JP2003041136A - Water-soluble polymer dispersion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a water-soluble polymer dispersion containing a dispersing agent enabling the efficient production of the water-soluble polymer without thickening the polymerization dispersion, in a dispersion polymerization method in the coexistence of a polymer-dispersing agent in a salt aqueous solution, and to provide a method for producing the water-soluble polymer dispersion, by which the water-soluble polymer dispersion can efficiently be produced. SOLUTION: This water-soluble polymer dispersion contains one or more kinds of water-soluble polymer fine particles selected from cationic water-soluble polymer fine particles, nonionic water-soluble polymer fine particles and amphoteric water-soluble polymer fine particles and having a particle diameter of <=100 μm and one or more polycondensation polymers soluble in a salt aqueous solution as a dispersing agent, in the salt aqueous solution. One or more kinds of the water-soluble polymer fine particles selected from the cationic watersoluble polymer fine particles, the nonionic water-soluble polymer fine particles and the amphoteric water-soluble polymer fine particles are produced by stirring, dispersing and polymerizing a monomer (mixture) comprising 0 to 100 mol.% of monomers represented by the general formula (1) and/or (2), 0 to 50 mol.% of a monomer represented by the general formula (3), 0 to 100 mol.% of acrylamide and 0 to 30 mol.% of a copolymerizable nonionic monomer in the presence of at least one of polycondensation polymers soluble in the salt aqueous solution as a dispersing agent in the salt aqueous solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble polymer dispersion and a method for producing the same, and more specifically to a water-soluble aqueous solution having a particle size of 100 mμ or less selected from cationic, nonionic and amphoteric. The present invention relates to a water-soluble polymer dispersion liquid in which at least one kind of polycondensation type polymer which is soluble in the salt aqueous solution as a dispersant and a water-soluble polymer fine particle coexists.

[0002]

2. Description of the Related Art Water-soluble cationic polymers are used as coagulants for wastewater treatment or as papermaking agents, but since they are polymer compounds, they become highly viscous solutions when dissolved in water. Or to any product form for that is a big point in terms of commercialization. For example, in the static polymerization method of an aqueous solution, in order to obtain a high molecular weight polymer, 1
Since the polymerization is carried out at a monomer concentration of 0% by weight or more, the product becomes a gel containing water and is difficult to dissolve in the state as it is. Therefore, the product is further diluted to have a low fluidity and a low concentration. A post-polymerization step such as commercialization as a solution is required. One of the countermeasures is pulverization, which many products use. However, powdered products take a long time to dissolve during use, and the energy required for that
Also takes a lot. Emulsion products are the solution. It is polymerized in the state of a water-in-oil emulsion, and after the polymerization, it is sold in a state in which it is easily dissolved by adding a hydrophilic surfactant. The dissolution time is shorter than that of powders, and high molecular weight polymers with high degree of polymerization can also be obtained.

However, the water-in-oil type emulsion has the disadvantage that it has flammability and wastes valuable organic solvent. Further, in suspension polymerization in a hydrophobic solvent,
Since flammable substances such as cyclohexane and toluene are used, there is a drawback that a large amount of cost is required for manufacturing equipment. In order to overcome the drawbacks of the water-in-oil emulsion polymerization method, the polyvalent anion salt aqueous solution is dissolved in the polyvalent anion salt aqueous solution, for example, acryloyloxyethylbenzyldimethyldimethylammonium chloride (co) polymer. A method has been developed for producing a dispersion in which a non-polymer is dispersed as fine particles in salt water. This is special fair 4-3
It can be produced by the method described in Japanese Patent No. 9481 or Japanese Patent Publication No. 6-51755. The former publication discloses a method of allowing a polyvalent alcohol to coexist as a dispersant during polymerization, and the latter publication allows a cationic polymer soluble in a polyvalent anion salt aqueous solution to coexist as a dispersant during polymerization. A method is disclosed.

In these publications, a (meth) acryloyloxyethylbenzyldialkylammonium chloride-based monomer such as acryloyloxyethylbenzyldimethylammonium chloride is a cation used as an essential component during the polymerization and coexisting during the copolymerization. The polymerizable monomer is N, N-dialkylaminoethyl (meth) acrylate, which is an acrylic monomer containing a tertiary amino group or a quaternary ammonium salt group. Currently, a problem is that when the copolymerization rate of the benzylic monomer is reduced or is not used at all, the viscosity at the time of polymerization is so severe that dispersion polymerization is often impossible. As a dispersant, a cationic polymer that is soluble in a polyvalent alcohol or a polyvalent anion salt aqueous solution is mainly used, but the development of a dispersant suitable for suppressing thickening is a major theme. Has become.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to develop a water-soluble polymer dispersion liquid containing a dispersant capable of suppressing thickening during polymerization and efficiently producing water-soluble polymer molecules. , To develop a production method capable of efficiently producing the water-soluble polymer dispersion.

[0006]

Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have made earnest studies and, as a result, have arrived at the following invention. That is, the invention of claim 1 has a particle size of 1 in a salt solution.
A high water-solubility in which one or more water-soluble polymer fine particles selected from cationic, nonionic and amphoteric with a size of 00 μm or less and at least one polycondensation polymer soluble in the aqueous salt solution as a dispersant coexist. It is a molecular dispersion.

According to a second aspect of the present invention, one or more water-soluble polymer fine particles selected from cationic, nonionic and amphoteric are at least a polycondensation polymer soluble as a dispersant in the aqueous salt solution. The following general formula (1)
And / or 0 to 100 mol% of the monomer represented by (2),
A monomer (mixture) consisting of 0 to 50 mol% of the monomer represented by (3), 0 to 100 mol% of acrylamide, and 0 to 30 mol% of another copolymerizable nonionic monomer, A water-soluble polymer dispersion characterized by being produced by dispersion polymerization under stirring in an aqueous salt solution.

[Chemical 1] General formula (1) R1 is hydrogen or a methyl group, R2 and R3 are C1 to C3 alkyl or alkoxyl groups, R4 is hydrogen, a C1 to C3 alkyl group, alkoxyl group or benzyl go, May be different, A is oxygen or N
H and B represent an alkylene group having 2 to 4 carbon atoms or an alkoxylene group, and X1 represents an anion.

[Chemical 2] Formula (2) R5 represents hydrogen or a methyl group, R6 and R7 represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion.

[Chemical 3] General formula (3) R8 is hydrogen, a methyl group or a carboxymethyl group, A is SO3, C6H4SO3, CONHC (CH3) 2CH
2SO3, C6H4COO or COO, R9 is hydrogen or COOY2, Y1 or Y2 is hydrogen or cation

The invention of claim 3 is characterized in that the polycondensation polymer is a polycondensation product of one or more amines selected from ammonia, aliphatic monoamines and aliphatic polyamines with epihalohydrin. The water-soluble polymer dispersion according to claim 1.

A fourth aspect of the invention is the water-soluble polymer dispersion according to the eighth aspect, wherein the aliphatic polyamine is a polyethylene polyamine represented by the following general formula (4).

[Chemical 4] General formula (4) n is an integer of 1-10.

According to a fifth aspect of the present invention, in the water-soluble polymer dispersion liquid according to the third or fourth aspect, the ion equivalent value of the polycondensation polymer is 1.5 to 10 meq / g. is there.

According to a sixth aspect of the present invention, the weight average molecular weight of one or more water-soluble polymers selected from the cationic, nonionic and amphoteric constituents of the polymer dispersion is 2,000,000 or more and 20,000,000 or less. The water-soluble polymer dispersion according to claim 1, wherein

The invention according to claim 7 is the water-soluble polymer dispersion according to claim 1, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.

According to the invention of claim 8, in a salt solution, at least one polycondensation polymer soluble in the salt solution is allowed to coexist as a dispersant, and the general formula (1) and / or ( 0-100 mol% of the monomer represented by 2), 0-50 mol% of the monomer represented by (3) Acrylamide 0-10
0 mol% and other copolymerizable nonionic monomers 0-3
A method for producing a water-soluble polymer dispersion liquid comprising fine particles having a particle diameter of 100 mμ or less, which comprises dispersing and polymerizing 0 mol% of a monomer (mixture) under stirring.

The invention of claim 9 is characterized in that the polycondensation polymer is a polycondensation product of epihalohydrin with one or more amines selected from ammonia, aliphatic monoamines and aliphatic polyamines. The method for producing a water-soluble polymer dispersion according to claim 8.

The invention of claim 10 is the method for producing a water-soluble polymer dispersion according to claim 9, wherein the aliphatic polyamine is a polyethylene polyamine represented by the general formula (4). .

The invention of claim 11 is characterized in that the polycondensation polymer has an ion equivalent value of 1.5 to 10 meq / g, and the water-soluble polymer dispersion liquid according to claim 9 or 10. It is a manufacturing method.

The twelfth aspect of the invention is the method for producing a water-soluble polymer dispersion according to the eighth aspect, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt. .

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION One or more water-soluble polymer dispersions selected from cationic, nonionic and amphoteric of the present invention are polycondensation polymer dispersions which are soluble in an aqueous salt solution. 100 μm grain system produced by dispersion polymerization in the presence of agents
It consists of polymer fine particles of m or less. The specific manufacturing method is as follows. An aqueous solution of a polyvalent anion salt such as ammonium sulfate is prepared, and a (meth) acrylate-based quaternary ammonium salt group-containing monomer and acrylamide are used as the cationic monomer, or (meth) in the case of an amphoteric water-soluble polymer. Acrylic acid is added, and a polycondensation polymer as a dispersant is allowed to coexist before polymerization. The pH at this time is set to 2-6. After the mixture is uniformly dissolved, oxygen is removed from the reaction system by nitrogen substitution, and a radical polymerizable initiator is added to initiate polymerization, whereby a polymer can be produced. In addition, coexistence of a chain transfer agent, a cross-linking agent and the like before the start of polymerization is the same as in other polymerization methods.

First, the polycondensation polymer used as the dispersant will be described. The polycondensation polymer used in the present invention is a polycondensation product of epihalohydrin with at least one compound selected from ammonia, aliphatic monovalent amines and aliphatic polyamines. Examples of the aliphatic monovalent amine include monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and the like. Aliphatic polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, hexamethylenediamine and the like. Particularly preferred among these amines are monomethylamine, dimethylamine, trimethylamine, ethylenediamine or pentaethylenehexamine.

The polycondensate may be the ammonia, the aliphatic monovalent amine or the aliphatic polyamine, or may be a product obtained by reacting epihalohydrin with a mixture of two or more kinds. A product having a molecular weight increased by reacting a group monovalent amine with epihalohydrin to form a condensate and reacting with ammonia or an aliphatic polyamine in the second stage of the reaction may be used. The molecular weight of the polycondensate is several hundreds to about 2,000,000.

The composition of these polycondensation type polymers with respect to the monomers is selected according to the monomers to be polymerized. In particular, when carrying out the copolymerization in which the ratio of the cationic monomer is low, it is effective to use a polycondensation polymer having high ionicity, for example, a polycondensation polymer of polyethylene polyamine and epihalohydrin. On the contrary, when the copolymerization ratio of the ionic monomer is high, it is effective to use a polycondensation polymer having low ionicity, for example, a polycondensation polymer of diethylamine and epihalohydrin.
The dispersant of the present invention is not limited to being used in two or more kinds, but it is very complicated in management to combine with three or four kinds, and preferably one or two kinds are used in combination. The amount of the polycondensation polymer dispersant added to the monomer is 1/100 to 20/100, preferably 2/100 to 15/100 with respect to the monomer.

The reason why the use of the polycondensation type polymer in the present invention is effective, many theoretically unknown parts cannot be elucidated. However, when estimated from the viewpoint of phenomena, it becomes as follows.
That is, as the polymerization proceeds in a salt aqueous solution, the concentration of the produced polymer becomes equal to or higher than the solubility and precipitation of polymer particles begins, but before that, the polymer itself (polymerization system) is not formed because the polymer is dissolved. The viscosity also increases, and the dissolved polymer and precipitated particles coexist. After that, the ratio of the precipitated polymer increases, the viscosity of the polymer gradually decreases, and the polymer changes into a dispersed state. In this coexistence state, the slip between the precipitated particles and the gelled dissolved polymer is improved, and the phase change from the thickened state before the phase change to the dispersed state is smoothly transferred. It is considered to be the main role of the agent.
The polycondensation polymer has a considerably lower molecular weight than the acrylic cationic polymer and has a relatively high cation density. Therefore, the adsorbed polycondensation polymer closely covers the surface of the deposited particles, stabilizes the dispersion by electrical repulsion between the particles, and causes microscopic phase separation between the deposited particles and the dissolved gel polymer. . This effect reduces the viscosity around the particles and improves the slip between the precipitated particles and the dissolved gelled polymer,
It is estimated to achieve a smooth phase change.

Among the cationic monomers used when polymerizing a water-soluble polymer selected from cationic, nonionic and amphoteric, examples of the cationic monomer represented by the general formula (1) are: Examples of the tertiary amino group-containing monomer include dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide. Examples of the quaternary ammonium group-containing monomer include (meth) acryloyloxyethyl trimethylammonium chloride and (meth) acryloyl which are quaternized products of the tertiary amino-containing monomer with methyl chloride or benzyl chloride. Oxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxy2-hydroxypropyldimethylbenzylammonium chloride, (meth ) Acryloylaminopropyldimethylbenzyl ammonium chloride and the like. Further, examples of the cationic monomer represented by the general formula (2) include diallylmethylamine, diallylbenzylamine, dimethyldiallylammonium chloride diallylmethylbenzylammonium chloride and the like.

The anionic monomer used may be a sulfone group or a carboxyl group, and both may be used in combination. Examples of the sulfonic group-containing monomer are vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, and the like.
Examples of the carboxyl group-containing monomer are methacrylic acid,
Examples thereof include acrylic acid, itaconic acid, maleic acid and p-carboxystyrene.

When polymerizing a nonionic water-soluble polymer, acrylamide is used. Further, a nonionic monomer other than acrylamide may be copolymerized. Further, when a cationic or amphoteric water-soluble polymer is polymerized, another nonionic monomer may be copolymerized. As such examples, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide,
N-vinylpyrrolidone, N-vinylformamide, N-
Examples thereof include vinylacetamide and acryloylmorpholine.

When the dispersion of the cationic water-soluble polymer is prepared, the molar ratio of the cationic monomer is 1 to 100 mol%, preferably 5 to 100 mol%, preferably 10 to 100 mol%. Mol%. When a dispersion liquid of an amphoteric water-soluble polymer is produced, the content of the cationic monomer is 10 to 90 mol%, preferably 20 to 90 mol%. The anionic monomer content is preferably 5 to 50 mol%, more preferably 5 to 40 mol%. Acrylamide is 0
It is 95 mol%, preferably 0 to 85 mol%.

Further, polyfunctional monomers such as N, N-methylenebisacrylamide and ethylene glycol (meth) acrylate, or N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) ) It is also possible to copolymerize a thermally crosslinkable monomer such as acrylamide to synthesize a crosslinked or branched polymer and modify it.

The polymerization conditions are usually determined appropriately depending on the monomers used and the copolymerization mol%, and the temperature is from 0 to 10
Perform in the range of 0 ° C. A radical polymerization initiator is used to initiate the polymerization. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo type, peroxide type and redox type. Examples of oil-soluble azo initiators include 2,2′-azobisisobutyronitrile,
1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropione-
G), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile, etc., which are dissolved in a water-miscible solvent and added.

Examples of water-soluble azo initiators include:
2'-azobis (amidinopropane) dihydrochloride,
2,2'-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 4,4 '
-Azobis (4-cyanovaleric acid) and the like. Further, examples of the redox system include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like. Further examples of peroxides include ammonium or potassium peroxodisulfate,
Examples thereof include hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate and the like. Most preferred of these initiators are water-soluble azo initiators2,
2'-azobis (amidinopropane) dihydrochloride,
2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride.

The salt to be used is a salt of an alkali metal ion such as sodium or potassium or an ammonium ion with a halide ion, a sulfate ion, a nitrate ion or a phosphate ion, but a salt with a polyvalent anion. Is more preferable. The salt concentration of these salts is 7% by weight to
Can be used up to saturation concentration.

The water-soluble polymer dispersion liquid selected from the cationic, nonionic and amphoteric of the present invention is used for dehydration of pulp sludge in the paper industry, other wastewater treatment of food industry, metal and petroleum refining, and building materials. It is also applicable to mixed sludge containing organic sludge and coagulated sludge generated in general industrial wastewater treatment. As a particularly effective target, it exerts an excellent effect on sewage, digested sludge of human waste, or excess sludge of food industry wastewater. These sludges are prepared by dissolving the amphoteric water-soluble polymer dispersion of the present invention in water to form an aqueous solution, and then adding and coagulating it, and then using a dehydrator such as a belt press, a filter press, a decanter or a screw press. Dehydrate. The amount added varies depending on the type of wastewater, the concentration of suspended matter, etc.
It is about 0.1 to 1000 ppm with respect to the liquid amount. Moreover, it is 0.1 to 3 weight% with respect to sludge ss.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

(Synthesis Example-1) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rikakikai), and a condenser. A 50% aqueous solution of dimethylamine (90.0 g) and ion-exchanged water (97.8 g) were charged therein. Then, while cooling the reactor with ice water, the temperature is raised to 50 ° C.
While keeping the temperature below, 101.8 g of epichlorohydrin was supplied over 1 hour. The molar ratio is 1: 1.1. Then 5
After reacting for an hour, the process was completed. After the reaction, the cation equivalent and the weight average molecular weight by the light scattering method were measured. This is a dispersant
Set to 1. The results are shown in Table 1.

(Synthesis Example-2) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rikakikai), and a condenser. 54.0 g of 50% aqueous solution of dimethylamine, 31.0 g of 40% aqueous solution of monomethylamine, and 95.6 g of ion-exchanged water were charged therein. Then, while cooling the reactor with ice water, the temperature was kept at 50 ° C or lower, and 101.8 g of epichlorohydrin was supplied over 1 hour. The molar ratio is dimethylamine: monomethylamine: epichlorohydrin = 0.6: 0.4: 1.1. Then, the reaction was carried out for 5 hours to complete the reaction, and the cation equivalent and the molecular weight were measured. This is designated as dispersant-2. The results are shown in Table 1.

(Synthesis example-3) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rikakikai), and a condenser. 54.0 g of 50% aqueous solution of dimethylamine, 59.0 g of 40% aqueous solution of trimethylamine, and 90.0 g of ion-exchanged water were charged therein. Then, while cooling the reactor with ice water, the temperature was kept at 50 ° C or lower, and 101.8 g of epichlorohydrin was supplied over 1 hour. The molar ratio is dimethylamine: trimethylamine: epichlorohydrin = 0.6: 0.4: 1.1. Then, the reaction was carried out for 5 hours to complete the reaction, and the cation equivalent and the molecular weight were measured. This is designated as dispersant-3. The results are shown in Table 1.

(Synthesis Example-4) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rikakikai), and a condenser. 50% aqueous solution of dimethylamine 72.0 g and diethylenetriamine 20.6
g, and ion-exchanged water 120.4 g was added. Then, while cooling the reactor with ice water, the temperature was kept at 50 ° C or lower, and 101.8 g of epichlorohydrin was supplied over 1 hour. The molar ratio is dimethylamine: diethylenetriamine: epichlorohydrin = 0.8: 0.2: 1.1. Then, the reaction was carried out for 5 hours to complete the reaction, and the cation equivalent and the molecular weight were measured. This is designated as dispersant-4. The results are shown in Table 1.

(Synthesis Example-5) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a monomer supply tube connected to a peristaltic pump (SMP-21 type, manufactured by Tokyo Rikakikai), and a condenser. 50% aqueous solution of dimethylamine 45.0g and 29% aqueous solution of ammonia water 2
0.6 g and ion-exchanged water 89.5 g were added. And keep the temperature below 50 ℃ while cooling the reactor with ice water,
101.8 g of epichlorohydrin was fed over 1 hour. The molar ratio is dimethylamine: ammonia: epichlorohydrin = 0.5: 0.5: 1.1. Then 5
The reaction was carried out for a time and then terminated, and the cation equivalent and the molecular weight were measured. This is designated as dispersant-5. The results are shown in Table 1.

(Synthesis Example-6) 200 g of Test Product-1 was collected, and 13.3 g of pentaethylenehexamine (5 mol% based on the number of moles of embedding epichlorohydrin) was added.
The reaction was carried out at 40 ° C, and when an increase in viscosity was observed, hydrochloric acid was added to terminate the reaction. The cation equivalent and the molecular weight were measured in the same manner as in other synthesis examples. This is designated as dispersant-6. The results are shown in Table 1.

(Synthesis Example-7) 200 g of Test Product-1 was sampled, and 9.7 g of ammonia water corresponding to 15 mol% of ammonia based on the mole number of embedding epichlorohydrin was added. The reaction was carried out at 40 ° C, and when an increase in viscosity was observed, hydrochloric acid was added to terminate the reaction. Similarly, the cation equivalent and the molecular weight were measured. This is designated as dispersant-7. The results are shown in Table 1.

[0040]

Example 1 In a five-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 13.8 g (pairs of Dispersant-1 (50% aqueous solution) prepared in Synthesis Example 1) (Monomer 5.5%), ion-exchanged water 244.1 g, ammonium sulfate 115.0 g, acrylamide 50% aqueous solution 6
Charge 7.4 g and acryloyloxyethyl trimethyl ammonium chloride, 115.0 g 80% aqueous solution,
It was completely dissolved. The internal temperature was maintained at 33 to 35 ° C., and after substituting with nitrogen for 30 minutes, 2,2′-azobis [2-
(5-Methyl-2-imidazolin-2-yl) propane] 1.9 g of a 1% aqueous solution of dihydrochloride (0.015% based on the monomer) was added to initiate polymerization. 2.5 hours after the start of the reaction, a slight increase in the viscosity of the reaction product was observed, but the state was maintained for 25 minutes, but immediately after that, the reaction product stopped and was transferred to the dispersion liquid. After 6 hours from the start, the initiator solution was added to 0.
An additional 5 g was added and polymerization was carried out for 6 hours. The concentration of the lumped monomer in the obtained dispersion was 22.0%, the particle size of the polymer was 10 μm or less, and the viscosity of the dispersion was 210 mPa · s. Moreover, the weight average molecular weight was measured by a molecular weight measuring device (DLS-7000 manufactured by Otsuka Electronics) by the static light scattering method. This sample is referred to as prototype-1. The results are shown in Table 2.

[0041]

Example 2 By the same operation as in Example 1, using Dispersant-3, acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethylbenzyldimethylammonium chloride = 60/20/2
0 copolymer dispersion, trial-2 was synthesized. The results are shown in Table 2.
Shown in.

[0042]

Example 3 By the same operation as in Example 1, using Dispersant-4, a copolymer dispersion of acrylamide / acryloyloxyethyltrimethylammonium chloride = 80/20, Trial Production-3 was synthesized. The results are shown in Table 2.

[0043]

Example 4 A copolymer dispersion of acrylamide / acryloyloxyethyltrimethylammonium chloride / methacryloyloxyethyltrimethylammonium chloride = 30/40/30 was prepared by using Dispersant-6 in the same manner as in Example 1. Prototype-4 was synthesized. The results are shown in Table 2.

[0044]

Example 5 In a five-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 59.0 g of 50% aqueous solution of acrylamide and 2% aqueous solution of 60% acrylic acid were placed.
5.0g was added and 35% sodium hydroxide aqueous solution 2
An equivalent amount of acrylic acid was neutralized with 3.8 g. To this, 15.6 g of Dispersant-5 of Synthesis Example 5 (40% aqueous solution)
(Vs. 5.0%), ion-exchanged water (175 g), ammonium sulfate (115.0 g), and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 10
0.6 g was charged and completely dissolved. Internal temperature is 33 to 3
Keep the temperature at 5 ° C and replace with nitrogen for 30 minutes.
Polymerization was initiated by adding 1.9 g of 1% aqueous solution of 2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride to 0.015% of the amount. It was After 2 hours from the start, a slight increase in the viscosity of the reaction product was observed, but this state continued for 20 minutes, and immediately after that, it settled and transferred to the dispersion liquid. After 6 hours from the start, 1.2 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The resulting dispersion had a loading content to concentration of 23%, a polymer particle size in the range of 10 to 30 μm, and a viscosity of the dispersion of 140 mPa · s. Moreover, the weight average molecular weight was measured by a molecular weight measuring device (DLS-7000 manufactured by Otsuka Electronics) by the static light scattering method. This sample is referred to as prototype-4. The results are shown in Table 2.

[0045]

Example 6 Dispersant-2 was used in the same manner as in Example 5, and acrylamide / acryloyloxyethyltrimethylammonium chloride / acrylic acid / itaconic acid =
A 45/40/10/5 copolymer dispersion, trial-6, was synthesized. The results are shown in Table 2.

[0046]

Example 7 By the same operation as in Example 5, using Dispersant-6, acrylamide / acryloyloxyethyltrimethylammonium chloride / acroyloxyethylbenzyldimethylammonium chloride / acrylic acid = 40.
/ 30/20/10 copolymer dispersion liquid, Prototype-7 was synthesized. The results are shown in Table 2.

[0047]

Example 8 Dispersant-1 was used in the same manner as in Example 5 except that acrylamide / acryloyloxyethyltrimethylammonium chloride / itaconic acid = 50/40 /
Ten copolymer dispersions, Trial-8, were synthesized. The results are shown in Table 2.

[0048]

Comparative Example 1 Acryloyloxyethyltrimethylammonium chloride homopolymer (comparative dispersant-1, 20% aqueous solution, was placed in a five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. Weight average molecular weight 80
10,000), 34.4 g (5.5% of monomer), 227.1 g of ion-exchanged water, 115.0 g of ammonium sulfate, 67.4 g of 50% acrylamide aqueous solution and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 115. 0 g was charged and completely dissolved. Inside temperature 33
After maintaining the temperature at ˜35 ° C. and substituting with nitrogen for 30 minutes, 1.9 g of a 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride as an initiator. (0.015% of monomer) was added to initiate polymerization. After 2 hours from the start, the reaction product showed a slightly large increase in viscosity, which continued for about 40 minutes, but gradually settled and transferred to the dispersion liquid. Six hours after the start, 0.5 g of the above-mentioned initiator solution was added, and polymerization was further performed for 6 hours. The obtained dispersion has a swelling monomer concentration of 22.0%, a polymer particle size of 10 μm or less, and a dispersion viscosity of 880 mPas.
・ It was s. Moreover, the weight average molecular weight was measured by a molecular weight measuring device (DLS-7000 manufactured by Otsuka Electronics) by the static light scattering method. This sample is designated as Comparison-1. The results are shown in Table 2.
Shown in.

[0049]

Comparative Example 2 Acryloyloxyethyltrimethylammonium chloride / acryloyloxyethylbenzyldimethylammonium chloride = 50/50 copolymer (dispersant-2,
20% aqueous solution, weight average molecular weight 500,000) and copolymer dispersion of acrylamide / acryloyloxyethyltrimethylammonium chloride = 50/50, comparison-2
Was synthesized. The results are shown in Table 1.

[0050]

[Comparative Example 3] In a five-necked separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 59.0 g of 50% aqueous solution of acrylamide and 2% aqueous solution of 60% acrylic acid were placed.
5.0g was added and 35% sodium hydroxide aqueous solution 2
An equivalent amount of acrylic acid was neutralized with 3.8 g. Acryloyloxyethyltrimethylammonium chloride homopolymer (comparative dispersant-1, 20% aqueous solution, weight average molecular weight 800,000), 34.4 g (to monomer 5.5).
%), Ion-exchanged water 160 g, ammonium sulfate 11
5.0 g, acryloyloxyethyltrimethylammonium chloride, and 100.6 g of an 80% aqueous solution were charged and completely dissolved. Keeping the internal temperature at 33-35 ° C, 3
After substituting with nitrogen for 0 minutes, 1.9 g of a 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride as an initiator (vs. unit amount vs. 0 (0.015%) g was added to initiate polymerization. After 1 hour and 35 minutes from the start, the reaction product showed a slightly large increase in viscosity, about 3
The state continued for 0 minutes, but it gradually settled and gradually moved to the dispersion liquid. 6 hours after the start, the initiator solution was added to 1.2
g was added, and polymerization was further performed for 8 hours. The resulting dispersion has a loading content of 23% and a polymer particle size of 10%.
~ 40 μm, the viscosity of the dispersion is 1100 mP
It was a.s. Moreover, the weight average molecular weight was measured by a molecular weight measuring device (DLS-7000 manufactured by Otsuka Electronics) by the static light scattering method. This sample is designated as Comparative-3. The results are shown in Table 2.

[0051]

Comparative Example 4 Acryloyloxyethyltrimethylammonium chloride / methacryloyloxyethyltrimethylammonium chloride = 70/30 copolymer (Comparative Dispersant-3, 20) was used as a dispersant by the same operation as in Comparative Example 5.
% Aqueous solution, weight average molecular weight 1.2 million) was used to synthesize a acrylamide / acryloyloxyethyltrimethylammonium chloride / acrylic acid = 40/40/20 copolymer dispersion, Comparative-4. The results are shown in Table 2.

[0052]

[Table 1] DA: dimethylamine, MMA: monomethylamine, T
MA: trimethylamine, DEA: trimethylamine AM: ammonia, PEH: pentaethylenehexamine, EPC: epichlorohydrin, DMM: dimethylaminoethyl methacrylate, DMA: dimethylaminoethyl acrylate

[0053]

[Table 2] DMQ: acryloyloxyethyltrimethylammonium chloride, DMC: methacryloyloxyethyltrimethylammonium chloride, DMPQ: acryloylaminopropyltrimethylammonium chloride, ABC: acryloyloxyethyldimethylbenzylammonium chloride, AAC: acrylic acid, AAM: acrylamide, Addition amount is based on monomer (wt%) Monomer concentration: wt%, monomer ratio is mol%, dispersion viscosity: mPa · s

[0054]

[Table 3] Monomer concentration: wt%, dispersion viscosity: mPa · s Molecular weight: Unit is 10,000

Claims (12)

[Claims] 1. A salt aqueous solution containing one or more water-soluble polymer fine particles having a particle size of 100 μm or less and selected from cationic, nonionic and amphoteric particles, and a polycondensation system soluble as a dispersant in the salt aqueous solution. A water-soluble polymer dispersion liquid in which at least one kind of molecules coexists. 2. One or more water-soluble polymer fine particles selected from cationic, nonionic and amphoteric coexist with at least one polycondensation polymer soluble in the salt aqueous solution as a dispersant, The following general formula (1) and / or (2)
0 to 100 mol% of the monomer represented by, 0 to 50 mol% of the monomer represented by (3), 0 to 100 mol% of acrylamide, and other nonionic monomer capable of copolymerization 0 to The water-soluble polymer dispersion according to claim 1, which is produced by dispersion-polymerizing 30 mol% of a monomer (mixture) in an aqueous salt solution with stirring. [Chemical 1] General formula (1) R1 is hydrogen or a methyl group, R2 and R3 are C1 to C3 alkyl or alkoxyl groups, R4 is hydrogen, a C1 to C3 alkyl group, alkoxyl group or benzyl go, May be different, A is oxygen or N
H and B represent an alkylene group having 2 to 4 carbon atoms or an alkoxylene group, and X1 represents an anion. [Chemical 2] Formula (2) R5 represents hydrogen or a methyl group, R6 and R7 represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X2 represents an anion. General formula (3) R8 is hydrogen, a methyl group or a carboxymethyl group, A is SO3, C6H4SO3, CONHC
(CH3) 2CH2SO3, C6H4COO or C
OO and R9 are hydrogen or COOY2, Y1 or Y2
Is hydrogen or cation 3. The polycondensation polymer is a polycondensation product of epihalohydrin with one or more amines selected from ammonia, aliphatic monoamines and aliphatic polyamines. Water-soluble polymer dispersion of. 4. The water-soluble polymer dispersion liquid according to claim 3, wherein the aliphatic polyamine is a polyethylene polyamine represented by the following general formula (4). [Chemical 4] General formula (4) n is an integer of 1-10. 5. The water-soluble polymer dispersion according to claim 3, wherein the polycondensation polymer has an ion equivalent value of 1.5 to 10 meq / g. 6. The weight-average molecular weight of one or more water-soluble polymers selected from cationic, nonionic and amphoteric constituents of the polymer dispersion is 2,000,000 or more and 20,000,000 or less. The water-soluble polymer dispersion liquid according to claim 1. 7. The water-soluble polymer dispersion liquid according to claim 1, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt. 8. In a salt aqueous solution, at least one polycondensation polymer soluble in the salt aqueous solution is allowed to coexist as a dispersant and is represented by the general formula (1) and / or (2). 0 to 100 mol% of the monomer, and the monomer 0 represented by (3)
.About.50 mol%, acrylamide 0 to 100 mol%, and another copolymerizable nonionic monomer 0 to 30 mol%, the monomer (mixture) is dispersed and polymerized under stirring. A method for producing a water-soluble polymer dispersion comprising fine particles having a particle size of 100 mμ or less. 9. The polycondensation polymer is a polycondensation product of epihalohydrin with one or more amines selected from ammonia, aliphatic monoamines and aliphatic polyamines. A method for producing the water-soluble polymer dispersion of. 10. The method for producing a water-soluble polymer dispersion according to claim 9, wherein the aliphatic polyamine is a polyethylene polyamine represented by the general formula (4). 11. The method for producing a water-soluble polymer dispersion according to claim 9, wherein the polycondensation polymer has an ion equivalent value of 1.5 to 10 meq / g. 12. The method for producing a water-soluble polymer dispersion according to claim 8, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.