CN100558751C - The method and the polymer dispersion liquid that prepare polymer dispersion liquid - Google Patents

The method and the polymer dispersion liquid that prepare polymer dispersion liquid Download PDF

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CN100558751C
CN100558751C CNB2006800175052A CN200680017505A CN100558751C CN 100558751 C CN100558751 C CN 100558751C CN B2006800175052 A CNB2006800175052 A CN B2006800175052A CN 200680017505 A CN200680017505 A CN 200680017505A CN 100558751 C CN100558751 C CN 100558751C
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acid
sulfonic acid
dispersion liquid
polymer
polymer dispersion
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CN101180321A (en
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C·普日比拉
O·施特鲁克
A·拉舍夫斯基
B·保尔克
M·哈恩
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Akzo Nobel NV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Akzo Nobel NV
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/20Aqueous medium with the aid of macromolecular dispersing agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide

Abstract

The present invention relates to a kind of method for preparing polymer dispersion liquid, it comprises: will be present in one or more soluble anionic monomers (m in the reaction mixture that further comprises polymer stabilizer (B) and polymkeric substance co-stabilizer (C) 1) and one or more nonionic ethylene base monomers (m 2) polymerization.It further relates to the application and the papermaking process of polymer dispersion liquid, polymer dispersion liquid.

Description

The method and the polymer dispersion liquid that prepare polymer dispersion liquid
The present invention relates to a kind of method for preparing polymer dispersion liquid.It also relates to the application and the papermaking process of polymer dispersion liquid, polymer dispersion liquid.
Background of invention
The important application of the aqueous dispersion of the polymkeric substance of band anionic charge is reservation and the chemical conditioner in the paper industry.Other application of this base polymer dispersion liquid be therein when handling waste water they serve as in the kinds of processes of flocculation agent for example as auxiliary agent or in other solid-liquid separating technologies for example in metal, pottery, printing, biotechnology and pharmaceutical industries as auxiliary agent.They can also for example be used as thickening material and soil improvement agent in chemistry, biotechnology, medicine and the cosmetic industry.
Generally speaking, these polymer dispersion liquids comprise dispersive polymkeric substance and dispersion agent, wherein this dispersion agent polymer dispersant normally.
Usually by in the presence of salt, the reaction mixture polymerization of water soluble anion and non-ionic monomer being prepared anionic polymer fluid dispersion.Final polymkeric substance will precipitate from aqueous salt solution and form the stable polymer dispersion liquid by the suitable dispersion agent of use.WO 01/18063, US 5,837,776 and US 5,605,970 have disclosed the method for preparing water-soluble polymer dispersion, and it comprises the polymerisation that will contain in the aqueous reaction mixture of salt.
The factor of considering is for example to process viscosity, active quantities, stability, good retention and preparation polymer dispersion liquid, comprises the easiness for preparing stablizer sometimes.And some standards for example environment and safety problem are important.
Have many polymer dispersion liquids should satisfy in final the application, producing the standard of good results, and it have commercial benefits.These standards for example are low cost production, quick performance, effectively flocculation or dehydration and long storage time.
Described prior art anionic polymer fluid dispersion contains the salt of remarkable quantity, and it accounts for the major part of polymer dispersion liquid weight.Because environment and economic factors are wished minimizing at present or avoid using salt fully in polymer dispersion liquids.
When preparation during polymer dispersion liquid viscosity-" the processing viscosity " of reaction mixture should keep lower, and during the preparation polymer dispersion liquid, should avoid or reduce the viscosity peak value at least as much as possible.
The storage time of dispersion liquid, promptly polymer dispersion liquid is along with the stability of time is important performance.Not sedimentation is a settling in that dispersion liquid is stable to need effective dispersion agent to be used for keeping polymer beads.
Another factor of considering is an active quantities, i.e. the quantity of dispersive polymkeric substance in the polymer dispersion liquid.High reactivity content minimizes transportation cost and feasible easier processing when final the application.By using effective dispersion agent, the dispersion liquid that can obtain having high reactivity content can keep low with viscosity simultaneously.Yet the increase of active quantities on a certain degree may not can always produces improved reservation and dewatering in paper technology.
During the polymer dispersion liquid preparation, polymer precipitation may form and be bonded on reaction vessel and the agitator.This causes the cleaning process of time-consuming conversion unit.
An object of the present invention is to provide a kind of preferred salt-free water-soluble anionic polymer dispersion liquid with high stability and high reactivity content.This polymer dispersion liquid also will produce good reservation and dehydration results, for example serve as good flocculation agent, serves as good thickening material and can be used for soil improvement technology in multiple application examples such as cosmetic formulations in the wastewater treatment in other technologies when being used for paper technology.Another object of the present invention provides a kind of viscosity of wherein during preparation processing and keeps low and steadily and without any big viscosity peak value and do not produce the method for the preferred salt-free water-soluble anionic polymer dispersion liquid of sedimentary preparation.At last, the purpose of this invention is to provide a kind of papermaking process that wherein uses this polymer dispersion liquid.
The present invention
" stablizer " in this article refers to its effect is the polymkeric substance that dispersive polymer beads/drop is remained on dispersion state.
" co-stabilizer " in this article refers to and makes the polymkeric substance that is formed by one or more monomeric polymerizations be precipitated out the polymkeric substance that becomes solid particulate or drop from solution.
According to the present invention, be surprisingly found out that the high stability polymer dispersion liquid that can obtain to have high dispersed polymeres active quantities and low processing viscosity by a kind of method for preparing polymer dispersion liquid, this method comprises: will be present in one or more anionic monomers (m in the reaction mixture that further comprises polymer stabilizer (B) and polymkeric substance co-stabilizer (C) 1) and one or more nonionic ethylene base monomers (m 2) polymerization.
The present invention further comprises a kind of polymer dispersion liquid, and it comprises: one or more anionic monomers (m 1) and one or more nonionic ethylene base monomers (m 2) dispersed polymeres (A), polymer stabilizer (B) and polymkeric substance co-stabilizer (C).
Reaction medium is suitably water-bearing media.Polymer dispersion liquid is suitably the aqueous polymers dispersion liquid.This polymer dispersion liquid is suitably water miscible.Polymer beads/drop has about at the most 25 μ m aptly, also is suitably the about 25 μ m of about 0.01-, the about 15 μ m of preferably about 0.05-, the most preferably from about mean sizes (thickness) of the about 10 μ m of 0.2-.
Polymer stabilizer (B) is suitably organic polymer.Preferably, polymer stabilizer (B) is one or more polymer of monomers that belong to following group of material: vinylformic acid, methacrylic acid, methylene-succinic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, styrene sulfonic acid, toxilic acid, maleinamic acid and/or vinyl phosphonate.Other suitable polymers stablizers be toxilic acid or maleinamic acid respectively with the multipolymer of vinylbenzene or vinyl ether or alpha-olefin, this multipolymer can contain other comonomer.Preferably, polymer stabilizer (B) is acrylic or methacrylic acid and other listed monomer, the multipolymer of preferred 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS).
It is about 5 that the weight-average molecular weight of polymer stabilizer (B) is suitably, and 000-is about 5,000, and 000g/mol is preferred about 10, and 000-is about 1,000,000g/mol, and more preferably from about 20,000-is about 1,000,000g/mol, most preferably from about 35,000-is about 500,000g/mol.
Based on the gross weight of dispersion liquid or reaction mixture, this polymer dispersion liquid comprises the polymer stabilizer (B) of the about 5wt% of about 0.2-aptly, the about 3wt% of preferably about 0.5-, the most preferably from about about 1.5wt% of 0.8-.
Polymkeric substance promotor (C) is suitably organic polymer.Preferably, polymkeric substance co-stabilizer (C) is one or more polymer of monomers that belong to following group of material: vinylformic acid, methacrylic acid, sulfonic acid vinyl acetate, styrene sulfonic acid, methylene-succinic acid, vinyl phosphonate, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid and methacryloxypropyl sulfonic acid.
Preferably, in reaction mixture and polymer dispersion liquid, there are two or more co-stabilizers (C).
It is about 50 that the weight-average molecular weight of polymkeric substance co-stabilizer (C) is suitably about 100-, 000g/mol, and preferably about 500-is about 30,000g/mol, more preferably from about 1,000-is about 20,000g/mol, even more preferably from about 1,000-about 15,000g/mol, most preferably from about 1,000-is about 10,000g/mol.
Based on the gross weight of dispersion liquid or reaction mixture, this polymer dispersion liquid comprises one or more polymkeric substance co-stabilizers (C) of the about 50wt% of about 2-, the about 25wt% of preferably about 3-, the most preferably from about about 15wt% of 5-aptly.
Polymer stabilizer in reaction mixture or polymer dispersion liquid (B) is preferably made by different monomers with polymkeric substance co-stabilizer (C), if perhaps they are made by identical monomer, then contains different monomer ratio.
This polymer stabilizer (B) or polymkeric substance co-stabilizer (C) are not dextrin or dextrin derivative aptly.
Described one or more anionic monomers (m 1) belong to following group of material aptly: vinylformic acid, methacrylic acid, (styrene sulfonic acid), 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid and their an alkali metal salt, alkaline earth salt or ammonium salt.
Described one or more non-ionic monomers (m 2) belong to following classification material aptly: acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, the N-ethyl acrylamide, N-ethyl-methyl acrylamide, the N-N-isopropylacrylamide, N-isopropyl methyl acrylamide, N, the N-DMAA, N tert butyl acrylamide, N-tertiary butyl Methacrylamide, N-hydroxyethyl acrylamide, N-(three (methylol) methyl) acrylamide, the N-vinyl formamide, the N-vinyl acetamide, the hydroxyalkyl acrylate or the hydroxyalkyl methacrylate that have the C2-C4 alkyl, the alkyl acrylate or the alkyl methacrylate that have the C1-C4 alkyl, benzyl acrylate or benzyl methacrylate, acrylic or methacrylic acid and ester, perhaps acrylic or methacrylic acid and ester with mono methoxy hydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit with dihydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit.Preferably, one or more non-ionic monomers (m 2) belong to acrylamide, acrylate or methyl acrylic ester.
Anionic monomer (m 1) and non-ionic monomer (m 2) between mol ratio be suitably about 1: about 25: 75 of 99-, preferred about 3: about 20: 80 of 97-, most preferably from about 5: about 15: 85 of 95-.
It is about 1,000 that the weight-average molecular weight of dispersive polymkeric substance (A) is suitably, and 000-is about 15,000, and 000g/mol is preferred about 1,500, and 000-is about 10,000,000g/mol, and most preferably from about 2,000,000-is about 8,000,000g/mol.
Polymerization is suitably radical polymerization.Initiator is suitably the free radical precursor, is preferably water-soluble azo initiator, water-soluble peroxide or water soluble oxidized reduction initiator.Preferred initiator comprises: 2, two (amidine propane) hydrochlorides, 2 of 2 '-azo, 2 '-azo is two, and (2-methyl-N-(2-hydroxyethyl) propionic acid amide, 4,4 '-azo two (4-cyanopentanoic acid) and its an alkali metal salt and ammonium salt, tert-butyl hydroperoxide, perhydrol, peracetic dithionite or aforesaid superoxide and reductive agent be the combination of sodium metabisulfite or ferrous salt for example.
Based on the gross weight of dispersion liquid, this polymer dispersion liquid comprises the dispersed polymeres (A) of the about 40wt% of about 5-aptly, the about 30wt% of preferably about 10-, the most preferably from about about 25wt% of 12-.
Based on the gross weight of dispersion liquid or reaction mixture, the quantity of one or more inorganic salt is suitably the about 1.9wt% of 0-in the polymer dispersion liquid, the preferred about 1wt% of 0-, the more preferably about 0.5wt% of 0-, the about 0.1wt% of 0-most preferably, perhaps saliferous not substantially.
" inorganic salt " refer to any inorganic salt in this article aptly, preferably belong to the salt of inorganic base metal, alkaline-earth metal or ammonium halogenide, vitriol and phosphoric acid salt.
This polymer dispersion liquid can also comprise other material, for example linking agent and branching agent.
Polymerization temperature for example can depend on the monomer that uses and polymerization starter and change.Aptly, polymerization temperature is about 90 ℃ of about 30-, about 70 ℃ of preferably about 35-.This method is suitably semi-batch process, i.e. monomer m 1And m 2All be present in the beginning of polymerization process and further in later phases during reaction within a certain period of time with a or many parts or add continuously.Under the stir speed (S.S.) that is being suitable for method during the polymerization process, reaction mixture is stirred aptly.Aptly, stir speed (S.S.) is the about 1000rpm of about 100-.
The present invention further comprise polymer dispersion liquid as be used for the reservation of papermaking and chemical conditioner, as thickening material, as soil improvement agent and/or as the Application of Additives of the dry strength that improves paper.Polymer dispersion liquid of the present invention can more specifically be used as auxiliary agent and for example be used as flocculation agent when handling waste water in kinds of processes, perhaps for example be used as auxiliary agent in metal, pottery, printing, biotechnology and pharmaceutical industries in other solid-liquid separating technologies.This polymer dispersion liquid can also for example be used as thickening material in chemistry, biotechnology, medicine and the cosmetic industry.
At last, the present invention includes a kind of method of producing paper by the aq suspension that comprises the optional filler of cellulose fiber peacekeeping, it comprises: will add in the suspension according to aqueous polymers dispersion liquid of the present invention, make suspension moulding and it is drained on silk screen.
When polymer dispersion liquid being used for paper technology according to the present invention, dispersion liquid is joined in the suspension of the optional filler of cellulose fiber peacekeeping, this suspension will be with the quantity that can change in wide scope dehydration, and this quantity especially depends on the kind, filler content, filling kind, adding point of the kind of component and quantity, batching etc.Based on the dry-matter in the raw material that will dewater, the dispersive polymkeric substance is usually with at least 0.001%, and the quantity of 0.005wt% adding at least, and the upper limit usually is generally 3wt%, and is suitably 1.5wt%.Before adding it in cellulose suspension, aptly will be according to polymer dispersion liquid dilution of the present invention.Certainly, other conventional in papermaking additives and polymer dispersion liquid according to the present invention can be used in combination, for example silicon-dioxide-based sols, dry strength reagent, wet tenacity reagent, white dyes, dyestuff, sizing agent are such as rosin-Ji sizing agent and Mierocrystalline cellulose-active sizing agent, for example alkyl and alkenyl ketene dimers, alkyl and alkenyl ketenes polymer and succinyl oxide etc.This cellulose suspension or raw material can also contain the mineral filler of conventional kind, for example for example chalk, ground marble and precipitated chalk of kaolin, china clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate.Term used herein " paper " not only comprises paper and its production, and comprises the scraps of paper or the web-shaped product of other cellulose, for example plate and cardboard, and produce.This method can be used for preparing paper by the fibrous suspension of different types of cellulose, and based on dry-matter, this suspension comprises 25wt% and preferred these fibers of 50wt% at least at least aptly.This suspension can be based on deriving from dissolving pulp for example vitriol, sulphite and organosol paper pulp, mechanical pulp is thermomechanical pulp, chemical thermo-mechanical pulp, refiner paper pulp and grind the timber goods for example, derive from the fiber of hardwood and cork, and can be based on the regenerated fibre that randomly derives from de inked pulp and its mixture.
To further describe the present invention with the following Examples now, however the scope that these embodiment should not be construed as limiting the invention.
Embodiment
Embodiment 1:
The stablizer that preparation is made up of with 80: 20 mol ratios methacrylic acid (MAA) and 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS): the mixture of 85g ultrapure water, 8.24g AMPS (solid), 16.62g MAA and 11.5g NaOH (50%) is adjusted to pH 7 by means of NaOH (50%).0.02g EDTA (solid) is added mixture.Add other ultrapure water to reach the total mass of 127g.In its double-walled 150ml glass reactor that has anchor stirrer, nitrogen inlet, reflux exchanger and bottom valve of packing into.Be accompanied by 150/min mixture is stirred and use nitrogen purging.Reactor content is heated to 45 ℃.Add 0.05gV-50 (2, two (2-amidine propane) dihydrochlorides of 2 '-azo).After 60 minutes, temperature is increased to 50 ℃.In 72 hours under 50 ℃ and 150/min with polymerization of mixtures.Stablizer is refining and separate with lyophilize by ultrafiltration.Weight-average molecular weight is about 15,000g/mol.
Embodiment 2-7:
By in the presence of polymer stabilizer and polymkeric substance co-stabilizer, comprising acrylamide and acrylic acid monomer mixture polymerization prepares polymer dispersion liquid.
With 30g water, 24.3g co-stabilizer polyacrylic acid (45%, Sigma-Aldrich, Mw1,200), poly-(MAA-co-AMPS) (80: 20) of 1.2g stablizer multipolymer is (according to embodiment 1, Mw 15,000), the mixture of 28.1g acrylamide (50wt%), 1.07g vinylformic acid, 0.04g sodium formiate, 0.03g EDTA and 1.17g NaOH (50wt%) stirs and with pH regulator to 7.Add entry add to 100g and during 8 hours azo initiator VA-044 (4%) (2, two (N, N '-dimethylene NSC 18620) dihydrochloride, Wako) (progressively with the 0.5g) of 2 '-azo.Temperature is remained on 35 ℃.After 16 hours, stop to stir.
Use step same as described above, but change non-ionic monomer and anionic monomer ratio, in the dispersive polymkeric substance, use second kind of non-ionic monomer and use the combination of polyacrylic acid and polymethyl acrylic acid to prepare other 5 kinds of polymer dispersion liquids in some cases as co-stabilizer.The mol ratio of using 1.2wt% is that 80: 20 poly-(MMA-co-AMPS) is as stablizer.Active quantities in the stablizer (polymer content) is about 15wt%.Use the co-stabilizer of 11wt%.
In table 1, use following abbreviation:
The AAm=acrylamide
AA=vinylformic acid
The MMA=methyl methacrylate
The t-BuA=tert-butyl acrylate
The n-BuA=n-butyl acrylate
The PAA=polyacrylic acid
The PMAA=polymethyl acrylic acid
Table 1
Dispersion liquid Anionic monomer Non-ionic monomer Co-stabilizer Stablizer
Embodiment 2 AA(10mol-%) AAm (90mol-%) PAA(Mw 1,200) Poly--(MMA-co-AMPS) (Mw 15,000)
Embodiment 3 AA(15mol-%) AAm (85mol-%) PAA(Mw 1,200) Poly--(MMA-co-AMPS) (Mw 20,000)
Embodiment 4 AA(15mol-%) AAm (85mol-%) PAA (Mw 1,200) PMAA (Mw 9,500) (1: 1 ratio) Poly--(MMA-co-AMPS) (Mw 20,000)
Embodiment 5 MMA(10mol-%) AA(10mol-%) AAm (80mol-%) PAA(Mw 1,200) Poly--(MMA-co-AMPS) (Mw 20,000)
Embodiment 6 MMA(10mol-%) t-BuA(10mol-%) AAm (80mol-%) PAA(Mw 1,200) Poly--(MMA-co-AMPS) (Mw 20,000)
Embodiment 7 MMA(10mol-%) t-BuA(10mol-%) AAm (80mol-%) PAA (Mw 1,200) PMAA (Mw 9,500) (1: 1 ratio) Poly--(MMA-co-AMPS) (Mw 20,000)
For all dispersion liquids, processing viscosity lower (be lower than~2000mPas).
Embodiment 8:
By means of can be from Akribi, reservation and the dewatering of polymer dispersion liquid in paper technology that dynamic drainage analyzer (DDA) test that Sweden obtains prepares in embodiment 2-4.The batching of using is based on the 80/20 birch-pine tree paper pulp and the 40wt% lime carbonate of 60wt% bleaching.The raw material volume is 800ml, and pulp density is that 5g/L and electric conductivity are 1.5mS/cm.Under 1500rpm speed, stir raw material and simultaneously following material is added raw material: negatively charged ion waste collection agent (0.5kg/t), polymer dispersion liquid (1.0kg/t) and last anionic inorganic particle (0.5kg/t).Temperature is 22.5 ℃.Use 0.35 crust vacuum to be used for analyzing.Measure retention time (s) and turbidity (NTU).
Table 2. polymer dispersion liquid and application test
Figure C20068001750500151
Reach a conclusion: play the effect of reservation and chemical conditioner well according to dispersion liquid of the present invention.
Embodiment 9:
Test is according to the storage time of the dispersion liquid of embodiment 2-7, and it is measured as settling stability.Under 3000rpm with each dispersion liquid sample centrifugation of 10g 30 minutes.Measure the polymer precipitation quantity of each sample.There is not sample to produce any polymer precipitation.
Therefore reach a conclusion: the polymer dispersion liquid that can obtain to have long storage time and high reactivity content by the present invention.

Claims (31)

1. prepare the method for water-soluble polymer dispersion, it comprises: will be present in one or more soluble anionic monomers (m in the reaction mixture that further comprises polymer stabilizer (B) and polymkeric substance co-stabilizer (C) 1) and one or more nonionic ethylene base monomers (m 2) polymerization,
-described polymer stabilizer (B) is that one or more belong to the polymer of monomers of group material down: vinylformic acid, methacrylic acid, methylene-succinic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), the acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, the acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, styrene sulfonic acid, toxilic acid, maleinamic acid and/or vinyl phosphonate, or toxilic acid or maleinamic acid respectively with the copolymer analog of vinylbenzene or vinyl ether or alpha-olefin and
-described polymkeric substance co-stabilizer (C) is one or more polymer of monomers that belong to following group of material: vinylformic acid, methacrylic acid, sulfonic acid vinyl acetate, styrene sulfonic acid, methylene-succinic acid, vinyl phosphonate, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid and methacryloxypropyl sulfonic acid
Wherein the weight-average molecular weight of polymer stabilizer (B) is 20,000-1,000,000g/mol and wherein the weight-average molecular weight of polymkeric substance co-stabilizer (C) be 1,000-15,000g/mol.
2. according to the process of claim 1 wherein that this reaction mixture is that water-bearing media and this polymer dispersion liquid are the aqueous polymers dispersion liquids.
3. according to the process of claim 1 wherein that the mean sizes of polymer beads/drop is up to 25 μ m.
4. according to the method for claim 2, wherein the mean sizes of polymer beads/drop is up to 25 μ m.
5. according to each method of claim 1-4, wherein in this reaction mixture and polymer dispersion liquid, there are two or more co-stabilizers (C).
6. according to each method of claim 1-4, wherein polymer stabilizer (B) is made up of different monomers with polymkeric substance co-stabilizer (C).
7. according to each method of claim 1-4, wherein anionic monomer (m 1) belong to following group material aptly: vinylformic acid, methacrylic acid, (styrene sulfonic acid), 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid and their an alkali metal salt, alkaline earth salt or ammonium salt.
8. according to each method of claim 1-4, wherein one or more non-ionic monomers (m 2) belong to following group material: acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, the N-ethyl acrylamide, N-ethyl-methyl acrylamide, the N-N-isopropylacrylamide, N-isopropyl methyl acrylamide, N, the N-DMAA, N tert butyl acrylamide, N-tertiary butyl Methacrylamide, N-hydroxyethyl acrylamide, N-(three (methylol) methyl) acrylamide, the N-vinyl formamide, the N-vinyl acetamide, the hydroxyalkyl acrylate or the hydroxyalkyl methacrylate that have the C2-C4 alkyl, the alkyl acrylate or the alkyl methacrylate that have the C1-C4 alkyl, benzyl acrylate or benzyl methacrylate, acrylic or methacrylic acid and ester, perhaps acrylic or methacrylic acid and ester with mono methoxy hydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit with dihydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit.
9. according to each method of claim 1-4, wherein one or more monomers (m 2) belong to acrylamide, acrylate or methyl acrylic ester.
10. according to each method of claim 1-4, wherein based on the gross weight of dispersion liquid or reaction mixture, the quantity of inorganic salt is 0-1.9wt%.
11. according to each method of claim 1-4, wherein based on the gross weight of dispersion liquid or reaction mixture, the amount of one or more inorganic salt is 0-0.5wt%.
12. according to each method of claim 1-4, wherein reaction mixture comprises one or more soluble anionic monomers (m of 3-20mol% 1).
13. according to each method of claim 1-4, wherein reaction mixture comprises one or more nonionic ethylene base monomers (m of 80-97mol% 2).
14. according to each method of claim 1-4, wherein reaction mixture comprises the polymer stabilizer (B) of 0.5-3wt%.
15. according to each method of claim 1-4, wherein reaction mixture comprises the polymkeric substance co-stabilizer (C) of 3-25wt%.
16. water-soluble polymer dispersion, it comprises:
-one or more soluble anionic monomers (m 1) and one or more nonionic ethylene base monomers (m 2) dispersed polymeres (A),
-polymer stabilizer (B), it is that one or more belong to the polymer of monomers of group material down: vinylformic acid, methacrylic acid, methylene-succinic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), the acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, the acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, styrene sulfonic acid, toxilic acid, maleinamic acid and/or vinyl phosphonate, or toxilic acid or maleinamic acid respectively with the copolymer analog of vinylbenzene or vinyl ether or alpha-olefin and
-polymkeric substance co-stabilizer (C), it is one or more polymer of monomers that belong to following group of material: vinylformic acid, methacrylic acid, sulfonic acid vinyl acetate, styrene sulfonic acid, methylene-succinic acid, vinyl phosphonate, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid and methacryloxypropyl sulfonic acid
Wherein the weight-average molecular weight of polymer stabilizer (B) is 20,000-1,000,000g/mol and wherein the weight-average molecular weight of polymkeric substance co-stabilizer (C) be 1,000-15,000g/mol.
17. according to the polymer dispersion liquid of claim 16, wherein this reaction mixture is that water-bearing media and this polymer dispersion liquid are the aqueous polymers dispersion liquids.
18. according to the polymer dispersion liquid of claim 16, wherein the mean sizes of polymer beads/drop is up to 25 μ m.
19. according to the polymer dispersion liquid of claim 17, wherein the mean sizes of polymer beads/drop is up to 25 μ m.
20., wherein in this reaction mixture and polymer dispersion liquid, have two or more co-stabilizers (C) according to each polymer dispersion liquid of claim 16-19.
21. according to each polymer dispersion liquid of claim 16-19, wherein polymer stabilizer (B) is made up of different monomers with polymkeric substance co-stabilizer (C).
22. according to each polymer dispersion liquid of claim 16-19, wherein anionic monomer (m 1) belong to following group material aptly: vinylformic acid, methacrylic acid, (styrene sulfonic acid), 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (AMPS), 2-acrylamido-2-methyl-1-butene alkyl sulfonic acid (AMBS), acryloxy ethylsulfonic acid, methacryloxyethyl sulfonic acid, acryloxy propyl sulfonic acid, methacryloxypropyl sulfonic acid, vinyl sulfonic acid and their an alkali metal salt, alkaline earth salt or ammonium salt.
23. according to each polymer dispersion liquid of claim 16-19, wherein one or more non-ionic monomers (m 2) belong to following group material: acrylamide, Methacrylamide, N methacrylamide, N-methyl acrylamide, the N-ethyl acrylamide, N-ethyl-methyl acrylamide, the N-N-isopropylacrylamide, N-isopropyl methyl acrylamide, N, the N-DMAA, N tert butyl acrylamide, N-tertiary butyl Methacrylamide, N-hydroxyethyl acrylamide, N-(three (methylol) methyl) acrylamide, the N-vinyl formamide, the N-vinyl acetamide, the hydroxyalkyl acrylate or the hydroxyalkyl methacrylate that have the C2-C4 alkyl, the alkyl acrylate or the alkyl methacrylate that have the C1-C4 alkyl, benzyl acrylate or benzyl methacrylate, acrylic or methacrylic acid and ester, perhaps acrylic or methacrylic acid and ester with mono methoxy hydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit with dihydroxyl (polyethylene oxide) of 1-20 ethylene oxide unit.
24. according to each polymer dispersion liquid of claim 16-19, wherein one or more monomers (m 2) belong to acrylamide, acrylate or methyl acrylic ester.
25. according to each polymer dispersion liquid of claim 16-19, wherein based on the gross weight of dispersion liquid or reaction mixture, the quantity of inorganic salt is 0-1.9wt%.
26. according to each polymer dispersion liquid of claim 16-19, wherein based on the gross weight of dispersion liquid or reaction mixture, the amount of one or more inorganic salt is 0-0.5wt%.
27. according to each polymer dispersion liquid of claim 16-19, it comprises the dispersive polymkeric substance (A) of 10-30wt%.
28. according to each polymer dispersion liquid of claim 16-19, it comprises the polymer stabilizer (B) of 0.5-3wt%.
29. according to each polymer dispersion liquid of claim 16-19, it comprises the polymkeric substance co-stabilizer (C) of 3-25wt%.
30. according to each polymer dispersion liquid of claim 16-29 as the reservation of paper grade (stock) and chemical conditioner, as the additive of the dry strength that improves paper, as thickening material and/or as the application of soil improvement agent.
31. by the method that the aq suspension that comprises the optional filler of cellulose fiber peacekeeping is produced paper, it comprises: will add in the suspension according to each polymer dispersion liquid of claim 16-29, make suspension moulding and it is drained on silk screen.
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