.05 mole) and DMF (100 mL) was heated at about 95° C. for 5.0 hours. The reaction mixture was drowned into water (400 mL) and the yellow product was collected by filtration, washed with water and dried in air (yield—9.0 g). The solid was added to acetic acid (150 mL) and the mixture heated to boiling. After being allowed to cool, the yellow solid was collected by filtration, washed with acetic acid and dried in air (yield—6.75 g). FDMS confirmed that the product was the 1,5-bis(4-hydroxyphenylthio)anthraquinone used in Example 19. [0159]
    • EXAMPLE 20
  • A mixture of 1,4-bis-(2-carboxyphenylthio)anthraquinone (1.53 g, 0.003 m), 1,2-ethanediol, dimethanesulfonate (0.66 g, 0.003 mole), potassium carbonate (0.75 g) and DMF (8.0 mL) was heated at about 95° C. with occasional stirring for 2.0 hours. The reaction mixture was then drowned into methanol (100 mL) and the dark orange polydye was collected by filtration, washed with water containing some acetic acid then with hot water and dried in air (yield—0.50 g). GPC analysis indicated a weight average molecular weight of 8,686, a number average molecular weight of 1,356 and a polydispersity of 6.41. [0160]
    • EXAMPLE 20a
  • A mixture of 1,4-dichloroanthraquinone (2.77 g, 0.01 mole), thiosalicylic acid (3.85 g, 0.025 m), potassium carbonate (3.45 g, 0.025 m), cupric chloride dihydrate (0.1 g) and DMF (50 mL) was heated at 95-100° C. with stirring for 4.0 hours. The reaction mixture was drowned into acetone and the solid was collected by filtration and washed with acetone. The resulting potassium salt of the product was dissolved by stirring in water (200 mL). The red solution was neutralized to give the orange product which was collect by filtration, washed with water and dried in air (yield—4.58 g). FDMS indicated the structure to be that of the starting material for Example 20. An absorption maximum at 501 nm was observed in the visible light absorption spectrum. [0161]
    • EXAMPLE 21
  • A mixture of 1,8-bis- (2-carboxyphenylthio)-4,5-bis-(p-tolylthio)anthraquinone (1.51 g, 0.002 mole), 1,4-butanediol, dimethanesulfonate (0.49 g, 0.002 mole), potassium carbonate (0.60 g and DMF (8.0 mL) was heated at 90-95° C. with occasional stirring for 2.5 hours. The reaction mixture was drowned into methanol (106 mL) and the red polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—1.1 g). GPC analysis indicated a weight average molecular weight of 2,157, a number average molecular weight of 1,111 and a polydispersity of 1.94. An absorption maximum was observed at 529 nm in the visible light absorption spectrum in DMF. [0162]
    • EXAMPLE 21a
  • A mixture of thiosalicyclic acid (4.75 g, 0.03 mole), potassium carbonate (8.70 g, 0.06 mole) and DMF (75 mL), was heated at about 100° C. for 1.0 hour and the reaction mixture, which was allowed to cool, was added at 0-5° C. to a solution of 1,8-dichloro-4,5-dinitroanthraquinone (5.51 g. 0.015 mole) dissolved in DMF (150 mL) with good, stirring. Cooling was removed and the temperature of the reaction mixture allowed to come to ambient temperature and the mixture was stirred for about 3.0 hours. A solution of p-thiocresol (3.73 g, 0.03 mole) dissolved in DMF (80 mL) was added to the reaction mixture with stirring and the temperature raised to about 100° C. and held for 2.0 hours. After allowing to cool, the reacting mixture was drowned into water (300 mL) and the mixture gradually acidified by the addition of 10% aqueous hydrochloric acid. The red solid product was collected by filtration, washed with water and dried in air (yield—11.28 g). FDMS analysis indicated that the product consisted mostly of the starting material for Example 21. [0163]
    • EXAMPLE 22
  • A mixture of 1,5-bis(2-carboxyphenylthio)anthraquinone (1.54 g, 0.003 mole), 1,5-bis(2-carboxyhenylthio)-4,8-bis(isobutylamino)anthraquinone (1.31 g, 0.002 mole) (product of Example 2a), 1,2-ethandiol, dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.0 g) and DMF (10 mL) was heated at 90-95° C. with occasional stirring for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the green polydye was washed with methanol, water containing acetic acid, hot water and then dried in air (yield—1.30 g). GPC analysis indicated a weight average molecular weight of 1,839, a number average molecular weight of 1,040 and a polydispersity of 1.77. Absorption maxima were observed in the visible light absorption spectrum in DMF at 448, 603, and 645 nm. [0164]
    • EXAMPLE 23
  • A mixture of 1,5-bis(2-carboxyphenylthio)anthraquinone (1.28 g, 0.0025 mole), 1,4- cyclohexanedimethanol, dimethanesulfonate (1.75 g, 0.0025 mole), potassium carbonate (0.82 g) and DMF (7.5 mL) was heated at about 95° C. with occasional stirring for 3.0 hours. The reaction mixture was drowned into methanol (100 mL) and the yellow polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—0.31 g). GPC analysis indicated a weight average molecular weight of 1,158, a number average molecular weight of 1,008 and a polydispersity of 1.15. [0165]
    • EXAMPLE 24
  • Example 23 was repeated except that the disulfonate used was 1,3-propanediol, 2,2-dimethyl, dimethanesulfonate (0.65 g, 0.0025 mole) to give the yellow polydye (yield—0.76 g) which had a weight average molecular weight-of 1,056, a number average molecular weight of 979 and a polydispersity of 1.08 by GPC analysis. [0166]
    • EXAMPLE 25
  • Example 23 was repeated except that 1,6-hexanediol, dimethanesulfonate (0.68 g, 0.0025 mole) was used as the disulfonate to give the yellow polydye (yield—1.16 g) which had a weight average molecular weight of 1,827, a number average molecular weight of 961 and a polydispersity of 1.90 by GPC analysis. [0167]
    • EXAMPLE 26
  • Example 23 was repeated except that 1,2-ethanediol, bis(4-methylbenzenesulfonate (0.82 g, 0.0025 mole) was used as the disulfonate to yield the yellow polydye (yield—0.41 g) which had a weight average molecular weight of 2,442, a number average molecular weight of 1,885 and a polydispersity of 1.29 by GPC analysis. [0168]
    • EXAMPLE 27
  • A mixture of the acidic anthraquinone compound (2.02 g, 0.0027 mole) having the structure [0169]
    Figure US20040195552A1-20041007-C00048
  • the acidic UV light absorbing compound (0.29 g, 9×10[0170] −4 mole) having the structure
    Figure US20040195552A1-20041007-C00049
  • 1,2-ethanediol, dimethanesulfonate (0.78 g, 0.0036 mole), potassium carbonate (1.0 g) and DMF (25 mL) was heated and stirred at 90-95° C. for 2.0 hours. The cooled reaction mixture was drowned into water (200 mL) and made slightly acidic by the addition of acetic acid with stirring. The polymeric product was collected by filtration, washed well with water and dried in air (yield—2.00 g). GPC analysis indicated a weight average molecular average of 5,642, a number average molecular weight of 1,720 and a polydispersity of 3.28. [0171]
    • EXAMPLE 28
  • A mixture of the diacidic anthraquinone compound (1.27 g, 0.002 mole) having the structure [0172]
    Figure US20040195552A1-20041007-C00050
  • 1,2-ethanediol, dimethanesulfonate (0.44 g, 0.002 mole), potassium carbonate (0.75 g) and DMF (8.0 mL) was heated at 90-95° C. with occasional stirring for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the dark red polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—1.23 g). GPC analysis indicated a weight average-molecular weight of 1,545, a number average molecular weight of 1,213 and a polydispersity of 1.27. [0173]
    • EXAMPLE 28a
  • To a mixture of 1,5-bis(2-carboxyanilino)anthraquinone (9.57 g, 0.02 mole) in DMF (250 mL) was added portionwise N-bromosuccinimide (7.12 g, 0.04 mole) with stirring at room temperature. The reaction mixture was then heated at about 60° C. for 1.5 hours and allowed to cool. Water was added dropwise to precipitate the product, which was collected by filtration, washed with water and dried in air (yield—11.17 g). FDMS indicated the structure of the product to be that of the starting anthraquinone compound in Example 28. [0174]
    • EXAMPLE 29
  • A mixture of the diacidic anthraquinone compound (4.06 g, 0.01 mole) having the structure [0175]
    Figure US20040195552A1-20041007-C00051
  • 1,2-ethanediol, dimethanesulfonate (2.18 g, 0.01 mole), potassium carbonate (2.76 g) and DMF (150 mL) was heated at about 100° C. for 3.0 hours. The reaction mixture was drowned into water, acidified with acetic acid and the yellow polydye was collected by filtration, washed with water and dried in air. GPC analysis indicated a weight average molecular weight of 5,333, a number average molecular weight of 2,441, and a polydispersity of 2.18. [0176]
    • EXAMPLE 29a
  • A mixture of 1,5-dichloroanthraquinone (6.93 g, 0.025 mole), 3-mercapto-1(H)-1,2,4-triazole (5.56 g, 0.055 mole), potassium carbonate (6.91 g, 0.05 mole) and DMF (100 mL) was heated and stirred at about 95° C. for 5.0 hours. The mixture was drowned into water and the yellow product was collected by filtration, washed with water and air dried. The cake was reslurried in hot isopropanol and the product collected by filtration, washed with isopropanol and dried in air (yield 8.62 g). FDMS indicated the product to be 1,5-bis[1(H)-1,2,4-triazol-3-ylthio]anthraquinone used as the diacidic anthraquinone starting material in Example 29. [0177]
    • EXAMPLE 30
  • A mixture of diacidic anthraquinone compound (1.01 g, 0.0025 mole) having the structure [0178]
    Figure US20040195552A1-20041007-C00052
  • 1,2-ethanediol, dimethanesulfonate (0.55 g, 0.0025 mole), potassium carbonate (0.75 g) and DMF (10 mL) was heated at about 95° C. for 3.0 hours. The reaction mixture was then drowned into methanol (100 mL) and the yellow polydye was collected by filtration, water containing acetic acid, hot water and then air dried (yield—0.35 g). GPC analysis indicated a weight average molecular weight of 2,478, a number average molecular weight of 742 and a polydispersity of 3.34. An absorption maximum was observed in the visible light absorption spectrum at 425 nm in DMF. [0179]
    • EXAMPLE 30a
  • A mixture of 1,8-dichloroanthraquinone (6.93 g, 0.025 mole), 2-mercaptoimidazole (5.01 g, 0.05 mole), potassium carbonate (6.91 g) and DMF (60 mL) was heated and stirred at about 95° C. for 8.0 hours. The reaction mixture was drowned into water and acidified using acetic acid. The yellow product was collected by filtration, washed with water and dried in air. FDMS indicated the product to be the 1,8-bis(imidazol-2ylthio) anthraquinone diacidic compound used as the starting material in Example 30. [0180]
    • EXAMPLE 31
  • A mixture of 1,5-bis[1(H)-1,2,4-triazol-3ylthio] anthraquinone (1.80 g, 0.00443 mole) (product of Example 29a); 1,4-dibromobutane (0.96 g, 0.00444 mole), tributylamine (1.64 g, 0.00885 mole), and N-methyl-2-pyrrolidinone (30 mL) was heated at 8.0 hours at about 130° C. with stirring. The reaction mixture was drowned into acetone (150 mL) and the yellow polydye was collected by filtration, washed with acetone until filtrate was essentially clear and dried in air. GPC analysis indicated a weight average molecular weight of 5,022, a number average molecular weight of 3,220 and a polydispersity of 1.56. [0181]
    • EXAMPLE 32
  • A mixture of the diacidic anthraquinone compound (1.63 g, 0.003 mole) having the structure [0182]
    Figure US20040195552A1-20041007-C00053
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated at about 95° C. with occasional stirring for 2.0 hours. The mixture was drowned into methanol (100 mL) and the dark blue polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.92 g). Absorption maxima at 602 and 644 nm were observed in the visible light absorption spectrum in DMF. GPC analysis indicated a number average molecular weight of 1,860. [0183]
    • EXAMPLE 32a
  • A mixture of 1,4-diamino-2,3-dichloroanthraquinone (12.24 g, 0.04 mole), thiosalicylic acid (15.4 g, 0.10 mole), potassium carbonate (13.8 g, 0.10 mole) and DMF (150 mL) was heated at about 95° C. with stirring for 2.0 hours. A bathochromic shift in color from violet to blue was observed as the reaction progressed. The reaction mixture was drowned into acetone (500 mL) and the solid product was collected by filtration and washed well with acetone. The acetone-wet cake was added to water (600 mL) and the mixture acidified with acetic acid to precipitate the free acid compound, which was collected by filtration, washed with water and dried in air (yield—21.4 g). FDMS indicated the product to be the 1,4-diamino-2,3-bis(2-carboxyphenylthio) anthraquinone used in Example 32. [0184]
    • EXAMPLE 33
  • A mixture of 1,5-bis(2-carboxyphenylthio) anthraquinone (1.02 g, 0.002 mole), terephthalic acid (1.00 g, 0.006 mole), potassium carbonate (1.38 g) 1,2-ethanediol, dimethanesulfonate (1.74 g, 0.008 mole) and DMF (10 mL) was heated at about 95° C. with occasional stirring for 2.0 hours. The mixture was then drowned into methanol (100 mL) and the yellow polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.88 g). GPC analysis indicated a weight average molecular weight of 794, a number average molecular weight of 713 and a polydispersity of 1.11. [0185]
    • EXAMPLE 34
  • Example 33 was repeated using 1,5-bis(2-carboxyphenylthio) anthraquinone (1.02 g, 0.002 mole) and terephthalic acid (0.33 g, 0.002 mole), 1,2-ethanediol, dimethanesulfonate (0.87 g, 0.004 mole) and potassium carbonate (0.87 g) to yield the yellow polydye (0.90 g). GPC analysis indicated a weight average molecular weight of 875, a number average molecular weight of 811, and a polydispersity of 1.08. [0186]
    • EXAMPLE 35
  • A mixture of the diacidic anthraquinone compound (2.00 g, 0.00285 mole) having the following structure (Preparation 5 of IR Docket 70351): [0187]
    Figure US20040195552A1-20041007-C00054
  • 1,2-ethanediol, dimethanesulfonate (0.63 g, 0.00289 mole), potassium carbonate (0.80 g) and DMF (25 mL) was heated at 95° C. for 4.0 hours with stirring. The reaction mixture was drowned into methanol (100 mL) and the greenish-blue polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.01 g). GPC indicated a weight average molecular weight of 6,720, a number average molecular weight of 2,211 and a polydispersity of 3.04. Absorption maxima were observed at 599 and 647 nm in the visible absorption spectrum in DMF. [0188]
    • EXAMPLE 36
  • A mixture of the diacidic anthraquinone compound (0.41 g, 0.508 mmole) having the following structure (Preparation 4 in IR Docket 70351): [0189]
    Figure US20040195552A1-20041007-C00055
  • 1,2-ethanediol, dimethanesulfonate (0.11 g, 0.504 mmole), potassium carbonate (0.14 g) and DMF (5.0 mL) was heated with occasional stirring or about 95° C. for 3.0 hours. The reaction mixture was drowned into methanol (50 mL) and the greenish-blue polydye was collected by filtration; washed with methanol, water containing acetic acid, hot water and dried in air (yield 0.15 g). Absorption maxima were observed at 599 and 645 nm in the visible light absorption spectrum in DMF. [0190]
    • EXAMPLE 37-66
  • Colored EASTAR® copolyester 6763 film was produced by melt blending the polydyes of Examples 7-36 and extruding according to the following procedure to produce Examples 37-66 (Table 1). [0191]
  • EASTAR® PETG polyester 6763, a poly(ethylene-1,4-cyclohexanedimethylene) terephthalate (Eastman Chemical Company) (300 g of previously dried pellets) was dry blended with the anthraquinone polydye composition (0.12 g). The blend was extruded with a C. W. Brabender ¾ in extruder, equipped with a mixing screw, at 250° C. into a water bath and the extrudate pelletized. [0192]
  • The pellets were redried at 70° C. for 17 hrs. at a pressure of about 1-5 torr. A portion (1.40 g) of the dried pellets was pressed into a 18-20 mil film at 250° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4 inch ram). The transparent films contained about 300 ppm of the polydyes and each showed excellent color development to produce the colors indicated in Table 1. [0193]
    • EXAMPLE 67
  • A mixture of 1,4-bis(2-carboxyphenythio) anthraquinone (15.4 g, 0.03 mole) (prepared as in Example 20a), 1,5-bis(2-carboxyphenylthio)-4,8-bis(isobutylamino)anthraquinone (6.55 g, 0.01 mole) (Example 2a), 1,2-ethanediol, dimethanesulfonate (8.72 g, 0.04 mole), potassium carbonate (8.0 g) and DMF (100 mL) was stirred and heated at about 95° C. for 2.0 hours with occasional stirring. The reaction mixture was drowned into methanol (500 mL) and the black polydye was collected by filtration, washed with water containing acetic acid, hot water and dried in air (yield—9.5 g). GPC analysis indicated a weight average molecular weight of 7,512, a number average molecular weight of 1,700 and a polydispersity of 4.42. [0194]
    • EXAMPLE 68
  • EASTAR® PETG copolyester 6763 (291 g of previously dried pellets) was dry blended with the black polydye of Example 67 (9.0 g) and the blend extruded and a portion of the resulting pellets was pressed into a black film containing approximately 3.0% by weight of polydye by using the procedure described in Example 4. [0195]
    • EXAMPLE 69
  • A mixture of the diacidic azo compound (3.20 g, 0.005 mole) having the structure [0196]
    Figure US20040195552A1-20041007-C00056
  • 1,2-ethanediol, dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.5 g) and DMF (25 mL) was heated and stirred at about 95° C. for 3.0 hours. The reaction mixture was drowned into methanol and the violet polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.60 g). GPC analysis indicated a weight average molecular weight (Mw) of 6,403, a number average molecular weight (Mn) of 3,700 and a polydispersity (Mw/Mn) of 1.73. In the visible light absorption spectrum in DMF an absorption maximum was observed at 556 nm. [0197]
    • EXAMPLE 69a
  • A mixture of the dibromoazobenzene dye (6.01 g, 0.010 mole) having the structure [0198]
    Figure US20040195552A1-20041007-C00057
  • 3-mercapto-1(H)1,2,4-triazole (2.2 g, 0.022 mole), potassium carbonate (3.45 g, 0.025 mole) and DMF (100 mL) was stirred and heated at about 95° C. for 2.0 hours. TLC (75 parts THF: 25 parts cyclohexane) showed incomplete reaction. An additional quantity (1.01 g, 0.01 m) 3-mercapto-1(H)-1,2,4-triazole was added and heating and stirring were continued for 2.0 additional hours. TLC indicated essentially complete reaction to produce the violet product. The reaction mixture was drowned into water (400 mL) and the mixture was acidified by addition of acetic acid, heated to about 40° C. and filtered. The product was washed with warm water and dried in air (yield—5.60 g). FDMS indicated the product to have the structure of the diacidic azobenzene compound used in Example 69. [0199]
    • EXAMPLE 70
  • A mixture of the diacidic azo compound (1.59 g, 0.0025 mole) having the structure [0200]
    Figure US20040195552A1-20041007-C00058
  • 1,2-ethanediol, dimethanesulfonate (0.55 g, 0.0025 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated at 95° C. with occasional stirring for 3.0 hours. The reaction mixture was drowned into methanol (100 mL) and the blue polydye product was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.06 g). GPC analysis indicated a Mw of 5,497, a Mn of 2,648 and a Mw/Mn of 2.08. An absorption maximum was observed at 605 nm in DMF in the visible light absorption spectrum. [0201]
    • EXAMPLE 70a
  • A mixture of the dibromo azobenzene dye (2.38 g, 0.004 mole) having the structure [0202]
    Figure US20040195552A1-20041007-C00059
  • 3-mercapto-1(H)-1,2,4-triazole (1.21 g, 0.012 mole), potassium carbonate (1.65 g, 0.012 mole) and DMF (25 mL) was heated and stirred for 1.0 hour. TLC (50 parts THF:50 parts cyclohexane) showed complete reaction to produce the product. The reaction mixture was drowned into water (100 mL) and the mixture acidified with acetic acid. The dark blue product was collected by filtration, washed with water and dried in air (yield—2.55g). FDMS indicated the product to have the structure of the diacidic azobenzene compound used in Example 70. [0203]
    • EXAMPLE 71
  • A mixture of the diacidic disazo compound (1.59 g, 0.005 mole) having the structure [0204]
    Figure US20040195552A1-20041007-C00060
  • 1,2-ethanediol, dimethanesulfonate (1.09 g. 0.005 mole), potassium carbonate (1.5 g), DMF (10 mL) was heated and stirred at about 95° C. for 3.0 hours. The reaction mixture was drowned into methanol (100 mL) and the dark brown polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—0.66 g). GPC analysis indicated a Mw of 4,926, a Mw of 1,574 and a Mw/Mn of 3.13. [0205]
    • EXAMPLE 72
  • A mixture of the diacidic azo compound (1.88 g, 0.005 mole) having the structure [0206]
    Figure US20040195552A1-20041007-C00061
  • 1,2-ethanediol, dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.5 g) and DMF (20 mL) was heated at about 95° C. with stirring for 3.0 hours. The reaction mixture was drowned in methanol (100 mL) and the red polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.35 g). GPC analysis indicated a Mw of 6,888, a Mn of 2,127 and a Mw/Mn of 3.24. An absorption maximum was observed at 527 nm in the visible light absorption spectrum in DMF. [0207]
    • EXAMPLE 72a
  • To a stirred mixture of the azo compound (4.05 g, 0.01 mole) [4-(3′,5′-dicarbomethoxy-4′-methylthiophene-2-ylazo)-N-ethyl-N(2-hydroxyethyl)aniline) and 2-ethoxyethanol (50 mL) at room temperature was added aqueous 50% NaOH solution(3.75 g). After being heated at about 95° C. for 1.0 hour, the reaction product was drowned into acetone (300 mL). The disodium salt of the diacidic azo dye was collected by filtration washed with acetone and then quickly dissolved in water (200 mL). Acidification with acetic acid precipitated the free diacid dye, which was collected by filtration, washed with water and dried in air (yield—2.35 g). FDMS indicated the product to have the structure of the diacidic azo compound used in Example 72. [0208]
    • EXAMPLE 73
  • A mixture of the diacidic azobenzene compound (1.19 g, 0.003 mole) having the structure [0209]
    Figure US20040195552A1-20041007-C00062
  • 1,2-ethanediol, dimethanesulfonate (0.66 g., 0.003 mole), potassium carbonate (0.75 g), and DMF (8.0 mL) was stirred occasionally and heated at about 95° C. for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the orange polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.65 g). GPC analysis showed a Mw of 3,015, a Mn of 2,128 and a Mw/Mn of 1.42. An absorption maximum was observed in the visible light absorption at 479 nm in DMF. [0210]
    • EXAMPLE 73a
  • To a mixture of 3-acetamido-4-(3′,5′-dicarbomethoxyphenylazo)-N,N-diethylaniline (1.7 g, 0.004 mole) in 2-ethoxyethanol (20 mL) was added aqueous 50% NaOH (1.6 g). The reaction mixture was heated with stirring of 95° C. for 10 minutes and then drowned into water (100 mL). The solution was acidified with acetic acid to precipitate the diacid dye which was collected by I filtration, washed with water and dried in air (yield—1.6 g). FDMS indicated the structure to be that of the starting diacid azobenzene compound in Example 73. [0211]
    • EXAMPLE 74
  • A mixture of the diacidic azobenzene compound (1.10 g, 0.003 mole) having the structure [0212]
    Figure US20040195552A1-20041007-C00063
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.45 g) and DMF (8.0 mL) was heated at 95° C. with-occasional stirring for 2.0 hours. The reaction mixture was drowned into methanol (100 mL). A slightly sticky yellow product resulted. The methanol was removed by decantation and the product dissolved in DMF (10 mL) by heating and stirring. Water (100 mL) was added and the mixture acidified by addition of acetic acid. The solid yellow polydye was collected by filtration, washed with water and dried in air (yield—0.47 g). GPC analysis indicated a Mw of 9,314, a Mn of 3,208 and a Mw/Mn of 2.90. An absorption maximum at 428 nm was observed in the visible light absorption spectrum in DMF. [0213]
    • EXAMPLE 74a
  • To a mixture of 4-(2′,5′-dicarbomethoxyphenylazo)-N-(2-cyanoethyl)-N-ethylaniline (1.97 g, 0.005 mole) in 2-ethoxyethanol (20 mL) was added aqueous 50% NaOH (1.90 g). The reaction solution was heated at 95° C. for 15 minutes and then drowned into water (200 mL). The solution was acidified and the yellow dye which precipitated was collected by filtration, washed with water and dried in air (yield—1.75 g). FDMS indicated the structure to be that of the starting diacid azobenzene dye of Example 74. [0214]
    • EXAMPLE 75
  • A mixture of diacidic azo compound (38.6 g, 0.10 mole) having the structure [0215]
    Figure US20040195552A1-20041007-C00064
  • 1,6-hexanediol, dimethanesulfonate (27.4 g, 0.10 mole), potassium carbonate (27.6 g, 0.20 mole), and DMF (350 mL) was heated at 95-100° C. for 2.0 hours. The reaction mixture was drowned into a solution of acetic acid (70.0 mL) in water (1700 mL) with good stirring. After stirring for about 15 minutes, the yellow polydye was collected by filtration, washed with hot water and dried in air (yield—42.6 g). An absorption maximum at 422 nm was observed in the visible light absorption spectrum in DMF. [0216]
    • EXAMPLE 75a
  • To a mixture of the diester dye (41.4 g, 0.10 mole) [3-cyano-5-(3′,5′-dicarbomethoxyphenylazo)-6-hydroxy-N-(2-hydroxyethyl)-4-methyl-2-pyridone] in 2-ethoxyethanol (400 mL) was added aqueous 50% NaOH (40.0 g) and the reaction mixture was heated at 75-80° C. for about 30 minutes. Acetone (200 mL) was added to the slightly cooled reaction mixture. The yellow solid was collected by filtration, washed with acetone and then reslurried in warm water (750 mL). After acidification using conc. HCl (20 mL), the yellow diacid dye was collected by filtration, washed with hot water and dried in air (yield—36.0 g). FDMS indicated the structure to be that of the starting diacid azo compound of Example 75. [0217]
    • EXAMPLE 76
  • A mixture of the diacidic azo compound (2.03 g, 0.005 mole) having the structure [0218]
    Figure US20040195552A1-20041007-C00065
  • 1,2-ethanedioli dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.5 g) and DMF (20 mL) was heated at about 95° C. with occasional stirring for 5.0 hours. The reaction mixture was drowned into methanol. Acetic acid (1.0 mL) was added and the polydye was collected by filtration and washed with water and dried in air. GPC analysis indicated a Mw of 9,876, a Mn of 3,917 and a polydispersity of 2.52. An absorption maximum at 506. nm was observed in the visible light absorption spectrum in DMF. [0219]
    • EXAMPLE 77
  • A mixture of the diacidic azo compound (0.60 g, 0.00155 mole) having the structure [0220]
    Figure US20040195552A1-20041007-C00066
  • 1,2-ethanediol, dimethanesulfonate (0.34 g, 0.00155 mole), potassium carbonate (0.3 g) and DMF (4.0 mL) was heated at about 95° C. for 4.0 hours. The reaction mixture was drowned into methanol (20 mL) and the yellow polydye was collected by filtration, washed with methanol, water containing acetic acid, water and then air dried (yield—0.5 g). GPC analysis showed a Mw of 4,566, a Mn of 2,474 and a Mw/Mn of 1.84. In the visible light absorption spectrum in DMF an absorption maximum was observed at 420 nm. [0221]
    • EXAMPLE 77a
  • To a mixture of 3-(3′,5′-dicarboxymethoxyphenylazo)-2-phenylindole (1.0 g, 0.00242 mole) in 2-ethoxyethanol (10 mL) was added aqueous 50% NaOH (0.75 g) and the hydrolysis reaction carried out by heating at about 95° C. for 30 minutes. The reaction mixture was drowned into water (100 mL) and the solution treated with acetic acid to precipitate the product which was collected by filtration, washed with water and dried in air (yield—0.85 g). FDMS indicated the structure to be that of the starting diacidic azo compound in Example 77. [0222]
    • EXAMPLE 78
  • A mixture of the diacidic azo compound (0.99 g, 0.002 mole) having the structure [0223]
    Figure US20040195552A1-20041007-C00067
  • 1,2-ethanediol, dimethanesulfonate (0.42 g, 0.002 mole), potassium carbonate (0.5 g) and DMF (7.0 mL) was heated at about 95° C. for 3.0 hours. The reaction mixture was drowned into methanol (50 mL) and the scarlet polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—0.18 g). GPC analysis indicated a Mw of 8,246, a Mn of 2,619 and a polydispersity of 3.15. [0224]
    • EXAMPLE 79
  • A mixture of the diacidic azo dye (2.50 g, 0.00733 mole) having the following structure [0225]
    Figure US20040195552A1-20041007-C00068
  • 1,2-ethanediol, dimethanesulfonate (1.60 g, 0.00733 mole), potassium carbonate (2.07 g) and DMF (25 mL) was heated at 95° C. for 3.0 hours. The reaction mixture was drowned into methanol and a small amount of acetic acid added. The yellow polydye was collected by filtration, washed with a little methanol, water containing acetic acid, hot water and dried in air. GPC analysis indicated a Mw of 1,949, a Mn of 1,569 and a Mw/Mn of 1.24. An absorption maximum was observed at 411 nm the visible light absorption spectrum. [0226]
    • EXAMPLE 80
  • A mixture of the diacidic azo compound (1.22 g, 0.0025 mole) having the structure [0227]
    Figure US20040195552A1-20041007-C00069
  • 1,2-ethanediol, dimethanesulfonate (0.55 g, 0.0025 mole), potassium carbonate (0.75 g) and DMF (8.0 mL) was heated and stirred at about 95° C. for 3 hours with occasional stirring. The reaction mixture was drowned into methanol (50 mL) and the polydye was collected by filtration washed with methanol, water containing acetic acid, hot water and then dried in air (yield—0.68 g). GPC analysis indicated a Mw of 2,259, a Mn of 1,571 and a Mw/Mn of 1.44. An absorption maximum was observed at 503 nm in DMF in the visible light absorption spectrum. [0228]
    • EXAMPLE 81
  • A mixture of the diacidic azo compound (1.25 g, 0.003 mole) having the structure [0229]
    Figure US20040195552A1-20041007-C00070
  • 1,2-ethanediol, dimethanesulfonate (0.65 g, 0.003 mole), potassium carbonate (1.0 g) and DMF (10 mL) was heated at about 95° C. for 3.0 hours with occasional stirring. The reaction mixture was drowned into methanol (25 mL) and the orange polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.75 g). GPC analysis indicated a Mw of 2,014, a Mn of 1,520 and a Mw/Mn of 1.32. An absorption maximum was observed at 493 nm in the visible light absorption spectrum in DMF. [0230]
    • EXAMPLE 82
  • A mixture of the diacidic azo compound (1.11 g, 0.0025 mole) having the structure [0231]
    Figure US20040195552A1-20041007-C00071
  • 1,2-ethanediol, dimethanesulfonate (0.55 g, 0.0025 mole), potassium carbonate (0.80 g and DMF (8.0 mL) was heated at about 95° C. for 2.5 hours. The reaction mixture was drowned into methanol (100 mL) and the brown polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.30 g). GPC analysis indicated a Mw of 2,301, a Mn of 1,345 a Mw/Mn of 1.71. In the visible light absorption spectrum in DMF a maximum absorption was observed at 434 nm. [0232]
    • EXAMPLE 83
  • A mixture of the diacidic azo compound (2.40 g, 0.005 mole) having the structure [0233]
    Figure US20040195552A1-20041007-C00072
  • 1,2-ethanediol, dimethanesulfonate (1.09 g, 0.005 mole), potassium carbonate (1.5 g) and DMF (25 mL) was heated at about 95° C. for 3.0 hours with occasional stirring. The reaction mixture was drowned into methanol (200 mL) and the dark red polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—1.80 g). GPC analysis indicated Mw of 2,914, a Mn of 809 and a Mw/Mn of 3.60. An absorption maximum at 528 nm was observed in the visible light absorption spectrum in DMF. [0234]
    • EXAMPLE 84
  • A mixture of the diacidic azo compound (1.07 g, 0.002. mole) having the structure [0235]
    Figure US20040195552A1-20041007-C00073
  • 1,2-ethanediol, dimethanesulfonate (0.44 g, 0.002 mole), potassium carbonate (0.5 g) and DMF (10 mL) was heated at 95° C. with occasional stirring for 5 hours. The reaction mixture was drowned into methanol (50 mL) and the reddish-blue polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.83 g). GPC analysis indicated a Mw of 7,038, a Mn of 832 and a Mw/Mn at 8.44. An absorption maximum was observed at 574 nm in the visible light absorption spectrum in DMF. [0236]
    • EXAMPLE 85 Displacement of Bromine in Polydye of Example 84 with Cyano Group
  • A mixture of a portion (0.5 g) of the polydye of Example 84, sodium dicyanocuprate (0.2 g) and DMF (8.0 mL) was heated at about 95° C. with occasional stirring for 3.0 hours. The reaction mixture, the color of which changed from reddish-blue to neutral-blue as the displacement reaction occurred, was then drowned into methanol and the polydye was collected by filtration, washed with methanol and dried in air. GPC analysis indicated a Mw of 9,427, a Mw of 1,117 and a Mw/Mn of 8.44. An absorption maximum at 590 nm was observed in DMF in the visible light absorption spectrum. [0237]
    • EXAMPLE 86
  • A mixture of diacidic azo compound (1.53 g, 0.0025 mole) having the structure [0238]
    Figure US20040195552A1-20041007-C00074
  • 1,6-hexanediol, dimethanesulfonate (0.69 g, 0.0025 mole), K[0239] 2CO3 (0.8 g) and DMF (8.0 mL) was heated at about 95° C. with occasional stirring for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the brown polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and then dried in air (yield—0.62 g). GPC analysis indicated a Mw of 4,795, a Mn of 2,051 and a Mw/Mn of 2.33. An absorption maximum at 434 nm in DMF was observed in the visible light absorption spectrum.
    • EXAMPLE 86a
  • To conc. H[0240] 2SO4 (33.0 mL) was added 2,6-dichloro-4-nitroaniline (6.21 g, 0.03 mole) with stirring. The solution was cooled to 0-5° C. and stirred while a nitrosyl sulfuric acid mixture, prepared by adding sodium nitrite (2.19 g) to conc. H2SO4 (15 mL) portionwise with stirring and allowing the temperature to rise, was added below SOC with stirring. The diazotization reaction mixture was stirred at 0-5° C. for 2.0 hours. An aliquot of the diazonium salt solution (0.01 mole) was added to a chilled solution of the diacid coupler (3.95 g, 0.01 mole) (N,N-bis(4-carboxyphenylmethyl)-3-chloroaniline) dissolved in 1:5 (1 part propionic acid:5 parts acetic acid) (120 mL) containing some conc. HCl (5.0 mL) with stirring at 0-5° C. The coupling reaction mixture was neutralized by the addition of ammonium acetate with stirring and allowed to stand with occasional stirring at below 5° C. for about 1.0 hour. Water was added to precipitate the solid dye, which was collected by filtration, washed with water and dried in air (yield—4.0 g). The crude dye was reslurried in hot methanol and the mixture allowed to cool. The final dye was collected by filtration, washed with methanol and dried in air. An absorption maximum was observed at 431 nm in DMF. The diacid dye was used as the starting material in Example 86.
    • EXAMPLE 86b
  • A mixture of m-chloroaniline (2.56 g, 0.02 mole), methyl 4-(bromomethyl)benzoate (10.08 g, 0.044 mole), sodium carbonate (4.66 g) and sodium iodide (0.2 g) and 2-ethoxyethanol (50 mL) was heated under nitrogen at about 90° C. for 3.0 hours with stirring. The reaction mixture was drowned into water and the product was extracted into methylene chloride. Methylene chloride was removed to leave an oily product (11.0 g), which was added to 2-ethoxyethanol (100 mL). To the solution was added aqueous 50% NaOH solution (7.50 g) and the reaction mixture was warmed. At about 30° C., white solids began to precipitate and at about 50° C. the reaction mixture become very thick. When the temperature had reached 70° C., water (20 mL) was added to dissolve the salts of the diacidic product. After stirring at 70° C. for 1.5 hours the reaction mixture was clarified by filtering through Celite filter aid and the filtrate acidified by the addition of 10% aqueous HCl to pH of about 4.0. The white solid was collected by filtration, washed with water and dried in air (yield—7.20 g). FDMS indicated the product to have the structure of the coupler used in Example 86a. [0241]
    • EXAMPLE 87
  • A mixture of the diacidic azo compound (1.64 g, 0.003 mole) having the structure [0242]
    Figure US20040195552A1-20041007-C00075
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.5 g) and DMF (8.0 mL) was heated at about 95° C. for 25 hours with occasional stirring. The reaction mixture was drowned into methanol (150 mL) and the polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.5 g). GPC analysis indicated a Mw of 2,741, a Mn of 1,367 and a Mw/Mn of 2.00. An absorption maximum at 441 nm was observed in the visible light absorption spectrum in DMF. [0243]
    • EXAMPLE 87a
  • An aliquot (0.01 mole) of the diazonium salt from 2,6-dichloro-4-nitroaniline prepared in Example 86a was added to a chilled solution of the coupler (3.29 g, 0.01 mole) having the formula [0244]
    Figure US20040195552A1-20041007-C00076
  • dissolved in 1:5 acid (100 mL) with stirring at 0-5° C. Ammonium acetate was added with stirring until the coupling mixture was neutral to Congo Red Test paper. After allowing to stand for 1.0 hour, water was added to the coupling mixture to precipitate the dye, which was collected by filtration, washed with-water and dried in air (yield—4.27 g). An absorption maximum was observed at 460 nm in the visible light absorption spectrum in DMF. [0245]
    • EXAMPLE 87b
  • A mixture of N-(2-chloroethyl)-N-ethylaniline (46.0 g, 0.25 mole), dimethyl 5-hydroxyisophthalate (52.5 g, 0.25 mole), potassium carbonate (69.08), a trace of pulverized potassium iodide and DMF (350 mL) was heated at 125-30° C. for 3.5 hours with stirring. The reaction mixture was allowed to cool and drowned in water/ice mixture (1.0 L). The product separated as a brown oil and the aqueous layer was removed by decantation. To the oily product was added 2-ethoxyethanol (175 mL) and aqueous 50% NaOH (50.0 g) and the hydrolysis reaction mixture was heated at 60-65° C. for about 20 minutes. Acetone was added to the reaction mixture and the white solid was collected by filtration, washed with acetone and dried in air (yield—99.0 g). The disodium salt was dissolved in water (250 mL) by stirring. Acidification with conc. HCl to a pH of about 3.0 gave a slightly sticky product which solidified in a few minutes. The pale yellow granular solid was collected by filtration, washed with water and dried in air (yield—58.0 g). FDMS indicated the structure to be that of the coupler used in Example 87a. [0246]
    • EXAMPLE 88
  • A mixture of the diacid azo compound (0.70 g, 0.0013 mole) having the structure [0247]
    Figure US20040195552A1-20041007-C00077
  • 1,6-hexanediol, dimethanesulfonate (0.36 g, 0.0013 mole), potassium carbonate (0.35 g) and DMF (5.0 mL) was heated at about 95° C. with occasional stirring for 2.0 hours. The reaction mixture was drowned into methanol (50 mL) and the polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.55 g). GPC indicated a Mw of 7,353, a Mn of 2,431 and a Mw/Mn of 3.02. An absorption maximum at 537 nm was observed in the visible light absorption spectrum in DMF. [0248]
    • EXAMPLE 88a
  • To a mixture of the diester dye (1.75 g, 0.0013 mole) having the structure [0249]
    Figure US20040195552A1-20041007-C00078
  • and 2-ethoxyethanol (20 mL) was added aqueous 50% NaOH solution (1.2 g) and the hydrolysis mixture was heated at about 10 minutes at about 95° C. The reaction mixture was drowned into acetone and the solid material collected by filtration. The acetone-wet material was dissolved by stirring in water (200 mL) and the diacid dye precipitated by adding acetic acid. The product was collected by filtration washed with water and dried in air (yield—1.35 g). FDMS showed the product to be mostly [0250]
    Figure US20040195552A1-20041007-C00079
  • indicating hydrolysis of the acetamido group in addition to the ester group. All of the product was added to acetic acid (8.0 mL) and acetic anhydride (1.0 mL). The reaction mixture was heated at 95° C. for 30 minutes with occasional stirring. A bathochromic shift in color from red to magenta was observed as the amine group was acetylated. The reaction mixture was allowed to cool, whereupon a solid dark red product crystallized, and then was drowned into methanol (40 mL). The product was collected by filtration, washed with water and dried in air (yield—0.90 g). FDMS indicated the structure to be that of the diacidic azo dye in Example 88. [0251]
    • EXAMPLE 88b
  • A mixture of the dibromo azo dye (3.00 g, 0.0044 mole) having the structure [0252]
    Figure US20040195552A1-20041007-C00080
  • sodium dicyanocuprate (0.69 g, 0.005 mole) and DMF (30 mL) was heated at 95° C. for 1.0 hour. The reaction mixture was drowned into methanol (150 mL) and the dye was collected by filtration, washed with methanol and dried in air (yield—1.91 g). FDMS indicated the structure to be that of the dicyano dye used in Example 88a. [0253]
    • EXAMPLE 88c
  • To conc. H[0254] 2SO4 (7.5 mL) was added dry NaNO2 (1.08 g) portionwise with stirring and the temperature allowed to rise. The nitrosyl sulfuric acid mixture was cooled and 1:5 acid (15 mL) was added at less than 10° C. with stirring. To this mixture was added at 0-5° C. with stirring dimethyl 5-(4′-amino,2′,6′-dibromophenoxy)isophthalate (6.86 g, 0.015 mole), followed by an additional 15 mL of 1:5 acid. The diazotization reaction mixture was stirred at 0-5° C. for 2.0 hours and then an aliquot (0.0075 mole) was added to a solution of 3-acetamido-N,N-diethylaniline (1.54 g, 0.0075 mole) dissolved in 1:5 acid (75 mL) at 0-5° C. Ammonium acetate was added with stirring to the coupling mixture until neutral to Congo Red test paper. Coupling was allowed to continue at 0-5° C. for 1.0 hour and the dye then precipitated by addition of water, collected by filtration, washed with water and dried in air. FDMS indicated the structure to be that of the starting dibromo azo dye in Example 88b. An absorption maximum at 546 nm was observed in the visible light absorption spectrum in DMF.
    • EXAMPLE 88d
  • A mixture of the dimethyl 5-(4′-aminophenoxy)isophthalate (15.0 g, 0.05 mole). (Example 12c), anhydrous sodium acetate (9.6 g) and acetic acid (85 mL) was treated with stirring with bromine (17.4 g, 0.11 mole) allowing the temperature to rise. The reaction mixture was heated at 70-80° C. for 1.5 hours, allowed to cool, and then drowned into ice water (350 mL). The product was collected by filtration, washed with water and dried in air (yield—21.9 g). FDMS indicated the structure to be that of the amine compound diazotized in Example 88c. [0255]
    • EXAMPLE 89
  • A mixture of the diacidic azo compound (1.39 g, 0.0025 mole) having the structure [0256]
    Figure US20040195552A1-20041007-C00081
  • 1,6-hexanediol, dimethanesulfonate (0.68 g, 0.0025 mole), potassium carbonate (1.0 g) and DMF (8.0 mL) was heated at 95° C. for 2.5 hrs with occasional stirring. The reaction mixture was drowned into methanol (100 mL) and the red polydye was collected by filtration, washed with water containing acetic acid, hot water and dried in air (0.85 g). GPC analysis indicated a Mw of 2,772, a Mn of 1,306 and a Mw/Mn of 2.12. An absorption maximum was observed at 538 nm in the visible light absorption spectrum in DMF. [0257]
    • EXAMPLE 90
  • A mixture of the diacidic azo compound (1.23 g, 0.004 mole) having the formula [0258]
    Figure US20040195552A1-20041007-C00082
  • 1,2-hexanediol, dimethanesulfonate (1.1 g, 0.004 mole), potassium carbonate (0.55 g) and DMF (8.0 mL) was heated at 95° C. for 1 hour. The reaction mixture was drowned into water (250 mL) containing acetic acid (5.0 mL). The yellow polydye was collected by filtration, washed with water and dried in air (yield—1.21 g). GPC analysis indicated a Mw of 1,726, a Mn of 1,079 and a Mw/Mn of 1.6. An absorption maximum at 400 nm was observed in the visible light absorption spectrum in DMF. [0259]
    • EXAMPLE 91
  • A mixture of the diacidic azo compound (1.71 g, 0.003 mole) having the formula [0260]
    Figure US20040195552A1-20041007-C00083
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.85 g) and DMF (8.0 mL) was heated with occasional stirring at 95° C. for 2.0 hours. The reaction mixture was drowned into methanol (100 ml) and the red polydye was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.5 g). GPC indicated a Mw of 2,090, a Mn of 1,235 and a Mw/Mn of 1.69. An absorption maximum was observed at 545 nm in the visible light absorption spectrum in DMF. [0261]
    • EXAMPLE 91a
  • To conc. H[0262] 2SO4(5.0 mL) was added dry NaNO2 (0.72 g) portionwise with stirring, allowing the temperature to rise. The nitrosyl sulfuric acid solution was stirred and cooled and 1:5 acid (10 ml was added below about 15° C., followed by 5-amino-4-cyano-3-methylisothiazole (1.39 g, 0.01 mole) and 1:5 acid (10 ml) both added at 0-5° C. After being stirred at 0-5° C. for 2.0 hours an aliquot (0.005 mole) of the diazonium solution was added to a stirred solution of 3-acetamido-N,N-bis-(4-carboxyphenylmethyl)aniline (2.09 g, 0.005 mole) dissolved in 1:5 acid (30 ml) at 0-5° C. Ammonium acetate was added to neutralize the coupling mixture until neutral to Congo Red test paper. Water was added to the coupling mixture to precipitate the red dye, which was collected by filtration and dried in air (yield—2.67 g). The product was reslurried in hot methanol, allowed to cool and the solid collected by filtration, washed with methanol and dried in air (yield—2.10 g). FDMS indicated the structure to be that of the diacid azo compound used as a starting material for Example 91.
    • EXAMPLE 91b
  • To a slurry of the diester compound (12.00 g, 0.0269 mole) having the structure [0263]
    Figure US20040195552A1-20041007-C00084
  • in water (150 ml) was added aqueous 50% NaOH solution (10.80 g) and 2-ethoxyethanol (20 ml). The reaction mixture was heated at about 70-80° C. for 2.0 hours and allowed to cool. The cloudy reaction mixture was clarified by filtering through Celite filter aid and the filtrate was drowned into ice/water mixture (150 g). Conc. HCl was added dropwise with stirring to bring the pH to about 2.5. The tan solid was collected by filtration, washed with water and dried at 40° C. under nitrogen (yield—10.04 g). FDMS indicated the product to have the structure of the coupler used in Example 91a. [0264]
    • EXAMPLE 92
  • A mixture of the diacidic azo compound (0.83 g, 0.002 mole) having the structure [0265]
    Figure US20040195552A1-20041007-C00085
  • 1,2-ethanediol, dimethanesulfonate (0.44 g, 0.002 mole), potassium carbonate (0.5 g) and DMF (7.5 ml) was heated at about 95° C. for 3.0 hours. The polydye was isolated by drowning the reaction mixture into water and acidifying with acetic acid, followed by filtering, washing with water and drying in air. GPC analysis indicated a Mw of 2,379, a Mn of 1,363 a Mw/Mn of 1.74. An absorption maximum was observed-in DMF in the visible absorption spectrum at 480 nm. [0266]
    • EXAMPLE 93
  • A mixture of the diacidic azo compound (1.26 g, 0.003 mole) having the structure [0267]
    Figure US20040195552A1-20041007-C00086
  • 1,6-hexanediol, dimethanesulfonate (0.82 g, 0.003 mole), potassium carbonate (0.50 g) and DMF (8.0 mL) was heated at about 95° C. for 1.5 hours. The reaction mixture was drowned into methanol (100 mL) and acetic acid (1.0 mL) was added The initially sticky polydye solidified after standing for about 1.0 hour and was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.60 g). GPC analysis indicated a Mw of 2,667, a Mn of 1,695 and a Mw/Mn of 1.57. An absorption maximum at 508 nm was observed in the visible light absorption spectrum in DMF. [0268]
    • EXAMPLE 93a
  • A mixture of the diacidic azo compound (3.62 g, 0.005 m) having the structure [0269]
    Figure US20040195552A1-20041007-C00087
  • 1,2-ethanediol, dimethanesulfonate (1.10 g, 0.005 m), potassium carbonate (1.50 g) and DMF (30 mL) was heated at about 95° C. with stirring for 2.0 hours. The reaction mixture was drowned into methanol (100 mL) and the red polydye was collected by vacuum filtration and washed with methanol, water containing acetic acid, hot water and dried in air (yield—3.08 grams). GPC analysis indicated a Mw of 7,176, a Mn of 3,533 and a Mw/Mn of 2.02. An absorption maximum was observed in the visible light absorption spectrum at 525 nm. [0270]
    • EXAMPLE 93b
  • To conc. H[0271] 2SO4 (5.0 mL) was added dry NaNO2 (0.72 g) portionwise with stirring, allowing the temperature to rise. The nitrosyl sulfuric acid solution was stirred and cooled and 1:5 acid (1 part propionic:5 parts acetic acid) (10 mL) was added below about 15° C., followed by 2,6-dicyano-3,5-diphenylaniline (2.95 g, 0.01 m) and 1:5 acid (10 mL) both added at 0-5° C. After being stirred for 2.0 hours at 0-5° C., the diazonium solution was added to a stirred solution of 3-acetamido-N,N-bis (4-carboxyphenylmethyl)aniline (4.18 g, 0.01 m) dissolved in a mixture of 1:5 acid (75 mL) plus 15% aqueous sulfuric acid (15 mL) at 0-5° C. Ammonium acetate was added portionwise until the coupling mixture was neutral to Congo Red test paper. After about 1.0 hour, water was added to the coupling mixture and the resulting slurry heated to about 60° C. The red product was collected by filtration, washed well with hot water and dried in air (yield—5.43 g). FDMS analysis indicated the structure to be that of the starting material for Example 93-1.
    • EXAMPLE 93c
  • A mixture of the diacidic azo compound (1.80 g, 0.003 m) having the structure [0272]
    Figure US20040195552A1-20041007-C00088
  • 1,2-ethanediol, dimethanesulfonate (0.66 g, 0.003 m), potassium carbonate (1.0 g) and DMF (8 mL) was heated at about 95° C. with occasional stirring. The polydye was isolated by drowning the reaction mixture into methanol (100 mL) followed by filtration and washing with methanol, water containing acetic acid, water and was then dried in air (yield—0.52 g). GPC analysis using NMP (N-methyl-2-pyrrolidinone) solvent indicated a Mw of 5,413, a Mn of 2,196 and a Mw/Mn of 2.46. An absorbance maximum at 517 nm was observed in the visible absorption maximum in DMF. [0273]
    • EXAMPLE 93d
  • A sample of 2-amino-5-ethylthio-1,3,4-thiadiazole (1.61 g, 0.01 m) was diazotized and coupled with 3-acetamido-N,N-bis(4-carboxyphenylmethyl)aniline (4.18 g, 0.01 m) and the red product isolated using the procedure described above in Example 93-1a. FDMS indicated the structure of the azo compound to be that of the starting material for Example 93-2. [0274]
    • EXAMPLES 94-118
  • Colored EASTAR® PETG 6763 film was produced by melt blending the polydyes of Examples 69-93 and extruding according to the following procedures to produce Examples 94-118 (Table 2). [0275]
  • EASTAR® PETG polyester 6763, a poly(ethylene-cyclohexanedimethylene) terephthalate, (Eastman Chemical Company) (300 g of previously dried pellets) was dry blended with the azo dye composition (0.12 g) and the blend extruded and finally a 18-20 mil thick film prepare as described above for Examples 37-66. [0276]
    • EXAMPLE 119
  • A mixture of the diacidic anthrapyridone compound (0.93 g, 0.002 mole) having the structure [0277]
    Figure US20040195552A1-20041007-C00089
  • 1,2-ethandiol, dimethanesulfonate (0.44 g, 0.002 mole), potassium carbonate. (0.5 g) and DMF (8.0 mL) was heated at about 95° C. for 3.0 hours with occasional stirring. The reaction mixture was drowned into methanol (100 mL) and the violet polydye was collected by filtration, washed with methanol, water containing acetic acid, water and dried in air (yield—1.09 g). A number average molecular weight of 1,228 was obtained by GPC analysis. Absorption maxima at 544 and 583 nm were observed in the visible light absorption spectrum in DMF. [0278]
    • EXAMPLE 119a
  • To a mixture of 1-cyano-6-(3′,5′-dicarbomethoxyphenylamino)-3-methyl-3H-dibenz[f,ij]isoquinoline-2,7-dione (2.00 g, 0.00405 mole) stirred in 2-ethoxyethanol (50 mL) was added aqueous 50% NaOH solution (2.47 g). The reaction mixture was heated at 90-95° C. for 50 minutes and then was drowned into water. The mixture was acidified by addition of acetic acid and the solid product was collected by filtration, washed with water and dried in air (yield—1.78 g). FDMS indicated the product to be the diacidic anthrapyridone compound reacted in Example 119. [0279]
    • EXAMPLE 119b
  • A mixture of 6-bromo-1-cyano-3-methyl-3H-dibenz[f,ij]isoquinoline-2,7-dione (11.0 g, 0.03 mole), dimethyl 5-aminoisophthalate (25.1 g, 0.12 mole), cupric acetate (3.6 g), potassium carbonate (3.0 g) and DMF (90 mL) was heated and stirred under nitrogen to about 135-40° C. The reaction mixture became very thick and turned violet. Additional DMF (40 mL) was added and heating was continued at 135-40° C. for 2.0 hours. The reaction mixture was allowed to cool to about 60° C. and poured on a coarse fritted glass funnel for vacuum filtration. The product was washed with DMF and water and the water-wet cake was reslurried in boiling acetone (250 mL). After cooling, the product was collected by filtration, washed with acetone and dried in air (yield—10.8 g). FDMS indicated the product to be the diester anthrapyridone compound used in Example 119a. [0280]
    • EXAMPLE 120
  • A mixture of the diacidic nitroarylamine compound (2.50 g, 0.0057 mole) having the structure [0281]
    Figure US20040195552A1-20041007-C00090
  • 1,2-ethanediol, dimethanesulfonate (1.25 g, 0.0057 mole), potassium carbonate (1.6 g) and DMF (15 mL) was heated at 95° C. for 2.5 hours. The reaction mixture was drowned into methanol (200 mL) and the yellow polydye was collected by filtration, washed containing acetic acid, water and dried at 40° C. (yield—0.77 g). An absorption maximum was observed at 412 nm in the visible absorption spectrum in DMF. [0282]
    • EXAMPLE 121
  • A mixture of the diacidic nitroarylamine compound (4.40 g, 0.015 mole) having the structure [0283]
    Figure US20040195552A1-20041007-C00091
  • 1,2-ethanediol, dimethanesulfonate (3.27 g, 0.015 mole), potassium carbonate (2.0 g) and DMF 40 mL) was heated at 90-95° C. with stirring for 4.0 hours. The reaction mixture was drowned into methanol (200 mL) and the yellow polydye was collected by filtration, washed with methanol, water containing acetic acid, water and dried in air (yield—1.80 g). GPC analysis indicated a Mw of 1,585, a Mn of 1,024, a Mw/Mn of 1.54. An absorption maximum at 416 nm was observed in the visible light absorption spectrum in DMF. [0284]
    • EXAMPLES 122-124
  • Colored polyester film was produced by melt blending and extruding EASTAR® PETG polyester 6763 (Eastman Chemical Company) (300 g previously dried pellets) which had dry blended with the polydyes of Examples 119, 120, 121 to produce Examples 122-124, respectively, according to the procedure used to produce Examples 37-66. The film of Example 122 was violet and those of Examples 123 and 124 were bright yellow. [0285]
    • EXAMPLE 125
  • A mixture of the benzotriazole UV light absorbing compound. (3.27 g, 0.01 mole) having the structure [0286]
    Figure US20040195552A1-20041007-C00092
  • 1,2-ethanediol, dimethanesulfonate (2.18 g, 0.01 mole), potassium carbonate (2.76 g) and DMF (25 mL) was heated at about 95° C. for 6.0 hours. The reaction mixture was drowned into methanol (200 mL) and a little acetic acid added. The polymeric UV light absorbing compound was collected by filtration, washed with water containing a little acetic acid, hot water and then dried in air (yield—2.88 g). GPC analysis indicated a Mw of 7,561, a Mn of 2,632 and a Mw/Mn of 2.87. An absorption maximum was observed at 350 nm in the UV light absorption spectrum in methylene chloride. [0287]
    • EXAMPLE 126
  • A benzylidene type UV light fluorescent compound (1.0 g, 0.0028 mole) having the structure [0288]
    Figure US20040195552A1-20041007-C00093
  • 1,6-hexenediol, dimethanesulfonate (0.0028 mole), potassium carbonate (0.97 g) and DMF (10 mL) were mixed and the reaction mixture was heated at for 3.0 hours at about 120-130° C. The reaction mixture was drowned into methanol (100 mL) and the polymer was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—0.69 g). GPC indicated a Mw of 50,717, a Mn of 16,044 and a MW/Mn of 3.16. [0289]
    • EXAMPLE 127
  • EASTAPAK® PET 7352, a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of previously dried pellets) was dry blended with the polymeric UV light fluorescent material of Example 126 (0.16 g). The blend was extruded with a C. W. Brabender ¾ inch extruder, equipped with a mixing screw, at 285° C. into a water bath and the extrudate pelletized. The pellets which contained about 400 ppm of the UV light absorber showed a strong blue white fluorescence under UV light. [0290]
    • EXAMPLE 128
  • Example 127 was repeated except that 8 mg of the UV light fluorescent material of Example 126 was added to the EASTAPAK® PET 7352. The resulting pellets showed a strong blue-white fluorescence under UV light and appeared very white in sunlight. [0291]
    • EXAMPLE 129
  • A mixture of Pc-Al—O—C[0292] 6H3-3,5-diCO2H (Pc=phthalocyanine) (1.74 g, 0.0024 mole), 1,6-hexanediol, dimethanesulfonate (0.66 g, 0.0024 mole), potassium carbonate (0.83 g) and DMF (10 mL) was heated and stirred at about 125° C. for 1 hour and then at about 140° C. for 1 hour. The reaction mixture was drowned into methanol (50 mL) and the polymeric product was collected by filtration, washed with methanol, water containing acetic acid, hot water and dried in air (yield—1.48 g).
    • EXAMPLE 130
  • EASTAPAK® PET 7352, a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of previously dried pellets) was dry blended with the polymeric phthalocyanine compound of Example 129 (0.12 g). The blend was extruded with a C. W. Brabender ¾ inch extruder, equipped with a mixing screw, at 2850 into a water bath and the extrudate pelletized. The cyan pellets were redried at 70° C. for about 17 hrs at a pressure of about 1-5 torr. A portion of the dried pellets (1.40 g) was pressed into a film at 285° C. using a 2-inch diameter circular mold in a Pasadena Hydraulic, Inc. press using 12,000 pounds ram force (4-inch ram). A transparent cyan film was produced by quenching in water and had an absorption maximum at 684 nm in the light absorption spectrum. [0293]
    • EXAMPLE 131
  • Example 130 was repeated except that 4 mg of the polymeric phthalocyanine compound of Example 129 was added to the PET. The final film contained-about 10 ppm and had a light absorption maximum at 685 nm. [0294]
    • EXAMPLE 132
  • EASTAPAK® PET 7352, a poly(ethyleneterephthalate) (Eastman Chemical Company) (400 g of dried pellets) was dry blended with the polydye of Example 18 (0.6 g). The blend was extruded with a C. W. Brabender ¾ inch extruder, equipped with a mixing screw, at 285° C. into a water bath and the extrudate pelletized. Good color production resulted with no evidence of color loss by sublimation to give dark red pellets containing about 0.15% by weight of the polydye. [0295]
    • EXAMPLE 133
  • Example 132 was repeated using 0.6 g of the polydye of Example 75 as the colorant to give yellow pellets having about 0.15% by weight of the polydye. No loss of color by sublimation was observed. [0296]
    • EXAMPLES 134-182
  • The diacidic azo compounds of Formula VI in Table 3 are reacted with essentially equimolar amounts of 1,2-ethanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 134-182 in Table 3. [0297]
    • EXAMPLES 183-193
  • The diacidic diazo compounds of Formula VII in Table 4 are reacted with essentially equimolar amounts of 1,4-butanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 183-193 in Table 4. [0298]
    • EXAMPLES 194-202
  • The diacidic bisazo compounds of Formula VIIa in Table 5 are reacted with essentially equimolar amounts of 1,3-propanediol, dimethanesulfonate in DMF in the presence of sodium carbonate to yield the polydyes of Examples 194-202 in Table 5. [0299]
    • EXAMPLES 203-211
  • The diacidic benzylidene (methine) compounds in Table 6 are reacted with essentially equimolar amounts of 1,4-cyclohexanedimethanol, dimethanesulfonate in DMF in the presence of sodium carbonate to yield the polydyes of Examples 203-211 in Table 6. [0300]
    • EXAMPLES 212-220
  • The diacidic 3-aryl-2,5-dioxypyrroline compounds of Formula X in Table 7 are reacted with essentially equimolar amounts of diethylene glycol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 212-220 in Table 7. [0301]
    • EXAMPLES 221-230
  • The diacidic 3-aryl-5-dicyanomethylene-2-oxypyrroline compounds of Formula XI in Table 8 are reacted with essentially equimolar amounts of triethylene glycol, dimethanesulfonate to yield the polydyes of Examples 221-230 in Table 8. [0302]
    • EXAMPLES 231-239
  • The diacidic azo-methine compounds of Formula XIII in Table 9 are reacted with essentially equimolar amounts of 1,4-butanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 231-239 in Table 9. [0303]
    • EXAMPLES 240-269
  • The diacidic anthraquinone compounds of Formula XIV in Table 10 are reacted with essentially equimolar amounts of 2,2,4,4-tetramehtyl-1,3-cyclobutanediol, dimethanesulfonate in N,N-dimethylacetamide in the presence of potassium carbonate to yield the polydyes of Examples 240-269 in Table 10. [0304]
    • EXAMPLES 270-326
  • The diacidic anthraquinone compounds of Formula XV in Table 11 are reacted with essentially equimolar amounts of 1,2-ethanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 270-326 in Table 11. [0305]
    • EXAMPLES 327-344
  • The diacidic anthraquinone compounds of Formula XVI in Table 12 are reacted with essentially equimolar amounts of 1,6-hexanediol, dimethanesulfonate in N-methyl-2-pyrrolidinone in the presence of sodium carbonate to yield the polydyes of Examples 327-344 in Table 12. [0306]
    • EXAMPLES 345-361
  • The diacidic anthrapyridine compounds of Formula XVIII in Table 13 are reacted with essentially equimolar amounts of 1,4-butanediol, di-p-toluenesulfonate in the presence of DMF to yield the polydyes of Examples 345-361 in Table 13. [0307]
    • EXAMPLES 362-381
  • The diacidic anthraquinone compounds of Formula XIX in Table 14 are reacted with 2,2-dimethyl-1,3-propanediol, dimethanesulfonate in essentially equimolar amounts in DMF in the presence of potassium carbonate to yield the polydyes of Examples 362-381 in Table 14. [0308]
    • EXAMPLES 382-396
  • The diacidic anthraquinone compounds of Formula XIXc of Table 15 are reacted with essentially equimolar amounts of 1,2-ethanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 382-396 in Table 15. [0309]
    • EXAMPLES 397-414
  • The diacidic anthraquinone compounds of Formula XIXd in Table 16 are reacted with essentially equimolar amounts of 1,6-hexanediol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 397-414 in Table 16. [0310]
    • EXAMPLES 415-435
  • The diacidic anthraquinone compounds of Formula XIXe in Table 17 are reacted in essentially equimolar amounts with ethylene glycol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 414-435 in Table 17. [0311]
    • EXAMPLES 436-449
  • The diacidic anthraquinone compounds of Formula XIXf in Table 18 are reacted in essentially equimolar amounts with 1,4-cyclohexanedimethanol, dimethanesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 436-449 in Table 18. [0312]
    • EXAMPLES 450-455
  • The diacidic anthrapyridine compounds of Table 19 are reacted with essentially equimolar amounts of 1,6-hexanediol, di-p-toluenesulfonate in DMF in the presence of potassium carbonate to yield the polydyes of Examples 450-455 in Table 19. [0313]
    • EXAMPLES 456-465
  • The diacidic nitroarylamine compounds of Table 20 are reacted with 1,4-butanediol, dimethanesulfonate in essentially equimolar amounts in DMF in the presence of potassium carbonate to yield the polydyes of Examples 456-465 in Table 20. [0314]
    • EXAMPLES 466-505
  • The miscellaneous diacidic compounds of Table 21 are reacted with essentially equimolar amounts of the disulfonate compounds of Table 21 in DMF in the presence of potassium carbonate to yield the polydyes of Examples 466-505 in Table 21. [0315]
    • EXAMPLES 506-522
  • The diacidic UV light absorbing compounds of Table 22 are reacted with essentially equimolar amounts of the disulfonate compounds of Table 22 in DMF in the presence of potassium carbonate to yield the polymeric UV absorbers of Examples 506-522 in Table 22. [0316]
    • EXAMPLES 523-536
  • The diacidic infrared light absorbing compounds of Table 23 are reacted with essentially equimolar amounts of the disulfonate compounds of Table 23 in DMF in the presence of potassium carbonate to yield the polymeric infrared light absorbing compounds of Examples 523-536 in Table 23. [0317]
    TABLE 1
    Anthraquinone Polydyes in EASTAR ® PETG
    (300 ppm)
    Example Polydye Melt Blended and Extruded
    No. With EASTAR ® PETG Color of Film
    37 Polydye of Example 7 Blue
    38 Polydye of Example 8 Blue
    39 Polydye of Example 9 Blue
    40 Polydye of Example 10 Blue
    41 Polydye of Example 11 Blue
    42 Polydye of Example 12 Blue
    43 Polydye of Example 13 Greenish-blue
    44 Polydye of Example 14 Reddish-blue
    45 Polydye of Example 15 Blue
    46 Polydye of Example 16 Green
    47 Polydye of Example 17 Bright blue
    48 Polydye of Example 18 Bluish-red
    49 Polydye of Example 19 Yellow
    50 Polydye of Example 20 Orange
    51 Polydye of Example 21 Red
    52 Polydye of Example 22 Green
    53 Polydye of Example 23 Yellow
    54 Polydye of Example 24 Yellow
    55 Polydye of Example 25 Yellow
    56 Polydye of Example 26 Yellow
    57 Polydye of Example 27 Blue
    58 Polydye of Example 28 Red
    59 Polydye of Example 29 Greenish-yellow
    60 Polydye of Example 30 Yellow
    61 Polydye of Example 31 Greenish-yellow
    62 Polydye of Example 32 Blue
    63 Polydye of Example 33 Yellow
    64 Polydye of Example 34 Yellow
    65 Polydye of Example 35 Greenish-blue
    66 Polydye of Example 36 Greenish-blue
  • [0318]
    TABLE 2
    Azo Polydyes in EASTAR ® PETG 6763
    (300 ppm)
    Example Polydye Melt Blended and Extruded
    No. With EASTAR ® PETG Color of Film
    94 Polydye of Example 69 Violet
    95 Polydye of Example 70 Blue
    96 Polydye of Example 71 Yellow-brown
    97 Polydye of Example 72 Red
    98 Polydye of Example 73 Orange
    99 Polydye of Example 74 Yellow
    100 Polydye of Example 75 Greenish-yellow
    101 Polydye of Example 76 Scarlet
    102 Polydye of Example 77 Yellow
    103 Polydye of Example 78 Scarlet
    104 Polydye of Example 79 Yellow
    105 Polydye of Example 80 Red
    106 Polydye of Example 81 Orange
    107 Polydye of Example 82 Reddish-brown
    108 Polydye of Example 83 Red
    109 Polydye of Example 84 Reddish-blue
    110 Polydye of Example 85 Blue
    111 Polydye of Example 86 Brown
    112 Polydye of Example 87 Reddish-brown
    113 Polydye of Example 88 Magenta
    114 Polydye of Example 89 Magenta
    115 Polydye of Example 90 Yellow
    116 Polydye of Example 91 Red
    117 Polydye of Example 92 Orange
    118 Polydye of Example 93 Scarlet
  • [0319]
    TABLE 3
    Polydyes From Diacidic Compounds of Formula VI
    R6—N═N—Z
    Example
    No. R4 Z Color
    134
    Figure US20040195552A1-20041007-C00094
    Figure US20040195552A1-20041007-C00095
         		violet
    135
    Figure US20040195552A1-20041007-C00096
    Figure US20040195552A1-20041007-C00097
         		red
    136
    Figure US20040195552A1-20041007-C00098
    Figure US20040195552A1-20041007-C00099
         		magenta
    137
    Figure US20040195552A1-20041007-C00100
    Figure US20040195552A1-20041007-C00101
         		violet
    138
    Figure US20040195552A1-20041007-C00102
    Figure US20040195552A1-20041007-C00103
         		scarlet
    139
    Figure US20040195552A1-20041007-C00104
    Figure US20040195552A1-20041007-C00105
         		red
    140
    Figure US20040195552A1-20041007-C00106
    Figure US20040195552A1-20041007-C00107
         		violet
    141
    Figure US20040195552A1-20041007-C00108
    Figure US20040195552A1-20041007-C00109
         		blue
    142
    Figure US20040195552A1-20041007-C00110
    Figure US20040195552A1-20041007-C00111
         		orange
    143
    Figure US20040195552A1-20041007-C00112
    Figure US20040195552A1-20041007-C00113
         		scarlet
    144
    Figure US20040195552A1-20041007-C00114
    Figure US20040195552A1-20041007-C00115
         		magenta
    145
    Figure US20040195552A1-20041007-C00116
    Figure US20040195552A1-20041007-C00117
         		magenta
    146
    Figure US20040195552A1-20041007-C00118
    Figure US20040195552A1-20041007-C00119
         		bluish-red
    147
    Figure US20040195552A1-20041007-C00120
    Figure US20040195552A1-20041007-C00121
         		violet
    148
    Figure US20040195552A1-20041007-C00122
    Figure US20040195552A1-20041007-C00123
         		blue
    149
    Figure US20040195552A1-20041007-C00124
    Figure US20040195552A1-20041007-C00125
         		red
    150
    Figure US20040195552A1-20041007-C00126
    Figure US20040195552A1-20041007-C00127
         		violet
    151
    Figure US20040195552A1-20041007-C00128
    Figure US20040195552A1-20041007-C00129
         		violet
    152
    Figure US20040195552A1-20041007-C00130
    Figure US20040195552A1-20041007-C00131
         		orange
    153
    Figure US20040195552A1-20041007-C00132
    Figure US20040195552A1-20041007-C00133
         		red
    154
    Figure US20040195552A1-20041007-C00134
    Figure US20040195552A1-20041007-C00135
         		navy blue
    155
    Figure US20040195552A1-20041007-C00136
    Figure US20040195552A1-20041007-C00137
         		blue
    156
    Figure US20040195552A1-20041007-C00138
    Figure US20040195552A1-20041007-C00139
         		red
    157
    Figure US20040195552A1-20041007-C00140
    Figure US20040195552A1-20041007-C00141
         		orange
    158
    Figure US20040195552A1-20041007-C00142
    Figure US20040195552A1-20041007-C00143
         		red
    159
    Figure US20040195552A1-20041007-C00144
    Figure US20040195552A1-20041007-C00145
         		blue
    160
    Figure US20040195552A1-20041007-C00146
    Figure US20040195552A1-20041007-C00147
         		blue
    161
    Figure US20040195552A1-20041007-C00148
    Figure US20040195552A1-20041007-C00149
         		red
    162
    Figure US20040195552A1-20041007-C00150
    Figure US20040195552A1-20041007-C00151
         		red
    163
    Figure US20040195552A1-20041007-C00152
    Figure US20040195552A1-20041007-C00153
         		red
    164
    Figure US20040195552A1-20041007-C00154
    Figure US20040195552A1-20041007-C00155
         		orange
    165
    Figure US20040195552A1-20041007-C00156
    Figure US20040195552A1-20041007-C00157
         		yellow
    166
    Figure US20040195552A1-20041007-C00158
    Figure US20040195552A1-20041007-C00159
         		yellow
    167
    Figure US20040195552A1-20041007-C00160
    Figure US20040195552A1-20041007-C00161
         		orange
    168
    Figure US20040195552A1-20041007-C00162
    Figure US20040195552A1-20041007-C00163
         		yellow
    169
    Figure US20040195552A1-20041007-C00164
    Figure US20040195552A1-20041007-C00165
         		red
    170
    Figure US20040195552A1-20041007-C00166
    Figure US20040195552A1-20041007-C00167
         		red
    171
    Figure US20040195552A1-20041007-C00168
    Figure US20040195552A1-20041007-C00169
         		orange
    172
    Figure US20040195552A1-20041007-C00170
    Figure US20040195552A1-20041007-C00171
         		blue
    173
    Figure US20040195552A1-20041007-C00172
    Figure US20040195552A1-20041007-C00173
         		red
    174
    Figure US20040195552A1-20041007-C00174
    Figure US20040195552A1-20041007-C00175
         		yellow
    175
    Figure US20040195552A1-20041007-C00176
    Figure US20040195552A1-20041007-C00177
         		yellow
    176
    Figure US20040195552A1-20041007-C00178
    Figure US20040195552A1-20041007-C00179
         		yellow
    177
    Figure US20040195552A1-20041007-C00180
    Figure US20040195552A1-20041007-C00181
         		yellow
    178
    Figure US20040195552A1-20041007-C00182
    Figure US20040195552A1-20041007-C00183
         		orange
    179
    Figure US20040195552A1-20041007-C00184
    Figure US20040195552A1-20041007-C00185
         		yellow
    180
    Figure US20040195552A1-20041007-C00186
    Figure US20040195552A1-20041007-C00187
         		yellow
    181
    Figure US20040195552A1-20041007-C00188
    Figure US20040195552A1-20041007-C00189
         		orange
    182
    Figure US20040195552A1-20041007-C00190
    Figure US20040195552A1-20041007-C00191
         		red
  • [0320]
    TABLE 4
    Polydyes From Diacidic Compounds of Formula VII
    R6—N═N—R7—N═N—Z
    Example No. R6 R7 Z Color
    183
    Figure US20040195552A1-20041007-C00192
    Figure US20040195552A1-20041007-C00193
    Figure US20040195552A1-20041007-C00194
         		red
    184
    Figure US20040195552A1-20041007-C00195
    Figure US20040195552A1-20041007-C00196
    Figure US20040195552A1-20041007-C00197
         		red
    185
    Figure US20040195552A1-20041007-C00198
    Figure US20040195552A1-20041007-C00199
    Figure US20040195552A1-20041007-C00200
         		reddish yellow
    186
    Figure US20040195552A1-20041007-C00201
    Figure US20040195552A1-20041007-C00202
    Figure US20040195552A1-20041007-C00203
         		reddish yellow
    187
    Figure US20040195552A1-20041007-C00204
    Figure US20040195552A1-20041007-C00205
    Figure US20040195552A1-20041007-C00206
         		red
    188
    Figure US20040195552A1-20041007-C00207
    Figure US20040195552A1-20041007-C00208
    Figure US20040195552A1-20041007-C00209
         		yellow brown
    189
    Figure US20040195552A1-20041007-C00210
    Figure US20040195552A1-20041007-C00211
    Figure US20040195552A1-20041007-C00212
         		blue
    190
    Figure US20040195552A1-20041007-C00213
    Figure US20040195552A1-20041007-C00214
    Figure US20040195552A1-20041007-C00215
         		red
    191
    Figure US20040195552A1-20041007-C00216
    Figure US20040195552A1-20041007-C00217
    Figure US20040195552A1-20041007-C00218
         		red
    192
    Figure US20040195552A1-20041007-C00219
    Figure US20040195552A1-20041007-C00220
    Figure US20040195552A1-20041007-C00221
         		reddish yellow
    193
    Figure US20040195552A1-20041007-C00222
    Figure US20040195552A1-20041007-C00223
    Figure US20040195552A1-20041007-C00224
         		red
  • [0321]
    TABLE 5
    Polydyes From Diacidic Compounds of Formula VIIa
    R6—N═N—Y1—N═N—R6
    Example
    No. R6 Y1 Color
    194
    Figure US20040195552A1-20041007-C00225
    Figure US20040195552A1-20041007-C00226
         		red
    195
    Figure US20040195552A1-20041007-C00227
    Figure US20040195552A1-20041007-C00228
         		orange
    196
    Figure US20040195552A1-20041007-C00229
    Figure US20040195552A1-20041007-C00230
         		orange
    197
    Figure US20040195552A1-20041007-C00231
    Figure US20040195552A1-20041007-C00232
         		orange
    198
    Figure US20040195552A1-20041007-C00233
    Figure US20040195552A1-20041007-C00234
         		violet
    199
    Figure US20040195552A1-20041007-C00235
    Figure US20040195552A1-20041007-C00236
         		red
    200
    Figure US20040195552A1-20041007-C00237
    Figure US20040195552A1-20041007-C00238
         		violet
    201
    Figure US20040195552A1-20041007-C00239
    Figure US20040195552A1-20041007-C00240
         		yellow
    202
    Figure US20040195552A1-20041007-C00241
    Figure US20040195552A1-20041007-C00242
         		blue
  • [0322]
    TABLE 6
    Polydyes From Diacidic Compounds of Formula VIII
    R11—CH═D
    Example No. R11 D Color
    203
    Figure US20040195552A1-20041007-C00243
    Figure US20040195552A1-20041007-C00244
         		yellow
    204
    Figure US20040195552A1-20041007-C00245
    Figure US20040195552A1-20041007-C00246
         		yellow
    205
    Figure US20040195552A1-20041007-C00247
    Figure US20040195552A1-20041007-C00248
         		yellow
    206
    Figure US20040195552A1-20041007-C00249
    Figure US20040195552A1-20041007-C00250
         		blue
    207
    Figure US20040195552A1-20041007-C00251
    Figure US20040195552A1-20041007-C00252
         		yellow
    208
    Figure US20040195552A1-20041007-C00253
    Figure US20040195552A1-20041007-C00254
         		red
    209
    Figure US20040195552A1-20041007-C00255
    Figure US20040195552A1-20041007-C00256
         		red
    210
    Figure US20040195552A1-20041007-C00257
    Figure US20040195552A1-20041007-C00258
         		yellow
    211
    Figure US20040195552A1-20041007-C00259
    Figure US20040195552A1-20041007-C00260
         		yellow
  • [0323]
    TABLE 7
    Polydyes From Diacidic Compounds of Formula X
    Figure US20040195552A1-20041007-C00261
    Example No. R11 R12 Color
    212
    Figure US20040195552A1-20041007-C00262
         		C2H5 red
    213
    Figure US20040195552A1-20041007-C00263
         		H red
    214
    Figure US20040195552A1-20041007-C00264
         		H red
    215
    Figure US20040195552A1-20041007-C00265
         		CH2C6H5 red
    216
    Figure US20040195552A1-20041007-C00266
         		CH3 violet
    217
    Figure US20040195552A1-20041007-C00267
         		CH2CH2OH violet
    218
    Figure US20040195552A1-20041007-C00268
    Figure US20040195552A1-20041007-C00269
         		red
    219
    Figure US20040195552A1-20041007-C00270
         		CH2CH2CO2H red
    220
    Figure US20040195552A1-20041007-C00271
         		H red
  • [0324]
    TABLE 8
    Polydyes From Diacidic Compounds of Formula XI
    Figure US20040195552A1-20041007-C00272
    Example No. R11 R12 Color
    221
    Figure US20040195552A1-20041007-C00273
         		H blue
    222
    Figure US20040195552A1-20041007-C00274
         		H greenish blue
    223
    Figure US20040195552A1-20041007-C00275
         		CH2CH═CH2 reddish blue
    224
    Figure US20040195552A1-20041007-C00276
         		CH2C5H11 blue
    225
    Figure US20040195552A1-20041007-C00277
         		H blue
    226
    Figure US20040195552A1-20041007-C00278
         		H blue
    227
    Figure US20040195552A1-20041007-C00279
         		H blue
    228
    Figure US20040195552A1-20041007-C00280
         		H blue
    229
    Figure US20040195552A1-20041007-C00281
         		H blue
    230
    Figure US20040195552A1-20041007-C00282
    Figure US20040195552A1-20041007-C00283
         		blue
  • [0325]
    TABLE 9
    Polydyes From Diacidic Compounds of Formula XIII
    D═HC—R7—N═N—Z
    Example No. D R7 Z Color
    231
    Figure US20040195552A1-20041007-C00284
    Figure US20040195552A1-20041007-C00285
    Figure US20040195552A1-20041007-C00286
         		red
    232
    Figure US20040195552A1-20041007-C00287
    Figure US20040195552A1-20041007-C00288
    Figure US20040195552A1-20041007-C00289
         		blue
    233
    Figure US20040195552A1-20041007-C00290
    Figure US20040195552A1-20041007-C00291
    Figure US20040195552A1-20041007-C00292
         		blue
    234
    Figure US20040195552A1-20041007-C00293
    Figure US20040195552A1-20041007-C00294
    Figure US20040195552A1-20041007-C00295
         		blue
    235
    Figure US20040195552A1-20041007-C00296
    Figure US20040195552A1-20041007-C00297
    Figure US20040195552A1-20041007-C00298
         		blue
    236
    Figure US20040195552A1-20041007-C00299
    Figure US20040195552A1-20041007-C00300
    Figure US20040195552A1-20041007-C00301
         		blue
    237
    Figure US20040195552A1-20041007-C00302
    Figure US20040195552A1-20041007-C00303
    Figure US20040195552A1-20041007-C00304
         		blue
    238
    Figure US20040195552A1-20041007-C00305
    Figure US20040195552A1-20041007-C00306
    Figure US20040195552A1-20041007-C00307
         		blue
    239
    Figure US20040195552A1-20041007-C00308
    Figure US20040195552A1-20041007-C00309
    Figure US20040195552A1-20041007-C00310
         		blue
  • [0326]
    TABLE 10
    Polydyes From Diacidic Anthraquinone Compounds of Formula XIV
    Figure US20040195552A1-20041007-C00311
    Example
    No. Q R14 Color
    240 5-S 1,4-diNHCH2C(CH3)2CH2OH blue
    241 2-O— 1-NH2, 4-OH red
    242 2-S— 1-NH2, 4-NHSO2CH3 violet
    243 2-S— 1-NH2, 4-NHSO2C6H5 violet
    244 2-SO2— 1-NH2, 4-NHC6H5 blue
    245 2-SO2— 1-NH2, 4-NHC6H4-4-CH3 blue
    246 2-SO2— 1-NH2, 4-SC6H5 violet
    247 2-S— 1-NH2, 4-NHCOC2H5 violet
    248 4-S— 1-NH2 red
    249 4-S— 1-NHC6H11 violet
    250 4-S— 1-NHC6H5 violet
    251 4-NH— 1-NH2, 2-OCH3 violet
    252 4-NH— 1-NHC6H5 green
    253 4-NH— 1-NHC6H5-2,6-diC2H5 blue
    254 4-NH— 1-OH violet
    255 2-S— 1,4-di-OH orange
    256 2-SO2— 1,4-di-OH orange
    257 4-S— 1-NHCH3 violet
    258 4-S— 1-NHCH2CH(C2H5)C4H9 violet
    259 6(7)S— 1,4-diNHC6H5-2,5-diC2H5 cyan
    260 6(7)S— 1,4-diNHC6H2-2,4,6-triCH3 cyan
    261 6(7)SO2— 1,4-diNHC6H5-2-CH3, 6-C2H5 cyan
    262 4-NH— 1,8-diOH, 5-NO2 blue
    263 4-NH— 1,8-diOH, 5-NH2 blue
    264 4-NH— 1,8-diOH, 5-NHC6H5 blue
    265 4-NH— 1,5-diOH, 8-NO2 blue
    266 4-NH— 1-NH2, 2-CN cyan
    267 4-NH— 1-NH2, 2-S—C6H5 blue
    268 4-NH—
    Figure US20040195552A1-20041007-C00312
         		blue
    269 4-NH—
    Figure US20040195552A1-20041007-C00313
         		blue
  • [0327]
    TABLE 11
    Polydyes From Diacidic Anthraquinone Compounds of Formula XV
    Figure US20040195552A1-20041007-C00314
    Example No.
    Figure US20040195552A1-20041007-C00315
         		R14 Color
    270 2,4-di-S—C6H4-3-CO2H 1-NH2 red
    271 2,3-di-S—C2H4-4-CO2H 1,4-diNH2 blue
    272 2,4-di-S—C6H4-2-CO2H 1-NHCH3 violet
    273 2-SO2C6H4-2-CO2H, 4-NHC6H4-2- 1-NH2 blue
    CO2H
    274 2-OC6H4-4-CO2H, 4-NHC6H4-2- 1-NH2 violet
    CO2H
    275 2-OC6H4-3-CO2H, 4-S—NHC6H4-2- 1-NH2 red
    CO2H
    276 2,4-di-S—C6H4-2-CO2H 1-OH orange
    277 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH3 blue
    278 4,5-di-S—C6H4-3-CO2H 1,8-diNHCH2CH(CH3)2 blue
    279 4,5-di-S—C6H4-4-CO2H 1,8-diNH(CH2)7CH3 blue
    280 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2(C2H5)C2H9-n blue
    281 4,5-di-S—C6H4-2-CO2H 1,8-diNHC6H4-4-CH3 blue
    282 4,5-di-S—C6H4-2-CO2H 1,8-diNHC6H11 blue
    283 4,5-di-S—C6H4-2-CO2H 1,8-diNH(CH2)3OH blue
    284 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2C(CH3)2CH2OH blue
    285 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2C6H5 blue
    286 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2CH2C6H5 blue
    287 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2CH═CH2 blue
    288 4,5-di-S—C6H4-2-CO2H 1,8-diNHCH2C≡CH blue
    289 4,5-di-S—C6H4-2-CO2H
    Figure US20040195552A1-20041007-C00316
         		blue
    290 4,8-di-S—C6H4-2-CO2H 1,5-diNHC2H5 blue
    291 4,8-di-S—C6H4-2-CO2H 1,5-diNHCH2CH(CH3)CN blue
    292 4,8-di-S—C6H4-4-CO2H 1,5-diNHCH2CH2NHCOCH3 blue
    293 4,8-di-S—C6H4-2-CO2H 1,5-diNH(CH2)3OC2H5 blue
    294 4,8-di-S—C6H4-2-CO2H 1,5-diNHCH2C6H10-4-CH3 blue
    295 4,8-di-S—C6H4-2-CO2H
    Figure US20040195552A1-20041007-C00317
         		blue
    296 4,8-di-S—C6H4-2-CO2H
    Figure US20040195552A1-20041007-C00318
         		blue
    297 4,8-di-S—C6H4-2-CO2H 1,5-diNH(CH2)3OC6H5 blue
    298 4,8-di-S—C6H4-2-CO2H 1,5-diNHCH(CH3)(CH2)2C6H5 blue
    299 4,8-di-S—C6H4-2-CO2H 1,5-diNHCH(CH2CH3)2 blue
    300 4,8-di-S—C6H4-2-CO2H 1,5-diSCH2CH2OH red
    301 4,8-di-S—C6H4-2-CO2H 1,5-diSCH2C6H5 red
    302 4,8-di-S—C6H4-2-CO2H 1,5-diSC6H5 red
    303 4,8-di-S—C6H4-2-CO2H 1,5-diSC6H11 red
    304 4,8-di-S—C6H4-2-CO2H 1,5-diSC6H4-4-OCH3 red
    305 4,8-di-S—C6H4-2-CO2H 1,5-diSC6H4-4-Cl red
    306 4,5-di-S—C6H4-3-CO2H 1,8-diSC6H4-4-CH3 red
    307 4,5-di-S—C6H4-2-CO2H 1,8-diSC6H3-3,4-diCl red
    308 4,5-di-S—C6H4-2-CO2H 1,8-diSC6H4-2-NHCOCH3 red
    309 4,5-di-S—C6H4-2-CO2H 1,8-diSC6H4-4-NHCOC6H5 red
    310 4,5-di-S—C6H4-2-CO2H 1,8-diSCH2CH2OCOCH3 red
    311 4,8-di-S—C6H4-2-CO2H 1,5-diSC6H4-4-C(CH3)3 red
    312 4,8-di-S—C6H4-2-CO2H 1,5-dibenzothiazol-2-ylthio red
    313 4,8-di-S—C6H4-2-CO2H 1,5-dibenzoxazol-2-ylthio red
    314 4,8-di-S—C6H4-2-CO2H
    Figure US20040195552A1-20041007-C00319
         		red
    315 2,6-di-S—C6H4-2-CO2H 1,5-diNH2, 4,8-diOH blue
    316 2,6-di-O—C6H4-2-CO2H 1,4,5,8-tetra NH2 blue
    317 4,8-di-S—C6H4-2-CO2H 1,5-diNH2, 2,6-diBr blue
    318 2,7-di-S—C6H4-2-CO2H 1,8-diNH2, 4,5-diNHCO2CH3 blue
    319 2,7-di-SO2—C6H4-2-CO2H 1,8-diNH2, 4,5-diOH cyan
    320 4,5-di-S—C6H4-2-CO2H 1,8-diNHCOCH3 orange
    321 2,7-di-S—C6H4-2-CO2H 1,8-diNH2, 4,5-diNHC6H5 cyan
    322 2,6-di-O—C6H4-2-CO2H 1,8-diNH2, 4,5-diNHC6H11 blue
    323 2,8-di-SO2—C6H4-4-CO2H 1,4,5,8-tetra NH2 cyan
    324 4,8-di-S—C6H4-2-CO2H
    Figure US20040195552A1-20041007-C00320
         		blue
    325 2,3-di-O—C6H4-4-CO2H 1,4-diNH2 violet
    326 2,3-di-SO2—C6H4-2-CO2H 1,4-diNH2 blue
  • [0328]
    TABLE 12
    Polydyes From Diacidic Anthraquinone Compounds of Formula XVI
    Figure US20040195552A1-20041007-C00321
    Example No.
    Figure US20040195552A1-20041007-C00322
         		R14 Color
    327
    Figure US20040195552A1-20041007-C00323
         		1,4-diOH orange
    328
    Figure US20040195552A1-20041007-C00324
         		1-di-NH2 violet
    329
    Figure US20040195552A1-20041007-C00325
         		1-NH2, 4-OH red
    330
    Figure US20040195552A1-20041007-C00326
         		1-NH2, 4-NHC6H5 violet
    331
    Figure US20040195552A1-20041007-C00327
         		1-NH2, 4-NHC6H4-4-Cl blue
    332
    Figure US20040195552A1-20041007-C00328
         		1-NH2, 4-NHC6H4-4-OCH3 blue
    333
    Figure US20040195552A1-20041007-C00329
         		1-NH2, 4-NHSO2C4H9-n red
    334
    Figure US20040195552A1-20041007-C00330
    Figure US20040195552A1-20041007-C00331
         		red
    335
    Figure US20040195552A1-20041007-C00332
    Figure US20040195552A1-20041007-C00333
         		blue- green
    336
    Figure US20040195552A1-20041007-C00334
         		1-NH2, 2-Br blue
    337
    Figure US20040195552A1-20041007-C00335
         		1-NH2SO2C6H3-3,4-diCl blue
    338
    Figure US20040195552A1-20041007-C00336
         		1-NH2, 2-CN cyan
    339
    Figure US20040195552A1-20041007-C00337
         		1-NH2, 2-NO2 cyan
    340
    Figure US20040195552A1-20041007-C00338
         		1-NH2, 2-Br blue
    341
    Figure US20040195552A1-20041007-C00339
         		1-NH2, 2-SO2N(C2H5)2 blue
    342
    Figure US20040195552A1-20041007-C00340
         		1-NH2, 4-NHC6H4-3-Cl blue
    343
    Figure US20040195552A1-20041007-C00341
         		1,8-diOH, 5-NO2 blue
    344
    Figure US20040195552A1-20041007-C00342
         		1,5-diOH, 8-NH2 blue
  • [0329]
    TABLE 13
    Polydyes From Diacidic Anthrapyridone Compounds of Formula XVIII
    Figure US20040195552A1-20041007-C00343
    Example No.
    Figure US20040195552A1-20041007-C00344
         		R14 R15 R16 Color
    345
    Figure US20040195552A1-20041007-C00345
         		H CO2C2H5 CH3 red
    346
    Figure US20040195552A1-20041007-C00346
         		H CN CH2CH(CH3)2 violet
    347
    Figure US20040195552A1-20041007-C00347
         		H H C4H9-n red
    348
    Figure US20040195552A1-20041007-C00348
         		H Cl C6H11 red
    349
    Figure US20040195552A1-20041007-C00349
         		H
    Figure US20040195552A1-20041007-C00350
         		CH3 red
    350
    Figure US20040195552A1-20041007-C00351
         		H CN C6H5 violet
    351
    Figure US20040195552A1-20041007-C00352
         		H
    Figure US20040195552A1-20041007-C00353
         		CH3 violet
    352
    Figure US20040195552A1-20041007-C00354
         		H SO2C6H5 CH3 reddish blue
    353
    Figure US20040195552A1-20041007-C00355
         		4-CH3 CO2C2H5 H red
    354
    Figure US20040195552A1-20041007-C00356
         		H CO2C2H5 H orange
    355
    Figure US20040195552A1-20041007-C00357
         		H CN CH3 scarlet
    356
    Figure US20040195552A1-20041007-C00358
         		6-NHC6H5 CN CH3 violet
    357
    Figure US20040195552A1-20041007-C00359
         		6-NHC6H4-4-CH3 CO2C2H5 CH3 red
    358
    Figure US20040195552A1-20041007-C00360
         		6-NHC6H5 H CH3 red
    359
    Figure US20040195552A1-20041007-C00361
         		H COC6H5 CH2CH2OC2H5 red
    360
    Figure US20040195552A1-20041007-C00362
         		H CN (CH2)7CH3 violet
    361
    Figure US20040195552A1-20041007-C00363
         		4-Br CN CH3 violet
  • [0330]
    TABLE 14
    Polydyes From Diacidic Anthraquinone Compounds of Formula XIX
    Figure US20040195552A1-20041007-C00364
    Example No.
    Figure US20040195552A1-20041007-C00365
         		R14 Color
    362
    Figure US20040195552A1-20041007-C00366
         		H red
    363
    Figure US20040195552A1-20041007-C00367
         		H red
    364
    Figure US20040195552A1-20041007-C00368
         		H red
    365
    Figure US20040195552A1-20041007-C00369
         		H red
    366
    Figure US20040195552A1-20041007-C00370
         		1,4-diNH2 blue
    367
    Figure US20040195552A1-20041007-C00371
         		1,8-diNHCH2CH(CH3)2 blue
    368
    Figure US20040195552A1-20041007-C00372
         		1,5-diSC6H5 red
    369
    Figure US20040195552A1-20041007-C00373
    Figure US20040195552A1-20041007-C00374
         		red
    370
    Figure US20040195552A1-20041007-C00375
    Figure US20040195552A1-20041007-C00376
         		cyan
    371
    Figure US20040195552A1-20041007-C00377
    Figure US20040195552A1-20041007-C00378
         		cyan
    372
    Figure US20040195552A1-20041007-C00379
         		1,4-diNH2 violet
    373
    Figure US20040195552A1-20041007-C00380
         		1,8-diOH blue
    374
    Figure US20040195552A1-20041007-C00381
         		1,8-diNHC6H11 blue
    375
    Figure US20040195552A1-20041007-C00382
    Figure US20040195552A1-20041007-C00383
         		blue
    376
    Figure US20040195552A1-20041007-C00384
         		1,8-diNHCH2C(CH3)2CH2OH blue
    377
    Figure US20040195552A1-20041007-C00385
         		1,8-diNHCH2CH(C2H5)C4H9-n blue
    378
    Figure US20040195552A1-20041007-C00386
         		1,4,5,8-tetra NH2 blue
    379
    Figure US20040195552A1-20041007-C00387
         		1,8-diNH2, 4,5-diOH blue
    380
    Figure US20040195552A1-20041007-C00388
         		1,8-diNH2, 4,5-diNHC6H5 cyan
    381
    Figure US20040195552A1-20041007-C00389
         		H yellow
  • [0331]
    TABLE 15
    Polydyes From Diacidic Anthraquinone Compounds of Formula XIXc
    Figure US20040195552A1-20041007-C00390
    Example No.
    Figure US20040195552A1-20041007-C00391
         		R14 Color
    382
    Figure US20040195552A1-20041007-C00392
         		H green
    383
    Figure US20040195552A1-20041007-C00393
         		H blue
    384
    Figure US20040195552A1-20041007-C00394
         		H blue
    385
    Figure US20040195552A1-20041007-C00395
         		H blue
    386
    Figure US20040195552A1-20041007-C00396
         		H blue
    387
    Figure US20040195552A1-20041007-C00397
         		H blue
    388
    Figure US20040195552A1-20041007-C00398
         		1-NH2 red
    389
    Figure US20040195552A1-20041007-C00399
         		1,4-diNH2 violet
    390
    Figure US20040195552A1-20041007-C00400
         		1,4-diNH2 blue
    391
    Figure US20040195552A1-20041007-C00401
         		H red
    392
    Figure US20040195552A1-20041007-C00402
         		H red
    393
    Figure US20040195552A1-20041007-C00403
         		H red
    394
    Figure US20040195552A1-20041007-C00404
         		H red
    395
    Figure US20040195552A1-20041007-C00405
         		H red
    396
    Figure US20040195552A1-20041007-C00406
         		H red
  • [0332]
    TABLE 16
    Polydyes From Diacidic Anthraquinone Compounds of Formula XIXd
    Figure US20040195552A1-20041007-C00407
    Example No.
    Figure US20040195552A1-20041007-C00408
         		R14 Color
    397
    Figure US20040195552A1-20041007-C00409
         		H red
    398
    Figure US20040195552A1-20041007-C00410
         		1-NHC4H9-n blue
    399
    Figure US20040195552A1-20041007-C00411
         		1-NH2, 2-CN cyan
    400
    Figure US20040195552A1-20041007-C00412
         		1-NH2, 2-SO2N(CH3)C6H5 blue
    401
    Figure US20040195552A1-20041007-C00413
         		1-NH2, 2-CF2 cyan
    402
    Figure US20040195552A1-20041007-C00414
    Figure US20040195552A1-20041007-C00415
         		blue
    403
    Figure US20040195552A1-20041007-C00416
         		1-NH2-2-OCH2CH22OH violet
    404
    Figure US20040195552A1-20041007-C00417
         		1-NH2-2-Br blue
    405
    Figure US20040195552A1-20041007-C00418
         		1-NH2, 2-SO2C6H5 blue
    406
    Figure US20040195552A1-20041007-C00419
         		1-NH2-2-Br blue
    407
    Figure US20040195552A1-20041007-C00420
         		1-NH2-4-OH red
    408
    Figure US20040195552A1-20041007-C00421
         		1,4-diNH2 violet
    409
    Figure US20040195552A1-20041007-C00422
    Figure US20040195552A1-20041007-C00423
         		violet
    410
    Figure US20040195552A1-20041007-C00424
    Figure US20040195552A1-20041007-C00425
         		red
    411
    Figure US20040195552A1-20041007-C00426
    Figure US20040195552A1-20041007-C00427
         		red
    412
    Figure US20040195552A1-20041007-C00428
         		1-NH2, 4-NHC6H5 blue
    413
    Figure US20040195552A1-20041007-C00429
         		1-NH2, 4-NHC6H11 blue
    414
    Figure US20040195552A1-20041007-C00430
         		1-NH2, 4-NHC6H5 blue
  • [0333]
    TABLE 17
    Polydyes From Diacidic Anthraquinone Compounds of Formula XIXe
    Figure US20040195552A1-20041007-C00431
    Example No.
    Figure US20040195552A1-20041007-C00432
         		R14 Color
    415
    Figure US20040195552A1-20041007-C00433
         		H red
    416
    Figure US20040195552A1-20041007-C00434
         		1-NHCH3 blue
    417
    Figure US20040195552A1-20041007-C00435
         		1-OH violet
    418
    Figure US20040195552A1-20041007-C00436
         		1-NH2-2-Br blue
    419
    Figure US20040195552A1-20041007-C00437
         		1-NH2-2-OC6H5 violet
    420
    Figure US20040195552A1-20041007-C00438
         		1-NH2-2-SO2CH3 blue
    421
    Figure US20040195552A1-20041007-C00439
         		1-NH2-2-COC6H5 blue
    422
    Figure US20040195552A1-20041007-C00440
         		1-NH2-2-CF3 cyan
    423
    Figure US20040195552A1-20041007-C00441
         		1-NH2-2-CONH2 blue
    424
    Figure US20040195552A1-20041007-C00442
         		1-NH2-2-SO2N(CH3)2 blue
    425
    Figure US20040195552A1-20041007-C00443
         		1-NHC6H11 blue
    426
    Figure US20040195552A1-20041007-C00444
         		1-NHC6H5 green
    427
    Figure US20040195552A1-20041007-C00445
         		1-NH2, 4-OH red
    428
    Figure US20040195552A1-20041007-C00446
         		1-NH2, 4-NHSO2CH3 red
    429
    Figure US20040195552A1-20041007-C00447
         		1-NH2-4-NHCO2C2H5 red
    430
    Figure US20040195552A1-20041007-C00448
         		1-NH2-4-NHSO2C6H5 red
    431
    Figure US20040195552A1-20041007-C00449
         		1-NH2-4-NHCOC2H5 red
    432
    Figure US20040195552A1-20041007-C00450
         		1,4-diNH2 violet
    433
    Figure US20040195552A1-20041007-C00451
         		1-NH2-4-NHC6H5 blue
    434
    Figure US20040195552A1-20041007-C00452
         		1,8-diOH, 5-NO2 blue
    435
    Figure US20040195552A1-20041007-C00453
         		1-NH2-2-SO2C6H5 blue
  • [0334]
    TABLE 18
    Polydyes From Diacidic Anthraquinones of Formula XIXf
    Figure US20040195552A1-20041007-C00454
    Example No.
    Figure US20040195552A1-20041007-C00455
         		R14 Color
    436
    Figure US20040195552A1-20041007-C00456
         		H blue
    437
    Figure US20040195552A1-20041007-C00457
         		H blue
    438
    Figure US20040195552A1-20041007-C00458
         		H green
    439
    Figure US20040195552A1-20041007-C00459
         		H green
    440
    Figure US20040195552A1-20041007-C00460
         		H red
    441
    Figure US20040195552A1-20041007-C00461
         		H red
    442
    Figure US20040195552A1-20041007-C00462
         		1,4-diNH2 violet
    443
    Figure US20040195552A1-20041007-C00463
         		1,4-diNH2 blue
    444
    Figure US20040195552A1-20041007-C00464
         		H red
    445
    Figure US20040195552A1-20041007-C00465
         		4,8-diNH2, 3,7-diBr blue
    446
    Figure US20040195552A1-20041007-C00466
         		1-NH2 red
    447
    Figure US20040195552A1-20041007-C00467
         		6,7-diCl cyan
    448
    Figure US20040195552A1-20041007-C00468
         		H blue
    449
    Figure US20040195552A1-20041007-C00469
         		H blue
  • [0335]
    TABLE 19
    Polydyes From Diacidic Anthrapyridines
    Example No. Anthrapyridines Color
    450
    Figure US20040195552A1-20041007-C00470
         		red
    451
    Figure US20040195552A1-20041007-C00471
         		bluish-red
    452
    Figure US20040195552A1-20041007-C00472
         		red
    453
    Figure US20040195552A1-20041007-C00473
         		orange
    454
    Figure US20040195552A1-20041007-C00474
         		violet
    455
    Figure US20040195552A1-20041007-C00475
         		red
  • [0336]
    TABLE 20
    Polydyes From Diacidic Nitroarylamines
    Example No. Nitroarylamine Compound Color
    456
    Figure US20040195552A1-20041007-C00476
         		yellow
    457
    Figure US20040195552A1-20041007-C00477
         		yellow
    458
    Figure US20040195552A1-20041007-C00478
         		yellow
    459
    Figure US20040195552A1-20041007-C00479
         		yellow
    460
    Figure US20040195552A1-20041007-C00480
         		yellow
    461
    Figure US20040195552A1-20041007-C00481
         		yellow
    462
    Figure US20040195552A1-20041007-C00482
         		yellow
    463
    Figure US20040195552A1-20041007-C00483
         		yellow
    464
    Figure US20040195552A1-20041007-C00484
         		yellow
    465
    Figure US20040195552A1-20041007-C00485
         		yellow
  • [0337]
    TABLE 21
    Miscellaneous Polydyes
    Example No. Diacidic Compound Reacted Disulfonate Compound Reacted Color
    466
    Figure US20040195552A1-20041007-C00486
         		CH3SO2O(CH3)2OSO2CH3 red
    467
    Figure US20040195552A1-20041007-C00487
    Figure US20040195552A1-20041007-C00488
         		orange
    468
    Figure US20040195552A1-20041007-C00489
    Figure US20040195552A1-20041007-C00490
         		yellow
    469
    Figure US20040195552A1-20041007-C00491
    Figure US20040195552A1-20041007-C00492
         		blue
    470
    Figure US20040195552A1-20041007-C00493
    Figure US20040195552A1-20041007-C00494
         		yellow
    471
    Figure US20040195552A1-20041007-C00495
    Figure US20040195552A1-20041007-C00496
         		blue
    472
    Figure US20040195552A1-20041007-C00497
    Figure US20040195552A1-20041007-C00498
         		yellow
    473
    Figure US20040195552A1-20041007-C00499
         		CH3SO2(OCH2CH2)3OSO2CH3 yellow
    474
    Figure US20040195552A1-20041007-C00500
         		CH3SO2OCH2CH2SCH2CH2OSO2CH3 red
    475
    Figure US20040195552A1-20041007-C00501
    Figure US20040195552A1-20041007-C00502
         		red
    476
    Figure US20040195552A1-20041007-C00503
    Figure US20040195552A1-20041007-C00504
         		violet
    477
    Figure US20040195552A1-20041007-C00505
    Figure US20040195552A1-20041007-C00506
         		yellow
    478
    Figure US20040195552A1-20041007-C00507
         		CH3SO2OCH2CH2OSO2CH3 orange
    479
    Figure US20040195552A1-20041007-C00508
         		CH3SO2OCH2CH2OCH2CH2OSO2CH3 orange
    480
    Figure US20040195552A1-20041007-C00509
         		CH3SO2OCH2CH(CH3)CH2OSO2CH3 yellow
    481
    Figure US20040195552A1-20041007-C00510
         		CH3CH2SO2OCH2CH2CH2OSO2CH2CH3 red
    482
    Figure US20040195552A1-20041007-C00511
         		n-C4H9SO2OCH2CH2CH2CH2OSO2C4H9-n yellow
    483
    Figure US20040195552A1-20041007-C00512
         		CH3SO2(CH2)3OSO2CH3 red
    484
    Figure US20040195552A1-20041007-C00513
    Figure US20040195552A1-20041007-C00514
         		orange
    485
    Figure US20040195552A1-20041007-C00515
    Figure US20040195552A1-20041007-C00516
         		reddish- yellow
    486
    Figure US20040195552A1-20041007-C00517
    Figure US20040195552A1-20041007-C00518
         		yellow
    487
    Figure US20040195552A1-20041007-C00519
    Figure US20040195552A1-20041007-C00520
         		blue
    488
    Figure US20040195552A1-20041007-C00521
    Figure US20040195552A1-20041007-C00522
         		orange
    489
    Figure US20040195552A1-20041007-C00523
    Figure US20040195552A1-20041007-C00524
         		yellow
    490
    Figure US20040195552A1-20041007-C00525
         		CH3OCH2SO2O(CH2)3OSO2CH2OCH3 yellow
    491
    Figure US20040195552A1-20041007-C00526
         		ClCH3SO2OCH2CH2OSO2CH2Cl yellow
    492
    Figure US20040195552A1-20041007-C00527
         		CH3SO2OCH2CH2OCH2CH2OSO2CH3 blue
    493
    Figure US20040195552A1-20041007-C00528
    Figure US20040195552A1-20041007-C00529
         		greenish- blue
    494
    Figure US20040195552A1-20041007-C00530
    Figure US20040195552A1-20041007-C00531
         		greenish- blue
    495
    Figure US20040195552A1-20041007-C00532
    Figure US20040195552A1-20041007-C00533
         		red
    496
    Figure US20040195552A1-20041007-C00534
         		CH3SO2OCH2CH2SO2CH2CH2OSO2CH3 orange
    497
    Figure US20040195552A1-20041007-C00535
         		CH3SO2O(CH2)12OSO2CH3 red
    498
    Figure US20040195552A1-20041007-C00536
    Figure US20040195552A1-20041007-C00537
         		blue
    499
    Figure US20040195552A1-20041007-C00538
    Figure US20040195552A1-20041007-C00539
         		orange
    500
    Figure US20040195552A1-20041007-C00540
         		CH3SO2O(CH2)3OSO2CH3 red
    501
    Figure US20040195552A1-20041007-C00541
         		CH3SO2OCH2CH2OSO2CH3 blue
    502
    Figure US20040195552A1-20041007-C00542
         		CH3SO2OCH2CH2OCH2CH2OSO2CH3 blue
    503
    Figure US20040195552A1-20041007-C00543
         		CH3SO2OCH2CH2SCH2CH2OSO2CH3 yellow
    504
    Figure US20040195552A1-20041007-C00544
    Figure US20040195552A1-20041007-C00545
         		reddish- yellow
    505
    Figure US20040195552A1-20041007-C00546
         		CH3SO2OCH2CH2OSO2CH3 red
  • [0338]
    TABLE 22
    Polymeric UV Absorbers
    Example No. Diacidic Compound Reacted
    506
    Figure US20040195552A1-20041007-C00547
    507
    Figure US20040195552A1-20041007-C00548
    508
    Figure US20040195552A1-20041007-C00549
    509
    Figure US20040195552A1-20041007-C00550
    510
    Figure US20040195552A1-20041007-C00551
    511
    Figure US20040195552A1-20041007-C00552
    512
    Figure US20040195552A1-20041007-C00553
    513
    Figure US20040195552A1-20041007-C00554
    514
    Figure US20040195552A1-20041007-C00555
    515
    Figure US20040195552A1-20041007-C00556
    516
    Figure US20040195552A1-20041007-C00557
    517
    Figure US20040195552A1-20041007-C00558
    518
    Figure US20040195552A1-20041007-C00559
    519
    Figure US20040195552A1-20041007-C00560
    520
    Figure US20040195552A1-20041007-C00561
    521
    Figure US20040195552A1-20041007-C00562
    522
    Figure US20040195552A1-20041007-C00563
    Example No. Disulfonate Compound Reacted
    506 CH3SO2O(CH2)3OSO2CH3
    507 CH3SO2OCH2CH2OSO2CH3
    508
    Figure US20040195552A1-20041007-C00564
    509 CH3SO2O(CH2)4OSO2CH3
    510 CH3SO2O(CH2)3OSO2CH3
    511 CH3SO2O(CH2)6OSO2CH3
    512 CH3SO2OCH2CH2OSO2CH3
    513 CH3SO2O(CH2)4OSO2CH3
    514 CH3SO2O(CH2)6OSO2CH3
    515 CH3SO2OCH2CH(CH3)CH2OSO2CH3
    516 CH3SO2O(CH2CH2O)3SO2CH3
    517 CH3SO2OCH2CH2OSO2CH3
    518 CH3SO2OCH2CH2SCH2CH2OSO2CH3
    519 CH3SO2O(CH2)6OSO2CH3
    520
    Figure US20040195552A1-20041007-C00565
    521
    Figure US20040195552A1-20041007-C00566
    522
    Figure US20040195552A1-20041007-C00567
  • [0339]
    TABLE 23
    Polymeric Infrared Light Absorbers
    Example No. Diacidic Compound Reacted Disulfonate Compound Reacted
    523
    Figure US20040195552A1-20041007-C00568
         		CH3SO2OCH2CH3OSO2CH3
    524
    Figure US20040195552A1-20041007-C00569
         		CH3SO2O(CH2)3OSO2CH3
    525
    Figure US20040195552A1-20041007-C00570
         		CH3SO2O(CH2)4OSO2CH3
    526
    Figure US20040195552A1-20041007-C00571
         		CH3SO2O(CH2)6OSO2CH3
    527
    Figure US20040195552A1-20041007-C00572
         		CH3SO2O(CH2)12OSO2CH3
    528
    Figure US20040195552A1-20041007-C00573
         		CH3SO2OCH2CH2OCH2CH2OSO2CH3
    529
    Figure US20040195552A1-20041007-C00574
         		CH3SO2OCH2CH2OSO2CH3
    530
    Figure US20040195552A1-20041007-C00575
         		CH3SO2OCH2CH2CH2OSO2CH3
    531
    Figure US20040195552A1-20041007-C00576
         		CH3SO2OCH2CH2OSO2CH3
    532
    Figure US20040195552A1-20041007-C00577
         		CH3SO2OCH2CH2OSO2CH3
    533
    Figure US20040195552A1-20041007-C00578
         		CH3SO2OCH2CH2OSO2CH3
    534
    Figure US20040195552A1-20041007-C00579
         		CH3SO2OCH2CH2OSO2CH3
    Pc = phthalocyanine
    535
    Figure US20040195552A1-20041007-C00580
         		CH3SO2OCH2CH2OSO2CH3
    Nc = naphthalocyanine
    536
    Figure US20040195552A1-20041007-C00581
         		CH3SO2O(CH2)6OSO2CH3
    Pc = phthalocyanine
    • Example 537
  • To dimethylfomamide (DMF, 45.0 mL) was added 1,5-bis(2-carboxyphenyl-thio)anthraquinone (17.9 g, 0.035 mole). The mixture was stirred for about 10 minutes and then 1,8-diazabicyclo [5,4,0]undec-7-ene (DBU, 10.4 g, 0.068 mole) was added followed by 1,2-ethanediol, dimethanedisulfonate (7.64 g, 0.035 mole) and additional DMF (10.0 mL). The reaction mixture was stired at about 110° C. for 3.0 hours and allowed to cool to about 55° C. Methanol (35.0 g) was added dropwise with stirring followed by water (20 mL) and acetic acid (3.0 mL). The yellow solid was collected by filtration, washed with methanol (25 mL), warm water (50 mL) and then finally with methanol to facilitate drying. The yield of polymeric and cyclic yellow product was 18.2 g. [0340]
    • Examples 538-543
  • The procedure described in Example 537 was repeated exactly except that the reactant X-B-X[0341] 1 used in each example was as follows:
  • Example 538: 1,3-propanediol, dimethanedisulfonate [0342]
  • Example 539: 1,4-butanediol, dimethanedisulfonate [0343]
  • Example 540: diethylene glycol, dimethanedisulfonate [0344]
  • Example 541: 1,6-hexanediol, dimethanedisulfonate [0345]
  • Example 542: 1,4-cyclohexanedimethanol, dimethanedisulfonate [0346]
  • Example 543: 1,12-dodecanediol, dimethanedisulfonate [0347]
  • The weight yields (Weight, g), percent yields (Yield), weight average molecular weights (Mw), number average molecular weights (Mn), and polydispersities (Mw/Mn, by GPC) for each of the light absorbing (yellow) compositions prepared in Examples 537-543 are presented in Table 24. [0348]
  • The percent yields were calculated by dividing the actual weight of the polymer [0349]
  • A−n
  • obtained in grams by the theoretical number of moles of repeating unit multiplied by the gram molecular weight of the repeating unit and then multiplying the number thus obtained by 100. [0350]
    TABLE 24
    Example Weight Yield Mw Mn Mw/Mn
    537 18.2 96.6 7,512 1,106 6.8
    538 18.8 97.2 5,224 1,051 5.0
    539 19.4 98.0 13,856 1,202 11.5
    540 20.1 98.7 9,849 1,840 5.4
    541 20.2 97.4 7,396 870 8.5
    542 20.7 95.3 3,685 808 4.6
    543 22.7 95.5 5,503 1,116 4.9
  • The approximate amount of cyclic compounds of formula I-A present in each of the light absorbing compositions produced in Examples 537-543 was determined by a combination of GPC, NMR and FDMS analyses. The weight percentages of the cyclic compounds having the structure [0351]
    Figure US20040195552A1-20041007-C00582
  • wherein m is 1, 2, 3, or 4 present in the compostiion of Examples 537-543 is set forth in Table 25. The remainder or balance of the light absorbing compositions was presumed to be a linear polymer. [0352]
    TABLE 25
    Example m = 1 m = 2 m = 3 m = 4
    537 0.1 3.4 1.5 0.7
    538 0.8 3.3 1.3 <0.1
    539 6.9 4.1 1.3 0.2
    540 9.5 3.1 0.8 <0.1
    541 26.7 4.0 1.1 0.2
    542 20.4 4.0 0.7 <0.1
    543 20.1 2.2* 0.5* <0.1

Claims (11)

1-58. (canceled)
59. The diacidic anthraquinone compounds having Formulae
Figure US20040195552A1-20041007-C00583
wherein R14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylamino, halogen, C1-C6 alkoxy, C1-C6 alkylthio, aryl, aroyl, C1-C6 alkanoyl, C1-C6 alkanoyloxy, NHCO C1-C6 alkyl, NHCOaryl, NHCO2 C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl, C1-C6 alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO2C1-C6 alkyl, SO2 aryl, —SO2NH C1-C6 alkyl, —SO2N(C1-C6 alkyl)2, —SO2N(C1-C6 alkyl) aryl, CONFH C1-C6 alkyl, CON(C1-C6 alkyl)2, CON(C1-C6 alkyl) aryl, C1-C6 alkyl, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino,
Figure US20040195552A1-20041007-C00584
or hydroxy; Q and Q′ are independently selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; R16′ is selected from hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy; wherein each C1-C6 alkyl group and [[C1-C6 alkyl group]] C1-C6 alkyoxy group which is a portion of another group may contain at least one substituent selected from the group consisting of hydroxy, cyano, chlorine, fluorine, C1-C6 alkoxy, C3-C8 cycloalkoxy, C1-C6 alkylcyclohexyl, hydroxmethyl cyclohexyl, aryl and heteroaryl; with the provision that two acidic groups containing one acidic proton each or one acidic group containing two acidic hydrogens be present in the compounds of Formula XIV, XIXc, XIXd, XIXe XIXf.
60. The diacidic anthraquinone compounds having the following structures:
Figure US20040195552A1-20041007-C00585
wherein Sub is a substituent selected from the group consisting of halogen, trifluoromethyl, aroyl, C1-C6 alkanoyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, aryloxy, arylthio, heteroarylthio, cyano, nitro, SO2NHC1-C6 alkyl, SO2N (C1-C6 alkyl)2, SO2N (C1-C6 alkyl) aryl, CONH C1-C6 alkyl, CON (C1-C6 alkyl)2, CON (C1-C6 alkyl) aryl, C1-C6 alkyl, SO2 C1-C6 alkylsulfonyl and SO2 aryl; Sub1 is a substituent selected from the group consisting of amino, C1-C12 alkylarnino, arylamino and C3-C8 cycloalkylamino. Q′ is selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; and R16′ is selected from hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy.
61-62. (canceled)
63. The diacidic anthraquinone compounds having the formulae
Figure US20040195552A1-20041007-C00586
where R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy; and Sub3 is a substituent selected from C1-C6 alkylthio, arylthio and heteroarylthio and Sub2 is a substituent selected from the group consisting of amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylamino, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino, NHCO C1-C6 alkyl, NHCO aryl, NHCO2 C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl and
Figure US20040195552A1-20041007-C00587
64. The diacidic anthraquinone compounds of claim 59 having the formulae:
Figure US20040195552A1-20041007-C00588
wherein Sub2 is a substituent selected from the group consisting of amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylamino, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino, NHCO C1-C6 alkyl, NHCO aryl, NHCO2 C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl and
Figure US20040195552A1-20041007-C00589
Sub4 is selected from the group consisting of Sub2, NHCO C1-C6 alkyl, NHCO2 C1-C6 alkyl, NHCO aryl, NHSO2 C1-C6 alkyl, NHSO2 aryl, C1-C6 alkylthio, arylthio, heteroarylthio and hydroxy; Q is selected from the group consisting of —O—, S—, —SO2—; Q′ selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl.
65. A diacidic anthraquinone compounds having the formula
Figure US20040195552A1-20041007-C00590
wherein Sub is a substituent selected from the group consisting of halogen, trifluoromethyl, aroyl, C1-C6 alkanoyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxy, C1-C6 alkylthio, aryloxy, arylthio, heteroarylthio, cyano, nitro, SO2NHC1-C6 alkyl, SO2N (C1-C6 alkyl)2, SO2N (C1-C6 alkyl) aryl, CONH C1-C6 alkyl, CON (C1-C6 alkyl)2, CON (C1-C6 alkyl) aryl, C1-C6 alkyl, SO2 C1-C6 alkylsulfonyl and SO2 aryl; Sub1 is a substituent selected from the group consisting of amino, C1-C12 alkylamino, arylamino and C3-C8 cycloalkylamino, and R16′ is selected from hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy.
66. The diacidic anthraquinone compounds having the structures
Figure US20040195552A1-20041007-C00591
wherein Q is selected from the group consisting of —O—, —S— and —SO2—; Q′ is selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; and R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy.
67. The diacidic anthraquinone compounds having the structures:
Figure US20040195552A1-20041007-C00592
wherein Sub1 is a substituent selected from the group consisting of amino, C1-C12 alkylamino, arylamino and C3-C8 cycloalkylamino: Sub4 is selected from the group consisting of amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylaamino, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino, NHCO C1-C6 alkyl, NHCO aryl, NHCO2, C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl
Figure US20040195552A1-20041007-C00593
NHCO C1-C6 alkyl, NHCO2 C1-C6 alkyl, NHCO aryl, NHSO2 C1-C6 alkyl, NHSO2 aryl, C1-C6 alkylthio, arylthio, heteroarylthio and hydroxy: Q is selected from the group consisting of —O—, —S— and —SO2—; Q′ is selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; and R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy.
68. The diacidic anthraquinone compounds having the structures:
Figure US20040195552A1-20041007-C00594
wherein Q is selected from the group consisting of —O—, —S— and —SO2—; Sub1 is a substitutent selected from the group consisting of amino, C1-C12 alkylamino, arylamino and C3-C8 cycloalkylamino; Q′ is selected from the group consisting of —O—, —N(COR10)—, —N(SO2R10)—, —N(R10)—, —S—, —SO2—, —CO2—, —CON(R10)—, SO2N (R10)—, wherein R10 is selected from the group consisting of hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; and R16′ is selected from the group consisting of hydrogen or one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy.
69-108. (canceled)
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