CA1254344A - Carboxylate containing modified acrylamide polymers - Google Patents
Carboxylate containing modified acrylamide polymersInfo
- Publication number
- CA1254344A CA1254344A CA000529033A CA529033A CA1254344A CA 1254344 A CA1254344 A CA 1254344A CA 000529033 A CA000529033 A CA 000529033A CA 529033 A CA529033 A CA 529033A CA 1254344 A CA1254344 A CA 1254344A
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- CA
- Canada
- Prior art keywords
- mixtures
- ranges
- polymer
- occurrence
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- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
Abstract
ABSTRACT
A high temperature, pressurized process is described to synthesize substituted carboxylated modified acrylamide polymers represented by the structure:
wherein M is chosen from hydrogen, lower alkyl (C1-C4) groups, alkali metal, alkaline earth metal, primary, secondary or tertiary amine salts, quaternary amines and ammonium ion, and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic and olefinic groups, and mixtures thereof (functional groups);
X is chosen from -SO3M - PO3M2, -COOR' -OR, -R'NR"2, -R'N+R3 Hal (OCH2?H) OR, and mixtures thereof; wherein R" is (CH2?HO)pR, R and mixtures thereof, and R is individually chosen, at each occurrence, from H and lower alkyl (C1-C4) groups; and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a + b) is from 20:1 to 1:100; and wherein p ranges between 1 and 16, and m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is from 1 to 20. These water soluble polymers are useful in various water treatment procedures, such as heat exchanger scale inhibition.
A high temperature, pressurized process is described to synthesize substituted carboxylated modified acrylamide polymers represented by the structure:
wherein M is chosen from hydrogen, lower alkyl (C1-C4) groups, alkali metal, alkaline earth metal, primary, secondary or tertiary amine salts, quaternary amines and ammonium ion, and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic and olefinic groups, and mixtures thereof (functional groups);
X is chosen from -SO3M - PO3M2, -COOR' -OR, -R'NR"2, -R'N+R3 Hal (OCH2?H) OR, and mixtures thereof; wherein R" is (CH2?HO)pR, R and mixtures thereof, and R is individually chosen, at each occurrence, from H and lower alkyl (C1-C4) groups; and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a + b) is from 20:1 to 1:100; and wherein p ranges between 1 and 16, and m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is from 1 to 20. These water soluble polymers are useful in various water treatment procedures, such as heat exchanger scale inhibition.
Description
Water-soluble polymers are available through various procedures, including condensation polymerization, vinyl poly-merization using various free radical catalysts or other catalytic or initiation devices, and even chemical modification of existing polymers by subsequent chemical reaction, such as hydrolysis of pendant amide functional groups to carboxylic acid groups. Chemical modification of existing polymers to achieve water solubility can however lead to other difficulties such as loss of molecular weight and unwanted changes in molecular weight distribution or even cross-linking and possible loss of water solubility. It would therefore be an advance in the art if other water-soluble polymeric chemical structures could be synthesized on a polymeric backbone which structures would con-tain the carboxylate functional groups, either in the acid or base form, and which structures might also contain multiple and various functional groups which could enhance the use of these water-soluble polymers in certain applications such as disper-sants in water treatment, scale inhibitors in natural and in-dustrial waters, flocculants and coagulants, and the like.
Therefore, this invention seeks to provide water-soluble polymers containing various functional groups and, in addition, which polymers may also contain multiple functional groups which may be useful when applied to aqueous solutions or environments.
Additionally, this invention seeks to develop a synthetic procedure which can generally be applicable to the synthesis of various types of water-soluble polymers containing the various functional groups with or without the additional presence of other functional groups which may be useful when these polymers are added to aqueous systems.
*
i~S~3~
In another aspect this invention seeks both to syn-thesize and to recover certain types of carboxylate containing water-soluble polymers, which polymers may contain other functional groups such as sulfonate, ether, alkoxyl, ester groups, and/or mixtures thereof, which polymers have not hereto-fore been known or used.
THE INVENTION
A process is now provided for modifying water-soluble polymers containing pendant amide functional groups, such poly-mers primarily derived from acrylamide-containing vinylic polymers/copolymers or from alkyl substituted acrylamide-containing vinylic polymers or copolymers, and which polymers/
copolymers are water soluble and contain pendant amide functional groups derived from acrylamide, methyl acrylamide, ethylacryl-amide, and the like.
The process which has been discovered uses the equivalent of a transamidation reaction with the pendant amide group on the polymer and a chemical reactant represented by the structure (I):
R
HN ~R' ) ( COOM)n (I) (X)m wherein: R is individually chosen, in each occurrence, from the group consisting of hydrogen and lower alkyl groups containing from 1-4 carbon atoms;
M is chosen from the group consisting of hydrogen, lower alkyl (Cl-C4) groups, alkali metals, alkaline earth metals, protonated amines, quaternary ammonium and ammonium ions, and mixtures thereof;
1~543~
R' is a multi-valent hydrocarbonaceous bridging group which may be linear, branched, cyclic, aromatic, heterocyclic, and mixtures thereof, and having from 1-16 carbon atoms;
X is chosen from -S03M,-OR,-~OCH2CH~-pQR, -NR"3 -NR" 4 and mixtures thereof, and R" is chosen from (CH2CHO) pR, R-R' -NR" 3, -R' NR" 3, -PO3M2 R
and mixtures thereof:
0 and wherein, p ranges from 1-16 m ranges between 0 and 16, n ranges between 1 and 16, provided that the sum of m + n is between 1-20.
THE CHEMICAL REACTANT
The chemical reactant described above is primarily a primary or secondary amino substituted compound which also con-tains the carboxylate functional group in either the free acid form, an ester form, a salt form, or any combination thereof, and wherein the amine functional group contains at least one active hydrogen substituted on the amino nitrogen. Although carboxylate compounds having both primary and secondary amines can react under these transamidation reaction conditions to achieve modified carboxylate containing polymers, it is prefer-able that when a secondary amine is chosen to accomplish this modification of pendant amide containing polymers, that the alkyl group substituted on the amino nitrogen contain no more than 4 carbon atoms, i.e. the alkyl substitution should be limited to methyl, ethyl, propyl and butyl functionality, or isomers there-of.
12S~3'~'~
However, it is most preferred that the amine substitu-tion on the carboxylate containing chemical reactant be a primary amino functional group. When a primary amino functional group is used to accomplish the transamidation reaction, the reaction easily proceeds so as to incorporate at least 2, and preferably at least 60, mole percent of the chemical reactant used into the water-soluble polymer chain containing pendant amide groups.
In addition to the amine substitution in the chemical reactant described above, this chemical reactant does contain at least one carboxylate functional group in either its ester form, acid form or its salt form, wherein the salt form is chosen from a salt of an alkali metal, an alkaline earth metal, primary, sec-ondary or tertiary amines, quaternary amines and ammonium ions, and mixtures thereof. The salt form may be in existence prior to the transamidation reaction or it may be synthesized by vary-ing pH with bases containing alkali metals, alkaline earth metals, tertiary amines, quaternary amine bases, or ammonia either prior to, or during the transamidation reaction, or after the trans-amidation reaction has been completed.
In addition to the carboxylate functional group andthe amine functional group, the chemical reactant may also con-tain other functional groups chosen from the groups consisting of sulfonate, phosphonate, alcaholic, ether, ester, alkoxylgroups, tertiary amino, quaternary amino groups, and mixtures thereof.
Preferably, the chemical reactant is limited to contain a prim-ary amino group responsible for the transamidation reaction, at least one carboxylate group which allows the formation of an anionic carboxylate containing water-soluble polymer, and a sul-fonate, phosphonate, or alkoxyl functional group, the presenceof which may enhance the activity of water-soluble carboxylate containing polymers synthesized by this process.
Il iZS~3'~
Most preferably, the chemical reactant contains a primary amine, one or more carboxyl groups, and one or more carboxylate groups eithe- in the free acid form, salt form, or mixtures of the free acid and salt forms.
Several preferred species of the chemical reactant described above are demonstrated in the following formulations:
Formula II.
a. C-O
b. C=O
OH
ll C. O-CH2CH20H
H2N--CH2CH-C 02M 'i ll d. H2N-CH2-fH-CH2C2 OcH2cH2ocH2cH2oH
SO 3~a e. H2N - CH2cH2cH2 ~ COOH
i2S43'~
THE PENDdNT ACRYLAMIDf CONTAINING POLYMERS
The pendant acrylamide containing polymers are water-soluble polymers which have a general structure allowing f the presence of a pendant amide group as demonstrated in Formula III:
formula III.
R~ ~ R
1=o C=O
Po lyme ~L~ Ba~kbone ~C ~0 In Formula III, as one can observe, the pendant amide group may be a primary amide, a secondary amide, or a tertiary amide compound or mixtures therof. Preferably, to obtain reasonable conversions of these pendant amide groups to the carboxylate containing functional groups described above, the pendant amide group is a primary amide group.
The most likely water-soluble polymers containing pendant amide functionality which polymers are easily modified under the conditions of my transamidation reaction, are those water-soluble polymers described by formula IV:
Formula IV.
- CH2 - I ~ 2 o N R 2 ,1 ~2s~3~
where the monomer block units of a and b are randomly distributed within the polymer chain.
R is independently chosen, at each occurrence, from the group consisting of hydrogen, and lower alkyl groups containing from 1-4 carbon atoms;
M is independently chosen, at each occurrence, from hydrogen, lower alkyl (Cl-C4) groups, alkali metals, alkaline earth metal and, amine salts, quaternary ammonium ions, ammonium ions and mixtures thereof;
and a and b are integers having the following relationships:
a/b ranges between 0 to 100, and a I b is sufficient so as to provide a polymer having a molecular weight of at least 5ûO. Preferably the sum, a t b, is sufficient to provide a molecular weight ranging between about 1,000-20,000,000.
As can be seen, the polymers described above may be homopolymers or copolymers of acrylamide or its alkylated homologs, i.e. methacrylamide and the like, or they may be cooolymers of acrylamide and its homologs sPecifically with acrylic acid or its homologs such as methacrylic acid and the like, or they may be terpolymers and above with other vinylic monomers which terpolymers and above contain acrylamide or its amide homologs with acrylic acid, and their various homologs such as methyacrylic acid, methacylamide, and the like, and other additional vinylic monomers such as ethyl acrylate, methylacrylate, ethylene, propylene, vinyl sulfonate, and ~he like.
S4~
THE CHEMICAL REACTION
~ he chemical reaction which is preferred to obtain the carboxylated polymers of this invention is a reaction which can generally be referred to as a transamidation reaction~ This reaction substitutes an amine compound which may also contain other functional groups such as the carboxylate function group for the nitrogen portion of a pendant amide group contained on a polymeric backbone as described above. This transamidation reaction has been discovered to be a general reaction WhiCh can achieve the substitution ofthe amine and carboxylate containing reactant moiety for the amide nitrogen group of the pendant amide functionality of a water-soluble polymer, thereby obtaining unique carboxylated polymers.
The reaction conditions require that polymers containing pendant amide groups be dissolved or readily dispersed in a solvent which is a common solvent for the chemical reactant of the class described above. In other words, both the polymer which is to be modified and the chemical reactant should be soluble or dispersible in the same solvent system.
Common solvents which have ~een found useful in this reaction include, but are not limited to, ~ater, algiyme, dimethylformamide, dimethylsulfoxide, admixtures thereof, and admixtures of these solvents, either singly or taken together with other miscible solvents such as ethanol, tertiary butanol, glyme, and the like.
A Dreferred solvent which is a common solvent fo. both the polymer containing pendant ami~e groups and the chemical reactants above is water, Particularly if the polymer containing pendant amide group is initially water-soluble, as in the case of most acrylamide containing vinylic polymers. Another preferred 11 common solvent for my reaction is a water-in-oil emulsion wherein ¦
the dispersed water phase contains dissolved therein both the polymers containing pendant amide groups and the chemical eactants described above.
L lZS~34~
After having dissolved the polymers containing pendant amide groups in the common solvent, preferably water, the chemical reactant can be added to obtain a solution or dispersion of amide containing polymer and the chemical reactants of this invention. Whether the polymer or the reactant is first added to the common solvent is of no consequence. This admixture is then added to or contained in a reaction vessel capable of withstanding a pressurized chemical reaction, for example, a Parr Bomb type of vessel. The vessel is enclosed and then heated to a temperature of at least 100C, preferably at least 110C, and most preferably to a temperature of at least 120C. If the temperature is increased above 100C, the vessel contents can expand and the pressure within the vessel can exceed one atmosphere and depending upon the solvent, the carboxylate substituted reactants used and/or the reactants used, can reach up to about 5 to 15 atmospheres, and possibly more. The pressure within the reaction vessel is a non-controlled variable and is controlled only to the extent that the vessel is enclosed, that a reaction temperature of at least 100C or higher is reached, and the vessel may contain solvents or reactants of more or less volatile nature, which solvents and reactants have vapor pressures of such a nature that pressure vessels are required at temperatures above lû0C.
Once the reaction vessel contents have reached at least 100C, and preferably 110C, the reaction is allowed to occur for at least 3 minutes at this temperature, and preferably for whatever length of time is necessary to accomplish a minimum of at least a 2 percent conversion, and preferaoly at least from 25-6û percent conversion, of the added amount of chemical reactant. The chemical reactant is, of course, converted to a pendant carboxylate containlng substltuted amide, or the product of the transamidation chemical reaction summarizea above.
5~3 If the polymer is a homopolymer of acrylamide, methacrylamide, or a copolymer of vinyl amide containing monomers¦
such that no other pendant functional group is present besides amide functional groups, the condition of the reaction is such that at least some degree of amide hydrolysis may also occur in those reactions in which water or a water containing solvent is utilized. In such cases, a carboxylate functional group may also be obtained in addition to the carboxylate modified amide and any unreacted starting amide groups from the starting polymer. This is particularly true at very high pH, so it is advisable to operate the reactions in aqueous common solvents or in water-in-oil emulsion at initial pH of below 9.0, and preferably below 8Ø
Therefore, I have described the chemical reaction or process that accomplishes the synthesis of polymers with randomly distributed monomer units having the structure o formula V:
Formula V..
Li O=C O=C û=C
û NH2 ~R
. M (R') Xm ~COOM)n 5~
wherein M is chosen from hydrogen, a lower alkyl (Cl-C4) group, alkali metal, alkaline earth metal, primary, secondary or tertiary amine saltst quaternary amines and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous Dridging group having from one to sixteen carbon atoms and being chosen .
from linear, branched, cyclic, aromatic and heterocyclic (functional groups), and mixtures thereof;
X is chosen from -503M, -P03M2, -COOR, -OR, -R'NR"2, -R'NR"3,-~OCH2CH)pOR, and mixtures thereof; R
where R" is-~CH2CHO~-pR, R, and mixtures thereof;
R is individually chosen at each occurrence from H and lower alkyl (Cl-C4) groups;
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+o+d is sufficient to ~rovide a molecul3r weight of at least 1000, and the ratio of d:(a + o) is from 20:1 to 1:100;
and wherein p ranges between 1 and 16, and m ranges between O and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is between l-20;
I
43~
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, which polymer is represented by the structure:
~ C_C3~FC~
O:C O=C
M
wherein R, M, a, b have the same meanings as above;
with, 8. a chemical reactant having the structure:
R
HN--~--R' ) (COOM)n wherein R, R', M, X, m, and n have the meanings above; wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about 1:100; and the reaction occurs for an effective amount of time to accomplish at least a
Therefore, this invention seeks to provide water-soluble polymers containing various functional groups and, in addition, which polymers may also contain multiple functional groups which may be useful when applied to aqueous solutions or environments.
Additionally, this invention seeks to develop a synthetic procedure which can generally be applicable to the synthesis of various types of water-soluble polymers containing the various functional groups with or without the additional presence of other functional groups which may be useful when these polymers are added to aqueous systems.
*
i~S~3~
In another aspect this invention seeks both to syn-thesize and to recover certain types of carboxylate containing water-soluble polymers, which polymers may contain other functional groups such as sulfonate, ether, alkoxyl, ester groups, and/or mixtures thereof, which polymers have not hereto-fore been known or used.
THE INVENTION
A process is now provided for modifying water-soluble polymers containing pendant amide functional groups, such poly-mers primarily derived from acrylamide-containing vinylic polymers/copolymers or from alkyl substituted acrylamide-containing vinylic polymers or copolymers, and which polymers/
copolymers are water soluble and contain pendant amide functional groups derived from acrylamide, methyl acrylamide, ethylacryl-amide, and the like.
The process which has been discovered uses the equivalent of a transamidation reaction with the pendant amide group on the polymer and a chemical reactant represented by the structure (I):
R
HN ~R' ) ( COOM)n (I) (X)m wherein: R is individually chosen, in each occurrence, from the group consisting of hydrogen and lower alkyl groups containing from 1-4 carbon atoms;
M is chosen from the group consisting of hydrogen, lower alkyl (Cl-C4) groups, alkali metals, alkaline earth metals, protonated amines, quaternary ammonium and ammonium ions, and mixtures thereof;
1~543~
R' is a multi-valent hydrocarbonaceous bridging group which may be linear, branched, cyclic, aromatic, heterocyclic, and mixtures thereof, and having from 1-16 carbon atoms;
X is chosen from -S03M,-OR,-~OCH2CH~-pQR, -NR"3 -NR" 4 and mixtures thereof, and R" is chosen from (CH2CHO) pR, R-R' -NR" 3, -R' NR" 3, -PO3M2 R
and mixtures thereof:
0 and wherein, p ranges from 1-16 m ranges between 0 and 16, n ranges between 1 and 16, provided that the sum of m + n is between 1-20.
THE CHEMICAL REACTANT
The chemical reactant described above is primarily a primary or secondary amino substituted compound which also con-tains the carboxylate functional group in either the free acid form, an ester form, a salt form, or any combination thereof, and wherein the amine functional group contains at least one active hydrogen substituted on the amino nitrogen. Although carboxylate compounds having both primary and secondary amines can react under these transamidation reaction conditions to achieve modified carboxylate containing polymers, it is prefer-able that when a secondary amine is chosen to accomplish this modification of pendant amide containing polymers, that the alkyl group substituted on the amino nitrogen contain no more than 4 carbon atoms, i.e. the alkyl substitution should be limited to methyl, ethyl, propyl and butyl functionality, or isomers there-of.
12S~3'~'~
However, it is most preferred that the amine substitu-tion on the carboxylate containing chemical reactant be a primary amino functional group. When a primary amino functional group is used to accomplish the transamidation reaction, the reaction easily proceeds so as to incorporate at least 2, and preferably at least 60, mole percent of the chemical reactant used into the water-soluble polymer chain containing pendant amide groups.
In addition to the amine substitution in the chemical reactant described above, this chemical reactant does contain at least one carboxylate functional group in either its ester form, acid form or its salt form, wherein the salt form is chosen from a salt of an alkali metal, an alkaline earth metal, primary, sec-ondary or tertiary amines, quaternary amines and ammonium ions, and mixtures thereof. The salt form may be in existence prior to the transamidation reaction or it may be synthesized by vary-ing pH with bases containing alkali metals, alkaline earth metals, tertiary amines, quaternary amine bases, or ammonia either prior to, or during the transamidation reaction, or after the trans-amidation reaction has been completed.
In addition to the carboxylate functional group andthe amine functional group, the chemical reactant may also con-tain other functional groups chosen from the groups consisting of sulfonate, phosphonate, alcaholic, ether, ester, alkoxylgroups, tertiary amino, quaternary amino groups, and mixtures thereof.
Preferably, the chemical reactant is limited to contain a prim-ary amino group responsible for the transamidation reaction, at least one carboxylate group which allows the formation of an anionic carboxylate containing water-soluble polymer, and a sul-fonate, phosphonate, or alkoxyl functional group, the presenceof which may enhance the activity of water-soluble carboxylate containing polymers synthesized by this process.
Il iZS~3'~
Most preferably, the chemical reactant contains a primary amine, one or more carboxyl groups, and one or more carboxylate groups eithe- in the free acid form, salt form, or mixtures of the free acid and salt forms.
Several preferred species of the chemical reactant described above are demonstrated in the following formulations:
Formula II.
a. C-O
b. C=O
OH
ll C. O-CH2CH20H
H2N--CH2CH-C 02M 'i ll d. H2N-CH2-fH-CH2C2 OcH2cH2ocH2cH2oH
SO 3~a e. H2N - CH2cH2cH2 ~ COOH
i2S43'~
THE PENDdNT ACRYLAMIDf CONTAINING POLYMERS
The pendant acrylamide containing polymers are water-soluble polymers which have a general structure allowing f the presence of a pendant amide group as demonstrated in Formula III:
formula III.
R~ ~ R
1=o C=O
Po lyme ~L~ Ba~kbone ~C ~0 In Formula III, as one can observe, the pendant amide group may be a primary amide, a secondary amide, or a tertiary amide compound or mixtures therof. Preferably, to obtain reasonable conversions of these pendant amide groups to the carboxylate containing functional groups described above, the pendant amide group is a primary amide group.
The most likely water-soluble polymers containing pendant amide functionality which polymers are easily modified under the conditions of my transamidation reaction, are those water-soluble polymers described by formula IV:
Formula IV.
- CH2 - I ~ 2 o N R 2 ,1 ~2s~3~
where the monomer block units of a and b are randomly distributed within the polymer chain.
R is independently chosen, at each occurrence, from the group consisting of hydrogen, and lower alkyl groups containing from 1-4 carbon atoms;
M is independently chosen, at each occurrence, from hydrogen, lower alkyl (Cl-C4) groups, alkali metals, alkaline earth metal and, amine salts, quaternary ammonium ions, ammonium ions and mixtures thereof;
and a and b are integers having the following relationships:
a/b ranges between 0 to 100, and a I b is sufficient so as to provide a polymer having a molecular weight of at least 5ûO. Preferably the sum, a t b, is sufficient to provide a molecular weight ranging between about 1,000-20,000,000.
As can be seen, the polymers described above may be homopolymers or copolymers of acrylamide or its alkylated homologs, i.e. methacrylamide and the like, or they may be cooolymers of acrylamide and its homologs sPecifically with acrylic acid or its homologs such as methacrylic acid and the like, or they may be terpolymers and above with other vinylic monomers which terpolymers and above contain acrylamide or its amide homologs with acrylic acid, and their various homologs such as methyacrylic acid, methacylamide, and the like, and other additional vinylic monomers such as ethyl acrylate, methylacrylate, ethylene, propylene, vinyl sulfonate, and ~he like.
S4~
THE CHEMICAL REACTION
~ he chemical reaction which is preferred to obtain the carboxylated polymers of this invention is a reaction which can generally be referred to as a transamidation reaction~ This reaction substitutes an amine compound which may also contain other functional groups such as the carboxylate function group for the nitrogen portion of a pendant amide group contained on a polymeric backbone as described above. This transamidation reaction has been discovered to be a general reaction WhiCh can achieve the substitution ofthe amine and carboxylate containing reactant moiety for the amide nitrogen group of the pendant amide functionality of a water-soluble polymer, thereby obtaining unique carboxylated polymers.
The reaction conditions require that polymers containing pendant amide groups be dissolved or readily dispersed in a solvent which is a common solvent for the chemical reactant of the class described above. In other words, both the polymer which is to be modified and the chemical reactant should be soluble or dispersible in the same solvent system.
Common solvents which have ~een found useful in this reaction include, but are not limited to, ~ater, algiyme, dimethylformamide, dimethylsulfoxide, admixtures thereof, and admixtures of these solvents, either singly or taken together with other miscible solvents such as ethanol, tertiary butanol, glyme, and the like.
A Dreferred solvent which is a common solvent fo. both the polymer containing pendant ami~e groups and the chemical reactants above is water, Particularly if the polymer containing pendant amide group is initially water-soluble, as in the case of most acrylamide containing vinylic polymers. Another preferred 11 common solvent for my reaction is a water-in-oil emulsion wherein ¦
the dispersed water phase contains dissolved therein both the polymers containing pendant amide groups and the chemical eactants described above.
L lZS~34~
After having dissolved the polymers containing pendant amide groups in the common solvent, preferably water, the chemical reactant can be added to obtain a solution or dispersion of amide containing polymer and the chemical reactants of this invention. Whether the polymer or the reactant is first added to the common solvent is of no consequence. This admixture is then added to or contained in a reaction vessel capable of withstanding a pressurized chemical reaction, for example, a Parr Bomb type of vessel. The vessel is enclosed and then heated to a temperature of at least 100C, preferably at least 110C, and most preferably to a temperature of at least 120C. If the temperature is increased above 100C, the vessel contents can expand and the pressure within the vessel can exceed one atmosphere and depending upon the solvent, the carboxylate substituted reactants used and/or the reactants used, can reach up to about 5 to 15 atmospheres, and possibly more. The pressure within the reaction vessel is a non-controlled variable and is controlled only to the extent that the vessel is enclosed, that a reaction temperature of at least 100C or higher is reached, and the vessel may contain solvents or reactants of more or less volatile nature, which solvents and reactants have vapor pressures of such a nature that pressure vessels are required at temperatures above lû0C.
Once the reaction vessel contents have reached at least 100C, and preferably 110C, the reaction is allowed to occur for at least 3 minutes at this temperature, and preferably for whatever length of time is necessary to accomplish a minimum of at least a 2 percent conversion, and preferaoly at least from 25-6û percent conversion, of the added amount of chemical reactant. The chemical reactant is, of course, converted to a pendant carboxylate containlng substltuted amide, or the product of the transamidation chemical reaction summarizea above.
5~3 If the polymer is a homopolymer of acrylamide, methacrylamide, or a copolymer of vinyl amide containing monomers¦
such that no other pendant functional group is present besides amide functional groups, the condition of the reaction is such that at least some degree of amide hydrolysis may also occur in those reactions in which water or a water containing solvent is utilized. In such cases, a carboxylate functional group may also be obtained in addition to the carboxylate modified amide and any unreacted starting amide groups from the starting polymer. This is particularly true at very high pH, so it is advisable to operate the reactions in aqueous common solvents or in water-in-oil emulsion at initial pH of below 9.0, and preferably below 8Ø
Therefore, I have described the chemical reaction or process that accomplishes the synthesis of polymers with randomly distributed monomer units having the structure o formula V:
Formula V..
Li O=C O=C û=C
û NH2 ~R
. M (R') Xm ~COOM)n 5~
wherein M is chosen from hydrogen, a lower alkyl (Cl-C4) group, alkali metal, alkaline earth metal, primary, secondary or tertiary amine saltst quaternary amines and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous Dridging group having from one to sixteen carbon atoms and being chosen .
from linear, branched, cyclic, aromatic and heterocyclic (functional groups), and mixtures thereof;
X is chosen from -503M, -P03M2, -COOR, -OR, -R'NR"2, -R'NR"3,-~OCH2CH)pOR, and mixtures thereof; R
where R" is-~CH2CHO~-pR, R, and mixtures thereof;
R is individually chosen at each occurrence from H and lower alkyl (Cl-C4) groups;
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+o+d is sufficient to ~rovide a molecul3r weight of at least 1000, and the ratio of d:(a + o) is from 20:1 to 1:100;
and wherein p ranges between 1 and 16, and m ranges between O and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is between l-20;
I
43~
which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, which polymer is represented by the structure:
~ C_C3~FC~
O:C O=C
M
wherein R, M, a, b have the same meanings as above;
with, 8. a chemical reactant having the structure:
R
HN--~--R' ) (COOM)n wherein R, R', M, X, m, and n have the meanings above; wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about 1:100; and the reaction occurs for an effective amount of time to accomplish at least a
2 mole percent, and preferably from 25-60 mole per_ent conversion¦
of chemical reactant to water-soluble carboxylated polymer; ana then recovering the water-soluble carooxylated polymer.
Polymer recovery may be accomplisned in several ways known to the person familiar with the art. For example, the polymers may be precipitated by addition of precipitating solvents, or non-solvents, to the reaction mixture. For example, methan r acetone may be added to the ~eac~i D n mixture eitnet -14- 66530-~26 as is or after concentration by distillation or vacuum distil-lation to precipitate the polymers. The polymers may also be recovered by vacuum distillation of solvent and unreacted chemical reactant from the reaction product mixture. The polymers may also be recovered by gel permeation chromatographic techni-ques. However, for the most part the polymers are recovered simply as a solution in the common solvent used to perform the transamidation reaction, and used as such.
Preferably, my process is a method to synthesize water-soluble carboxylated polymers having randomly repeated mer units represented by the formula:
r H Rl rH R l r I lRl t c--C~tc_f ~c f I
O=C O=C O=C
o NH2 NR
M (IR') Xm (COOM)n wherein M is chosen from hydrogen, alkali metal ~partially sodium or potassium), alkaline earth metal, tertiary amine or tertiary amine salts, quaternary amines and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen (particularly one to eight) carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic and heterocyclic (functional groups) (particularly alkyl, cyclic or aromatic), and mixtures thereof;
X is chosen from -SO3M, - PO3M2, 1~S~
~OCH2CIH~pOR, -OR function of groups, and mixtures thereof (partic-ularly -SO3M, OH, (OCH2CH2)pOH or mixtures thereof);
R is indiYidually chosen at each occurence from H and lower alkyl (Cl-C4) groups (particularly hydrogen, methyl or ethyl);
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 3,000, and the ratio of d:(a + b) is from 20:1 to 1:100; and wherein p ranges between 1 and 16 (particularly 1-12), and m ranges between 0 and 16 (particularly 1-4), and n ranges between 1 and 16 (particularly 1-4), provided that when m is zero, the sum of m + n is from 1 to 20; which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
r I 11 r ¦ 1 1 t H O=l ~H 1 M
wherein R, M, a, b have the same meanings as above; with B. a chemical reactant having the structure:
``! ~, l~S~3~
HNt ~ CooM) n Xm wherein R, R', M, X, m, and n have the meanings above; and wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about 1:100; and wherein the reaction occurs for an effective amount of time within a pH
range of 2-9 in an aqueous solvent to accomplish at least a 50 percent conversion of chemical reactant to water-soluble carboxylated polymer; and then recovering the water-soluble carboxylated polymer, which preferably has a molecular weight range of about 2,000 to 20,000,000.
Most preferably, my process is a method for the synthesis of water-soluble carboxylated polymers represented by the ormula:
~ CH2 7 ~CH2 1 ~CH2 c ~
0=C aO=C O=C d i M ( ') Xm (CO2M)n ~herein M is individually chosen at each occurrence from hydrogen, alkali metals, tertiary amine salts and quaternary ammonium or ammonium ions, or a mixture thereof, particularly hydrogen, alkali metals, especially sodium or potassium, or ammonium ions or a mixture thereof;
R' is chosen from multi-covalent, branched alkyl, linear alkyl, alkenyl, aryl or cyclic hydrocarbonaceous bridging groups lZS~3~1 having from one to eight carbon atoms, particularly a linear or branched alkylene bridging group having from two to six carbon atoms;
X is chosen from -SO3M, OH, t OCH2CH2~tpOR, -O -~CH2-CHO~pR
and a mixture thereof;
p ranges between 1 to 12 (particularly 1 to 8);
m ranges between 0 to 6;
n ranges between 1 to 4;
R is individually chosen at each occurrence from hydrogen l.0 and Cl to C4 lower alkyl groups (particularly hydrogen or methyl);
a, b, and d are integers with the following relationships:
a/b ranges from 0 to 100, preferably 0 to 50, a/d ranges from 0 to 100, preferably 0 to 50, b/d ranges from O.01 to 100, preferably 0.01 to 10, and the ratio d:(a+b) is between about 5:1 to about 1:25, preferably between about 4:1 and 1:20, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b~d will achieve a molecular weight of at least 1000, preferably 2,000 to 20,000;
which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and represented by the structure:
2---I ~ ~ CH2 I
M
wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500; and B. a chemical reactant having the structure:
~:A
lZS~3~
-17a- 66530-426 H N~ R' ) (CO M) 2 1 2 n Xm wherein R', M, X, m, and n have the meanings above; under the following reaction conditions:
I. a reaction temperature of at least 100C and prefer-ably at least llOC;
II. a reaction time of at least 4 hour and preferably at least 2 hour;
' .~
~,,, 5~ 4 III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure, or more;
thereby achieving the synthesis of the carboxylated polymers described above.
It is particularly of interest that these ~vnthetic procedures permit the synthesis of a carboxylated polymer represented by:
~ CH2 - C ~ CH 2 - C ~ CH 2 -o-c o-f o-lc o NH 2 NH
M (CO,M~)n wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the group hydrogen, sodium, potassium, ammonium ions and mixtures thereof;
R' is linear alkylene bridging group having from 1 to 4 carbon atoms;
m is from 0 to 3;
n is from 1 to 3; and a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, - la -1~54~
the sum of a + b ~ d is sufficient to provide a molecular weight of at least 3,000; which process comprises the reaction, in an aqueous solvent, for at least 1/4 hour at a temperature of at least 110C, in a pressure controlling reactor, of the ingredients:
A. a reactant:
"~COOM)n ~ S03M)m wherein R', M, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by:
1 CH2 - C ~ CH2 - C
O=C O= I
wherein R, ~, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups ranges between about 1:1 to about 1:5;
and then recovering the carboxylated polymer.
To further illustrate this invention, the following examples are provided , .. . ..... . .. . .
l~S~
The compositions of the starting polymers vary from homopolyacrylamide to 50 mole percent acrylamide and acrylic acid copolymers. Terpolymer may be used as well as long as acrylamide r or its homologs are incorporated therein. The polymers and reactants were charged as aqueous solutions or dispersions to a Parr Bomb equipped with temperature and pressure measuring devices and also equipped with means to agitate the contents.
Temperatures were increased to at least 100C in each case.
Reaction times ranged from about 20 minutes to in excess of 4 hours to accomplish the synthesis of the polymers which are escribed in Table I.
125~4 TABLE I
MODIFICAtION OF AMIDE-CONTAINING POLYMERS IN WATER
Amine Reaction Reaction Recovered PolYmer (Mole % Changed) Temperature Time PolYmer 70 mole %Glycine 150C 4 Hours 85 mole ~ acrylic acid/
Acrylic Acid/ (25) /5 mole % acrylamide/
30 mole % 10 mole % carboxymethyl-Acrylamide acrylamide 25 mole %Aminocaproic 150 C5 Hours 50 mole % acrylic acid/
Acrylic Acid/ Acid 35 mole % acrylamide/
75 mole % (20) 15 mole % carboxypentyl-Acrylamide acrylamide 25 mole %Aspartic 150 C4 Hours Acrylic acid/acrylamide, Acrylic Acid/ Acid 12 mole % N-(1,2-75 mole % (20) dicarboxy) ethyl-Acrylamide acrylamide 25 mole %l-Amino-l- 150C 3 Hours Acrylic acid/acrylamide, Acrylic Acid/ Cyclohexane 15 mole % carboxycyclo-75 mole %Carboxylic hexylacrylamide AcrylamideAcid (20) 25 mole ~4-Aminobenzoic 150C 2 Hours Acrylic acid/acrylamide, Acrylic Acid/ Acid 3 mole % carboxyphenyl-75 mole % (20) acrylamide Acrylamide In addition, the following polymers would be expected to be synthesized if acrylamide containing polymers were reacted according to the procedures described above with the following chemical reactants, which are described with the anticipated r~u~t~
- 2~ -~S~344 TABLE II
Starting Chemical Anticipated Starting Polymer _ Reactant Product Polymer [AA ~ AcAm~/ CH2SO3H ~AA ~ Ac ~ ~Z CHId H- ~ CH2CO2H ~ N ~
Ho3scH2 CH2CO2H
AcAm ~H2N ~ 3 CH2CO2H ~AA~AcA~C o=~
R RO ~
R=C2H5 CIH2 Co2H
~AcAm ~ ICH3lAA ~ AcAm ~ h2-C~d H2N-CH2-C-cH2c02HCH20~ C~O
IH20RHO2C-CHa- C CH2 NH
where R is -CH3 ~AcAm ~ H2N-CH-cH20cH2cH2oH ~AA ~ AcAm ~ ~2~C~d CH2CO2Na N~
Nat l~aC--CH~-.C~
~R20e~CR2 ~AcAm ~ H2N-CH2 ~ co2H~AA ~ Ac ~ ~2-CH~d COOCH3 C'O
HO2C~C~2_N~
1~5~3~
TA~LE II
(Continued) Starting Chemical Anticipated Starting Polymer Reactant Product Polymer ~CH2-CH~-~ACAm~bH2N-CH2CHS03H~C~2 ICH ~ AA~a[AcAm ~ ~2-C~
I x I C~=C C--O
0=C CH2 O N~
0 f H ~3 `CH-CEI2~2 tAA~ACA~3~C~2 I H~d ~AcAm~ H2N-CH-C02H f' H0~CC~
C02CH3 C~O
~AcAm~bH-N-cH2cH2so3H tAA~C~~ 2 C~t'd C:O
CH2cH2co2H HO S CH
OCH3 ~AA ~ Ac ~ 2~d C~O
~AcAm3b ~CH2CHCH2503H _N~
\cH2cHcH2co2H ; 2 ~ 2 o C H 3 CH 30C~ HCOCH 3 C~2 CH2 CO,H 503H
~AA~AcAm~b¦(CH2CH20)4H -1AA~CEI2 ~CH~d H2NCH2-CH-cH2c02H
NH
C~ R2 Hc-a ~CH,CEi20) 4H
-CH z _ ~AA ) ~ ( CH 2 - CH~CH 2 -CH
H~OCHzCH,~ N--CH3Cl O C O C
[AcAm] b CH2 ~H2 NH
H2N~CH2CH~CHaCOaH CH3 CH2 H-~OCH 2 CH~z-N-CH 2 -CH
CH 3Cl CH 2 -CO 2 l~S~
TABLE II
(Continued) Starting Chemical Anticipated Starting Polymer Reactant Product Polymer T ~ CH2-CH--~ T H2N-CH2CHS03Na+ ~C~2-CH ~ CH2-~H ~ H2~~CH~d ¦ b I O~C O~C O-C
O=C CH2 I ¦ NR2 NH
NH2 COOH M C~2 ~CH2COH
T = any terminal ~3 group Na~
{AA ~ AcAm ~ CH2-CH~d I I I CR OR OR NH
OR OR OR
HOaC-CH2-CH-CH-CH-CH2 I fCH2CH20H {A~AcAla~CH2-C~l~d H2N-CH2-CH-cH2-fH2 HOCH2C~2- Q N~
CO2Na+ N 020~cH2-cH-c~-cH2
of chemical reactant to water-soluble carboxylated polymer; ana then recovering the water-soluble carooxylated polymer.
Polymer recovery may be accomplisned in several ways known to the person familiar with the art. For example, the polymers may be precipitated by addition of precipitating solvents, or non-solvents, to the reaction mixture. For example, methan r acetone may be added to the ~eac~i D n mixture eitnet -14- 66530-~26 as is or after concentration by distillation or vacuum distil-lation to precipitate the polymers. The polymers may also be recovered by vacuum distillation of solvent and unreacted chemical reactant from the reaction product mixture. The polymers may also be recovered by gel permeation chromatographic techni-ques. However, for the most part the polymers are recovered simply as a solution in the common solvent used to perform the transamidation reaction, and used as such.
Preferably, my process is a method to synthesize water-soluble carboxylated polymers having randomly repeated mer units represented by the formula:
r H Rl rH R l r I lRl t c--C~tc_f ~c f I
O=C O=C O=C
o NH2 NR
M (IR') Xm (COOM)n wherein M is chosen from hydrogen, alkali metal ~partially sodium or potassium), alkaline earth metal, tertiary amine or tertiary amine salts, quaternary amines and ammonium ions and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen (particularly one to eight) carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic and heterocyclic (functional groups) (particularly alkyl, cyclic or aromatic), and mixtures thereof;
X is chosen from -SO3M, - PO3M2, 1~S~
~OCH2CIH~pOR, -OR function of groups, and mixtures thereof (partic-ularly -SO3M, OH, (OCH2CH2)pOH or mixtures thereof);
R is indiYidually chosen at each occurence from H and lower alkyl (Cl-C4) groups (particularly hydrogen, methyl or ethyl);
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 3,000, and the ratio of d:(a + b) is from 20:1 to 1:100; and wherein p ranges between 1 and 16 (particularly 1-12), and m ranges between 0 and 16 (particularly 1-4), and n ranges between 1 and 16 (particularly 1-4), provided that when m is zero, the sum of m + n is from 1 to 20; which process comprises reacting, in a common solvent, at a temperature of at least 100C:
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
r I 11 r ¦ 1 1 t H O=l ~H 1 M
wherein R, M, a, b have the same meanings as above; with B. a chemical reactant having the structure:
``! ~, l~S~3~
HNt ~ CooM) n Xm wherein R, R', M, X, m, and n have the meanings above; and wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about 1:100; and wherein the reaction occurs for an effective amount of time within a pH
range of 2-9 in an aqueous solvent to accomplish at least a 50 percent conversion of chemical reactant to water-soluble carboxylated polymer; and then recovering the water-soluble carboxylated polymer, which preferably has a molecular weight range of about 2,000 to 20,000,000.
Most preferably, my process is a method for the synthesis of water-soluble carboxylated polymers represented by the ormula:
~ CH2 7 ~CH2 1 ~CH2 c ~
0=C aO=C O=C d i M ( ') Xm (CO2M)n ~herein M is individually chosen at each occurrence from hydrogen, alkali metals, tertiary amine salts and quaternary ammonium or ammonium ions, or a mixture thereof, particularly hydrogen, alkali metals, especially sodium or potassium, or ammonium ions or a mixture thereof;
R' is chosen from multi-covalent, branched alkyl, linear alkyl, alkenyl, aryl or cyclic hydrocarbonaceous bridging groups lZS~3~1 having from one to eight carbon atoms, particularly a linear or branched alkylene bridging group having from two to six carbon atoms;
X is chosen from -SO3M, OH, t OCH2CH2~tpOR, -O -~CH2-CHO~pR
and a mixture thereof;
p ranges between 1 to 12 (particularly 1 to 8);
m ranges between 0 to 6;
n ranges between 1 to 4;
R is individually chosen at each occurrence from hydrogen l.0 and Cl to C4 lower alkyl groups (particularly hydrogen or methyl);
a, b, and d are integers with the following relationships:
a/b ranges from 0 to 100, preferably 0 to 50, a/d ranges from 0 to 100, preferably 0 to 50, b/d ranges from O.01 to 100, preferably 0.01 to 10, and the ratio d:(a+b) is between about 5:1 to about 1:25, preferably between about 4:1 and 1:20, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b~d will achieve a molecular weight of at least 1000, preferably 2,000 to 20,000;
which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and represented by the structure:
2---I ~ ~ CH2 I
M
wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500; and B. a chemical reactant having the structure:
~:A
lZS~3~
-17a- 66530-426 H N~ R' ) (CO M) 2 1 2 n Xm wherein R', M, X, m, and n have the meanings above; under the following reaction conditions:
I. a reaction temperature of at least 100C and prefer-ably at least llOC;
II. a reaction time of at least 4 hour and preferably at least 2 hour;
' .~
~,,, 5~ 4 III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure, or more;
thereby achieving the synthesis of the carboxylated polymers described above.
It is particularly of interest that these ~vnthetic procedures permit the synthesis of a carboxylated polymer represented by:
~ CH2 - C ~ CH 2 - C ~ CH 2 -o-c o-f o-lc o NH 2 NH
M (CO,M~)n wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the group hydrogen, sodium, potassium, ammonium ions and mixtures thereof;
R' is linear alkylene bridging group having from 1 to 4 carbon atoms;
m is from 0 to 3;
n is from 1 to 3; and a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, - la -1~54~
the sum of a + b ~ d is sufficient to provide a molecular weight of at least 3,000; which process comprises the reaction, in an aqueous solvent, for at least 1/4 hour at a temperature of at least 110C, in a pressure controlling reactor, of the ingredients:
A. a reactant:
"~COOM)n ~ S03M)m wherein R', M, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by:
1 CH2 - C ~ CH2 - C
O=C O= I
wherein R, ~, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups ranges between about 1:1 to about 1:5;
and then recovering the carboxylated polymer.
To further illustrate this invention, the following examples are provided , .. . ..... . .. . .
l~S~
The compositions of the starting polymers vary from homopolyacrylamide to 50 mole percent acrylamide and acrylic acid copolymers. Terpolymer may be used as well as long as acrylamide r or its homologs are incorporated therein. The polymers and reactants were charged as aqueous solutions or dispersions to a Parr Bomb equipped with temperature and pressure measuring devices and also equipped with means to agitate the contents.
Temperatures were increased to at least 100C in each case.
Reaction times ranged from about 20 minutes to in excess of 4 hours to accomplish the synthesis of the polymers which are escribed in Table I.
125~4 TABLE I
MODIFICAtION OF AMIDE-CONTAINING POLYMERS IN WATER
Amine Reaction Reaction Recovered PolYmer (Mole % Changed) Temperature Time PolYmer 70 mole %Glycine 150C 4 Hours 85 mole ~ acrylic acid/
Acrylic Acid/ (25) /5 mole % acrylamide/
30 mole % 10 mole % carboxymethyl-Acrylamide acrylamide 25 mole %Aminocaproic 150 C5 Hours 50 mole % acrylic acid/
Acrylic Acid/ Acid 35 mole % acrylamide/
75 mole % (20) 15 mole % carboxypentyl-Acrylamide acrylamide 25 mole %Aspartic 150 C4 Hours Acrylic acid/acrylamide, Acrylic Acid/ Acid 12 mole % N-(1,2-75 mole % (20) dicarboxy) ethyl-Acrylamide acrylamide 25 mole %l-Amino-l- 150C 3 Hours Acrylic acid/acrylamide, Acrylic Acid/ Cyclohexane 15 mole % carboxycyclo-75 mole %Carboxylic hexylacrylamide AcrylamideAcid (20) 25 mole ~4-Aminobenzoic 150C 2 Hours Acrylic acid/acrylamide, Acrylic Acid/ Acid 3 mole % carboxyphenyl-75 mole % (20) acrylamide Acrylamide In addition, the following polymers would be expected to be synthesized if acrylamide containing polymers were reacted according to the procedures described above with the following chemical reactants, which are described with the anticipated r~u~t~
- 2~ -~S~344 TABLE II
Starting Chemical Anticipated Starting Polymer _ Reactant Product Polymer [AA ~ AcAm~/ CH2SO3H ~AA ~ Ac ~ ~Z CHId H- ~ CH2CO2H ~ N ~
Ho3scH2 CH2CO2H
AcAm ~H2N ~ 3 CH2CO2H ~AA~AcA~C o=~
R RO ~
R=C2H5 CIH2 Co2H
~AcAm ~ ICH3lAA ~ AcAm ~ h2-C~d H2N-CH2-C-cH2c02HCH20~ C~O
IH20RHO2C-CHa- C CH2 NH
where R is -CH3 ~AcAm ~ H2N-CH-cH20cH2cH2oH ~AA ~ AcAm ~ ~2~C~d CH2CO2Na N~
Nat l~aC--CH~-.C~
~R20e~CR2 ~AcAm ~ H2N-CH2 ~ co2H~AA ~ Ac ~ ~2-CH~d COOCH3 C'O
HO2C~C~2_N~
1~5~3~
TA~LE II
(Continued) Starting Chemical Anticipated Starting Polymer Reactant Product Polymer ~CH2-CH~-~ACAm~bH2N-CH2CHS03H~C~2 ICH ~ AA~a[AcAm ~ ~2-C~
I x I C~=C C--O
0=C CH2 O N~
0 f H ~3 `CH-CEI2~2 tAA~ACA~3~C~2 I H~d ~AcAm~ H2N-CH-C02H f' H0~CC~
C02CH3 C~O
~AcAm~bH-N-cH2cH2so3H tAA~C~~ 2 C~t'd C:O
CH2cH2co2H HO S CH
OCH3 ~AA ~ Ac ~ 2~d C~O
~AcAm3b ~CH2CHCH2503H _N~
\cH2cHcH2co2H ; 2 ~ 2 o C H 3 CH 30C~ HCOCH 3 C~2 CH2 CO,H 503H
~AA~AcAm~b¦(CH2CH20)4H -1AA~CEI2 ~CH~d H2NCH2-CH-cH2c02H
NH
C~ R2 Hc-a ~CH,CEi20) 4H
-CH z _ ~AA ) ~ ( CH 2 - CH~CH 2 -CH
H~OCHzCH,~ N--CH3Cl O C O C
[AcAm] b CH2 ~H2 NH
H2N~CH2CH~CHaCOaH CH3 CH2 H-~OCH 2 CH~z-N-CH 2 -CH
CH 3Cl CH 2 -CO 2 l~S~
TABLE II
(Continued) Starting Chemical Anticipated Starting Polymer Reactant Product Polymer T ~ CH2-CH--~ T H2N-CH2CHS03Na+ ~C~2-CH ~ CH2-~H ~ H2~~CH~d ¦ b I O~C O~C O-C
O=C CH2 I ¦ NR2 NH
NH2 COOH M C~2 ~CH2COH
T = any terminal ~3 group Na~
{AA ~ AcAm ~ CH2-CH~d I I I CR OR OR NH
OR OR OR
HOaC-CH2-CH-CH-CH-CH2 I fCH2CH20H {A~AcAla~CH2-C~l~d H2N-CH2-CH-cH2-fH2 HOCH2C~2- Q N~
CO2Na+ N 020~cH2-cH-c~-cH2
3 ~ N/
- H2N ~ ~ C02H -{AA ~ AcAm ~ CH2--CH~d, OCH2CH20CH2CH20H CH3 N}I
CE~ H :~CH 2t;~H
~AA~a ~ACQm~b OR fOOH ~AA ~ ACA~ ~ C~2-c~d HN-CH2 CH CH CH2-SO3H o O~C
I C~H 0~ N-C~
CH3 ~C~2 C~ ~C~C~Z
~03S
herein ~AA] = acrylic acid [QcAm] = acrylamide a, b, d, R, M, have meanings as described above.
_ 25 -
- H2N ~ ~ C02H -{AA ~ AcAm ~ CH2--CH~d, OCH2CH20CH2CH20H CH3 N}I
CE~ H :~CH 2t;~H
~AA~a ~ACQm~b OR fOOH ~AA ~ ACA~ ~ C~2-c~d HN-CH2 CH CH CH2-SO3H o O~C
I C~H 0~ N-C~
CH3 ~C~2 C~ ~C~C~Z
~03S
herein ~AA] = acrylic acid [QcAm] = acrylamide a, b, d, R, M, have meanings as described above.
_ 25 -
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process to synthesize water-soluble carboxylated polymers having randomly repeated mer units represented by the formula:
wherein M is chosen from hydrogen, lower alkyl (C1-C4) groups, alkali metal, alkaline earth metal, primary, secondary or tertiary amine salts, quaternary amines an ammonium ion, and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chose from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic and olefinic groups, and mixtures thereof (functional groups);
X is chosen from -SO3M - PO3M2, -COOR, -OR, -R'NR"2 , -R'N+R3 Hal (OCH2?H)pOR, and mixtures thereof;
wherein R" is (CH2?HO)pR, R and mixtures thereof, and R is individually chosen, at each occurrence, from H and lower alkyl (C1-C4) groups;
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a + b) is from 20:1 to 1:100;
and wherein p ranges between 1 and 16, and m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a temperature of at least 100°C;
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
wherein R, M, a, b have the same meanings as above; witr.
B.a chemical reactant having the structure:
wherein R, R', M, X, m, and n have the meanings above; wherein the mole ratio of chemical reactant to pendant amide groups in the polymer ranges between about 5:1 to about 1:100; and reacting for an effective amount of time to accomplish at least a 2 percent conversion of chemical reactant to carboxylated pendant groups on the polymer; and then recovering the water-soluble carboxylated polymer.
wherein M is chosen from hydrogen, lower alkyl (C1-C4) groups, alkali metal, alkaline earth metal, primary, secondary or tertiary amine salts, quaternary amines an ammonium ion, and mixtures thereof;
R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chose from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic and olefinic groups, and mixtures thereof (functional groups);
X is chosen from -SO3M - PO3M2, -COOR, -OR, -R'NR"2 , -R'N+R3 Hal (OCH2?H)pOR, and mixtures thereof;
wherein R" is (CH2?HO)pR, R and mixtures thereof, and R is individually chosen, at each occurrence, from H and lower alkyl (C1-C4) groups;
and wherein a, b, and d are integers with the following relationships;
a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 1000, and the ratio of d:(a + b) is from 20:1 to 1:100;
and wherein p ranges between 1 and 16, and m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a temperature of at least 100°C;
A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure:
wherein R, M, a, b have the same meanings as above; witr.
B.a chemical reactant having the structure:
wherein R, R', M, X, m, and n have the meanings above; wherein the mole ratio of chemical reactant to pendant amide groups in the polymer ranges between about 5:1 to about 1:100; and reacting for an effective amount of time to accomplish at least a 2 percent conversion of chemical reactant to carboxylated pendant groups on the polymer; and then recovering the water-soluble carboxylated polymer.
2. The process of Claim 1 wherein:
R is individually chosen at each occurrence from hydrogen, methyl, and ethyl groups, M is individually chosen at each occurrence from hydrogen, sodium, potassium, tertiary amines, quarternary ammonium and ammonium ions and mixtures thereof, R' has from 1-8 carbon atoms and is linear or branched aliphatic, cyclic, aromatic and mixtures thereof;
X is -SO3M, OH, (OCH2CH2)pOH; and mixtures thereof p is from 1 to 12 m is from 0 to 4;
n is from 1 to 4;
and the molecular weight of the water-soluble carboxylated polymer ranges between about 2000 to about 20,000,000.
R is individually chosen at each occurrence from hydrogen, methyl, and ethyl groups, M is individually chosen at each occurrence from hydrogen, sodium, potassium, tertiary amines, quarternary ammonium and ammonium ions and mixtures thereof, R' has from 1-8 carbon atoms and is linear or branched aliphatic, cyclic, aromatic and mixtures thereof;
X is -SO3M, OH, (OCH2CH2)pOH; and mixtures thereof p is from 1 to 12 m is from 0 to 4;
n is from 1 to 4;
and the molecular weight of the water-soluble carboxylated polymer ranges between about 2000 to about 20,000,000.
3. The process of Claim 1 or 2 wherein the common solvent is chosen from the group consisting of water, dimethylformamide, dimethylsulfoxide, diglyme and mixtures thereof.
4. The process of Claim 1 or 2 wherein the common solvent is water-emulsified in a continuous oil phase such that the water-soluble carboxylated polymer is recovered as a water-in-oil emulsion.
5. A process for the synthesis of water-soluble carboxy-lated polymers represented by the formula:
wherein R is individually chosen at each occurrence from hydrogen and C1 to C4 lower alkyl, M is individually chosen at each occurrence from hydrogen, alkali metals, tertiary amine salts, and quarternary ammonium and ammonium ions, and mixtures thereof;
R' is chosen from multi-covalent, branched alkyl, linear alkyl, alkaryl, aryl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms;
X is chosen from -SO3H, , and mixtures thereof;
p ranges from 1 to 12 m ranges between 0 to 6;
n ranges between 1 to 4;
a, b, and d are integers with the following relationships:
a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a+b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b+d will achieve a molecular weignt of at least 1,000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functiûnal groups and represented by the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500;
and B. a reactant having the structure:
wherein R', M, X, m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100°C;
II. a reaction time of at least 1/4 hour;
III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure;
thereby achieving and thereafter recovering said carboxylated polymers.
wherein R is individually chosen at each occurrence from hydrogen and C1 to C4 lower alkyl, M is individually chosen at each occurrence from hydrogen, alkali metals, tertiary amine salts, and quarternary ammonium and ammonium ions, and mixtures thereof;
R' is chosen from multi-covalent, branched alkyl, linear alkyl, alkaryl, aryl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms;
X is chosen from -SO3H, , and mixtures thereof;
p ranges from 1 to 12 m ranges between 0 to 6;
n ranges between 1 to 4;
a, b, and d are integers with the following relationships:
a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a+b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b+d will achieve a molecular weignt of at least 1,000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functiûnal groups and represented by the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500;
and B. a reactant having the structure:
wherein R', M, X, m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100°C;
II. a reaction time of at least 1/4 hour;
III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1:50;
IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure;
thereby achieving and thereafter recovering said carboxylated polymers.
6. The process of Claim 5, wherein R is individually chosen at each occurrence from hydrogen or methyl M is individually chosen at each occurrence from hydrogen, sodium, potassium, ammonium and mixtures thereof, R' is a linear or branched alkylene bridging group having from 2 to 6 carbon atoms;
X is -SO3M, , and mixtures thereof, when p is from 1-8;
a, b and d are integers having the following relationships:
a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d:(a+b) ranges between about 4:1 and 1:20, and the sum of a+b+d is such that the carboxylated polymer has a molecular weight ranging from 2,000-20,000,000, and which process comprises reacting at a temperature of at least 110°C for at least 1/2 hour, in a common aqueous solvent, A. a polymer having the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b is such that the molecular weight of the polymer is at least 2,000; with B. a chemical reactant having the structure:
wherein R1, M, and X are defined above, and m is from 0 to 3, n is from 1 to 3, and the sum of m+n is from 1 to 4; and, the ratio of reactant to polymer ranges between about 1:1 to about 1:10, and the reaction pressure is at least 1.25 atmospheres; and then recovering said carboxylated polymer.
X is -SO3M, , and mixtures thereof, when p is from 1-8;
a, b and d are integers having the following relationships:
a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d:(a+b) ranges between about 4:1 and 1:20, and the sum of a+b+d is such that the carboxylated polymer has a molecular weight ranging from 2,000-20,000,000, and which process comprises reacting at a temperature of at least 110°C for at least 1/2 hour, in a common aqueous solvent, A. a polymer having the structure:
wherein R, M, a, and b have the meanings above and wherein the sum of a+b is such that the molecular weight of the polymer is at least 2,000; with B. a chemical reactant having the structure:
wherein R1, M, and X are defined above, and m is from 0 to 3, n is from 1 to 3, and the sum of m+n is from 1 to 4; and, the ratio of reactant to polymer ranges between about 1:1 to about 1:10, and the reaction pressure is at least 1.25 atmospheres; and then recovering said carboxylated polymer.
7. The process of Claim 5 or 6 wherein the aqueous solvent is from the group consisting of water and a water-in-oil emulsion.
8. A process for synthesizing a carboxylated polymer represented by:
wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the group hydrogen, sodium, potassium, tertiary amine salts, and ammonium ions and mixtures thereof;
R' is a linear or branched alkylene bridging group having from 1 to 6 carbon atoms;
p is from 1 to 12;
m is from 1 to 6;
n is from 1 to 6; and the sum, n+m, is from 1-10;
a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, the sum of a + b + d is sufficient to provide a molecular weight of at least 2,000; which process comprises reacting in an aqueous solvent, at a pH between about 3-8, for a least 1/4 hour at a temperature of at least 110°C, in a pressure controlling reactor, the ingredients:
A. a chemical reactant:
wherein R', M, p, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by:
wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups on the polymer ranges between about 1:1 to about 1:5; and then recovering the carboxylated polymer.
wherein: R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the group hydrogen, sodium, potassium, tertiary amine salts, and ammonium ions and mixtures thereof;
R' is a linear or branched alkylene bridging group having from 1 to 6 carbon atoms;
p is from 1 to 12;
m is from 1 to 6;
n is from 1 to 6; and the sum, n+m, is from 1-10;
a, b, and d are integers having the relationships:
a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, the sum of a + b + d is sufficient to provide a molecular weight of at least 2,000; which process comprises reacting in an aqueous solvent, at a pH between about 3-8, for a least 1/4 hour at a temperature of at least 110°C, in a pressure controlling reactor, the ingredients:
A. a chemical reactant:
wherein R', M, p, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by:
wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups on the polymer ranges between about 1:1 to about 1:5; and then recovering the carboxylated polymer.
9. The carboxylated polymer:
which is synthesized, in a pressure controlling reactor, by reacting a precursor polymer:
with a reactant:
in an aqueous reaction solvent at a temperature of at least 100°C for at least 1/4 hour at a mole ratio of precursor polymer to reactant ranging between about 20:1 to about 1:2, and wherein:
R is chosen individually, at each occurrence, from hydrogen and methyl groups;
M is chosen individually, at each occurrence, from hydrogen, alkali metal, tertiary amines, and ammonium ions and mixtures thereof;
p ranges, at each occurrence, between 0-12, a, b, and d are integers having the relationships:
a/d is from 0 to 100, a/b is from 0 to 100, b/d is from 0.01 to 100, and d:(a + b) ranges between about 10:1 to about 1:100, and wherein the sum a + b + d is such that the carboxylated polymer has a moleculr weight of at least 1000.
which is synthesized, in a pressure controlling reactor, by reacting a precursor polymer:
with a reactant:
in an aqueous reaction solvent at a temperature of at least 100°C for at least 1/4 hour at a mole ratio of precursor polymer to reactant ranging between about 20:1 to about 1:2, and wherein:
R is chosen individually, at each occurrence, from hydrogen and methyl groups;
M is chosen individually, at each occurrence, from hydrogen, alkali metal, tertiary amines, and ammonium ions and mixtures thereof;
p ranges, at each occurrence, between 0-12, a, b, and d are integers having the relationships:
a/d is from 0 to 100, a/b is from 0 to 100, b/d is from 0.01 to 100, and d:(a + b) ranges between about 10:1 to about 1:100, and wherein the sum a + b + d is such that the carboxylated polymer has a moleculr weight of at least 1000.
10. The carboxylated polymer of Claim 9 which is synthes-ized in an aqueous reaction solvent at a temperature of at least 120°C for at least 1 hour at a mole ratio of precursor polymer to reactant of from 10:1 to 1:1 and wherein:
R is hydrogen, M is from the group H, sodium, potassium, and ammonium ions and mixtures thereof, and the polymer has a molecular weight between about 2000 to about 20,000,000.
R is hydrogen, M is from the group H, sodium, potassium, and ammonium ions and mixtures thereof, and the polymer has a molecular weight between about 2000 to about 20,000,000.
11. The carboxylated polymer represented by the structure:
wherein R is individually chosen at each occurrence from hydrogen and methyl groups, or mixtures thereof;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium ammonium ions, and mixtures thereof;
a, b, d are integers such that:
the sum of a + b + d is sufficient to achieve a molecular weight of at least 1000;
p, at each occurrence, is from 0-6;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100, and the ratio d:(a + b) ranges between about 5:1 to 1:50.
wherein R is individually chosen at each occurrence from hydrogen and methyl groups, or mixtures thereof;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium ammonium ions, and mixtures thereof;
a, b, d are integers such that:
the sum of a + b + d is sufficient to achieve a molecular weight of at least 1000;
p, at each occurrence, is from 0-6;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100, and the ratio d:(a + b) ranges between about 5:1 to 1:50.
12. The carboxylated polymer represented by:
and wherein R, M, a, b, d and p have the meanings of Claim 11.
and wherein R, M, a, b, d and p have the meanings of Claim 11.
13. The carboxylated polymer represented by the structure:
wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof;
R' is a multivalent hydrocarbonaceous bridging group having from 1 - 6 carbon atoms and being from linear alkyl, branched alkyl, cyclic, and olefinic groups, and mixtures thereof;
X is -SC3M, OH and mixtures thereof, and wherein a, b, and d are integers, the sum of which is such that the molecular weight of the carboxylated polymer is at least 2,000, and wherein the following relationships exist:
a/b is from 0 to 100, a/d is from 0 to 100, b/d is from 0.01 to 1000, and the ratio d:(a + b) is between about 10:1 to about 1:100, and wherein:
m is equal to 1 to 6, n is equal to 1 to 6, and the sum of m+n is between 1-8.
wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof;
R' is a multivalent hydrocarbonaceous bridging group having from 1 - 6 carbon atoms and being from linear alkyl, branched alkyl, cyclic, and olefinic groups, and mixtures thereof;
X is -SC3M, OH and mixtures thereof, and wherein a, b, and d are integers, the sum of which is such that the molecular weight of the carboxylated polymer is at least 2,000, and wherein the following relationships exist:
a/b is from 0 to 100, a/d is from 0 to 100, b/d is from 0.01 to 1000, and the ratio d:(a + b) is between about 10:1 to about 1:100, and wherein:
m is equal to 1 to 6, n is equal to 1 to 6, and the sum of m+n is between 1-8.
14. The carboxylated polymer represented by the structure:
wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof; and, a, b, and d are the same as in Claim 13.
wherein R is individually chosen, at each occurrence, from hydrogen and methyl groups;
M is individually chosen, at each occurrence, from hydrogen, sodium, potassium, and, ammonium ions, and mixtures thereof; and, a, b, and d are the same as in Claim 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US831,964 | 1986-02-24 | ||
| US06/831,964 US4680339A (en) | 1986-02-24 | 1986-02-24 | Carboxylate containing modified acrylamide polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1254344A true CA1254344A (en) | 1989-05-16 |
Family
ID=25260310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529033A Expired CA1254344A (en) | 1986-02-24 | 1987-02-05 | Carboxylate containing modified acrylamide polymers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4680339A (en) |
| EP (1) | EP0238852B1 (en) |
| AT (1) | ATE88482T1 (en) |
| CA (1) | CA1254344A (en) |
| DE (1) | DE3785476T2 (en) |
| ES (1) | ES2054625T3 (en) |
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| US4879371A (en) * | 1986-12-24 | 1989-11-07 | Monsanto Company | Solid phase peptide synthesis |
| US4764594A (en) * | 1987-03-30 | 1988-08-16 | Monsanto Company | Resin support for solid phase peptide synthesis |
| US4764595A (en) * | 1986-12-24 | 1988-08-16 | Monsanto Company | Resin support for solid phase peptide synthesis |
| US5049310A (en) * | 1987-04-27 | 1991-09-17 | Nalco Chemical Company | Zinc stabilization with modified acrylamide based polymers and corrosion inhibition derived therefrom |
| US4898686A (en) * | 1987-04-27 | 1990-02-06 | Nalco Chemical Company | Zinc stabilization with modified acrylamide based polymers and corrosion inhibition derived therefrom |
| US4973428A (en) * | 1987-04-27 | 1990-11-27 | Nalco Chemical Company | Zinc stabilization with modified acrylamide based polymers and corrosion inhibition derived therefrom |
| DE3726285A1 (en) * | 1987-08-07 | 1989-02-16 | Basf Ag | POLYMERISATES WITH FUNCTIONAL GROUPS |
| US4952642A (en) * | 1987-10-26 | 1990-08-28 | Nalco Chemical Company | Process for making acrylamido methane sulfonic acid polymers |
| US4829121A (en) * | 1987-11-24 | 1989-05-09 | Nalco Chemical Company | Process for sulfoethylation of high molecular weight acrylamide containing polysoap latex polymers |
| US4959409A (en) * | 1988-01-14 | 1990-09-25 | The Procter & Gamble Company | Amino-functional compounds as builder/dispersants in detergent compositions |
| US5128419A (en) * | 1990-08-20 | 1992-07-07 | Nalco Chemical Company | Synthesis of tagged polymers by post-polymerization (trans) amidation reaction |
| US5478477A (en) * | 1994-11-04 | 1995-12-26 | Nalco Chemical Company | Use of alginates to treat bauxite red mud |
| WO1996038492A1 (en) * | 1995-06-02 | 1996-12-05 | Nippon Shokubai Co., Ltd. | Clathrate hydrate inhibitor and method of inhibiting the formation of clathrate hydrates using it |
| EP0807695A1 (en) * | 1996-05-15 | 1997-11-19 | Nalco Chemical Company | A non-phosphorus corrosion inhibitor for industrial cooling water systems and airwasher systems |
| US5880237A (en) * | 1997-01-31 | 1999-03-09 | Nalco Chemical Company | Preparation and utility of water-soluble polymers having pendant derivatized amide, ester or ether functionalities as ceramics dispersants and binders |
| US5726267A (en) * | 1997-01-31 | 1998-03-10 | Nalco Chemical Company | Preparation and utility of water-soluble polymers having pendant derivatized amide, ester or ether functionalities as ceramics dispersants and binders |
| US6017994A (en) * | 1997-01-31 | 2000-01-25 | Nalco Chemical Company | Utility of water-soluble polymers having pendant derivatized amide functionalities for scale control |
| US6299909B1 (en) | 1998-06-01 | 2001-10-09 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| US6652889B2 (en) | 1998-06-01 | 2003-11-25 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation and use |
| US8414932B2 (en) | 1998-06-01 | 2013-04-09 | Albemarie Corporation | Active bromine containing biocidal compositions and their preparation |
| US6352725B1 (en) | 1998-06-01 | 2002-03-05 | Albemarle Corporation | Continuous processes for preparing concentrated aqueous liquid biocidal composition |
| US6511682B1 (en) | 1998-06-01 | 2003-01-28 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| US8293795B1 (en) | 1998-06-01 | 2012-10-23 | Albemarle Corporation | Preparation of concentrated aqueous bromine solutions and biocidal applications thereof |
| US6348219B1 (en) | 1998-06-01 | 2002-02-19 | Albemarle Corporation | Processes for preparing concentrated aqueous liquid biocidal compositions |
| US7087251B2 (en) | 1998-06-01 | 2006-08-08 | Albemarle Corporation | Control of biofilm |
| US6068861A (en) | 1998-06-01 | 2000-05-30 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| US6506418B1 (en) | 1999-09-24 | 2003-01-14 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| DE10101671A1 (en) | 2000-08-25 | 2002-03-14 | Bayer Ag | Method of conditioning stagnant and flowing water systems |
| US6375991B1 (en) | 2000-09-08 | 2002-04-23 | Albemarle Corporation | Production of concentrated biocidal solutions |
| US6919364B2 (en) | 2001-06-28 | 2005-07-19 | Solution Biosciences, Inc. | Microbiological control in animal processing |
| US6986910B2 (en) | 2001-06-28 | 2006-01-17 | Albemarle Corporation | Microbiological control in poultry processing |
| WO2003011033A1 (en) * | 2001-06-28 | 2003-02-13 | Solution Biosciences, Inc. | Microbiological control in animal processing |
| JP2004091713A (en) * | 2002-09-03 | 2004-03-25 | Jsr Corp | Composition for polishing agent |
| DE10310414A1 (en) | 2003-03-11 | 2004-09-23 | Bayer Chemicals Ag | Water conditioner for use in still or flowing water (e.g. in oil exploration 'squeeze' operations) contains a polysuccinimide and a biostat |
| US7901276B2 (en) * | 2003-06-24 | 2011-03-08 | Albemarle Corporation | Microbiocidal control in the processing of meat-producing four-legged animals |
| EP1735414A2 (en) * | 2004-01-30 | 2006-12-27 | Huntsman Petrochemical Corporation | Surface-active polymers as detergents |
| EP1786266B1 (en) * | 2004-09-07 | 2014-12-03 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| CN101115392B (en) * | 2004-12-23 | 2011-05-11 | 雅宝公司 | Microbiocidal control in the processing of meat-producing four-legged animals |
| US8241618B2 (en) * | 2005-01-27 | 2012-08-14 | Lubrizol Advanced Materials, Inc. | Process for producing a hydrophobically modified polymer for use with personal care compositions |
| DE102005010855A1 (en) | 2005-03-10 | 2006-09-14 | Lanxess Deutschland Gmbh | Aqueous conditioning agent, useful as a pelleting agent, comprises polysuccinimide or its partial hydrolysate in combination with fatty acid amides |
| US9452229B2 (en) * | 2005-06-10 | 2016-09-27 | Albemarle Corporation | Highly concentrated, biocidally active compositions and aqueous mixtures and methods of making the same |
| WO2007065113A1 (en) | 2005-12-01 | 2007-06-07 | Solution Biosciences, Inc. | Microbiocidal control in the processing of meat-producing four-legged animals |
| US20090069522A1 (en) * | 2007-09-11 | 2009-03-12 | Hessefort Yin Z | Hydrophobically modified polymers |
| EP2897986A1 (en) | 2012-09-19 | 2015-07-29 | Dow Global Technologies LLC | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH526596A (en) * | 1970-07-14 | 1972-08-15 | Lonza Ag | Process for the preparation of N-substituted acrylic acid and / or methacrylic acid amide-containing polymers |
| CS171962B1 (en) * | 1974-02-01 | 1976-11-29 | ||
| CS177507B1 (en) * | 1974-02-12 | 1977-07-29 | ||
| FR2288113A1 (en) * | 1974-10-18 | 1976-05-14 | Anvar | Water sol polymethylol acrylamide polymers - with iminodiacetate gps, useful complexing agents |
| GB1482839A (en) * | 1974-10-29 | 1977-08-17 | Sanyo Trading Co | Vulcanisable rubber compositions and vulcanised rubber prepared therefrom |
| US4251410A (en) * | 1976-05-26 | 1981-02-17 | Sandoz Ltd. | Reaction products of a polyacrylamide formaldehyde, a secondary amine and an-nh group-containing functional derivative of an acid |
| US4330440A (en) * | 1977-02-08 | 1982-05-18 | Development Finance Corporation Of New Zealand | Activated matrix and method of activation |
| US4317893A (en) * | 1978-10-26 | 1982-03-02 | Mobil Oil Corporation | Oil recovery by waterflooding employing an anionic polymeric surfactant containing recurring succinimide or succinamide groups |
| FR2461724A1 (en) * | 1979-07-20 | 1981-02-06 | Christine Fougnot | GROUP-SUBSTITUTED POLYMERS CONFERRING THEM WITH ANTI-COAGULANT PROPERTIES AND METHOD FOR THE PREPARATION THEREOF, OBJECTS CONSISTING OF AND / OR COMPRISING THE SAID POLYMERS AND METHODS OF MAKING THEM, APPLICATION OF SAID OBJECTS IN SURGERY AND MEDICINE, AND PHARMACEUTICAL COMPOSITIONS CONTAINING SAID SUBSTITUTED POLYMERS |
| US4390659A (en) * | 1980-06-10 | 1983-06-28 | The Dow Chemical Company | Method for the preparation of quaternary carboxamide polymers |
| EP0171661B1 (en) * | 1984-08-13 | 1989-03-29 | AlliedSignal Inc. | Method of preparing cationic terpolymers and product derived therefrom |
-
1986
- 1986-02-24 US US06/831,964 patent/US4680339A/en not_active Expired - Lifetime
-
1987
- 1987-02-05 CA CA000529033A patent/CA1254344A/en not_active Expired
- 1987-02-19 DE DE8787102390T patent/DE3785476T2/en not_active Expired - Lifetime
- 1987-02-19 EP EP87102390A patent/EP0238852B1/en not_active Expired - Lifetime
- 1987-02-19 AT AT87102390T patent/ATE88482T1/en not_active IP Right Cessation
- 1987-02-19 ES ES87102390T patent/ES2054625T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ES2054625T3 (en) | 1994-08-16 |
| EP0238852A2 (en) | 1987-09-30 |
| ATE88482T1 (en) | 1993-05-15 |
| DE3785476D1 (en) | 1993-05-27 |
| EP0238852A3 (en) | 1990-12-27 |
| EP0238852B1 (en) | 1993-04-21 |
| US4680339A (en) | 1987-07-14 |
| DE3785476T2 (en) | 1993-08-12 |
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