JP2003073569A - Water-soluble polymer dispersion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion containing a dispersant, capable of producing a water-soluble polymer in good efficiency while suppressing thickening at the time of polymerization when a dispersion polymerization is carried out in an aqueous solution of a salt in the coexistence of a high-molecular dispersant, and further to provide a method for efficiently producing the dispersion. SOLUTION: This polymer dispersion contains both of fine particles of the water-soluble polymer having <=100 μm particle diameters and one or more kinds of ionicities selected from cationic, nonionic and ampholytic, and at least one kind or more of a specific polycondensed polymer and a polyhydric alcohol soluble in the aqueous solution of the salt as the dispersant, coexisting in the aqueous solution of the salt. The polymer dispersion is efficiently produced by making at least one kind or more of the polycondensed polymer and the polyhydric alcohol coexist at the time of polymerization.

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 selected from cationic, nonionic and amphoteric particles having a particle size of 100 μm or less. The present invention relates to a water-soluble polymer dispersion liquid in which at least one kind of polycondensation polymer soluble in an aqueous salt solution as a dispersant and a polyhydric alcohol coexist with a water-soluble polymer fine particle.

[0002]

2. Description of the Related Art Water-soluble cationic polymers are used as flocculants for wastewater treatment or as papermaking agents.
Since it is a high molecular compound, it becomes a highly viscous solution 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,
Since the polymerization is carried out at a monomer concentration of 10% by weight or more, the product becomes a gel containing water, and it is difficult to dissolve in the state as it is. Therefore, the product is further diluted to have a low concentration with fluidity. 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 containing a dispersant capable of suppressing viscosity increase during polymerization and efficiently producing a water-soluble polymer. Further, it is 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.
One or more kinds of water-soluble polymer fine particles selected from cationic, nonionic and amphoteric having a size of 00 μm or less, a polycondensation polymer soluble in the salt aqueous solution as a dispersant and a polyvalent alcohol, respectively. The present invention relates to a water-soluble polymer dispersion liquid in which at least one or more coexists.

According to a second aspect of the present invention, the one or more water-soluble polymer fine particles selected from the cationic, nonionic and amphoteric groups are used as a dispersant and a polycondensation type polymer soluble in the salt aqueous solution. Among the valent alcohols, at least one or more of them are allowed to coexist, and 0 to 100 mol% of the monomer represented by the following general formula (1) and / or (2), and the monomer represented by (3) A monomer (mixture) consisting of 0 to 50 mol%, 0 to 100 mol% of acrylamide, and another copolymerizable nonionic monomer is dispersed and polymerized in an aqueous salt solution with stirring. The water-soluble polymer dispersion according to claim 1.

[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, and the same or different. But, A is oxygen or NH,
B represents 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.

The invention according to claim 4 is the water-soluble polymer dispersion according to claim 1 or 2, wherein the polycondensation polymer has an ion equivalent value of 1.5 to 10 meq / g. is there.

In a fifth aspect of the present invention, the polyhydric alcohol is ethylene glycol, propylene glycol glycerin, pentaerythritolyl, sorbitol, or polyoxyalkylenated polyhydric alcohol. The water-soluble polymer dispersion according to claim 1, which is one or more selected from the group of terminal hydroxylated compounds.

According to a sixth aspect of the invention, the polyvalent alcohol is
The water-soluble polymer dispersion according to claim 1, which is polyethylene glycol and / or polypropylene glycol.

In the invention of claim 7, the weight average molecular weight of the one or more ionic water-soluble polymers selected from the cationic, nonionic and amphoteric constituents of the polymer dispersion is 20.
The polymer dispersion according to claim 1, wherein the polymer dispersion is from 0,000 to 20,000,000.

The invention according to claim 8 is the water-soluble polymer dispersion according to claim 1, characterized in that the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.

According to a ninth aspect of the present invention, in a salt aqueous solution, at least one or more of a polycondensation polymer soluble in the salt aqueous solution as a dispersant and a polyvalent alcohol are allowed to coexist, and the following general formula is used. Monomers 0 to 1 represented by (1) and / or (2)
00 mol%, the monomer represented by (3) 0 to 50 mol%,
A particle size of 100 μm, characterized in that 0-100 mol% of acrylamide and 0-30 mol% of another non-ionic copolymerizable monomer (mixture) are dispersed and polymerized under stirring. It is a method for producing a water-soluble polymer dispersion comprising the following fine particles.

The invention of claim 10 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 9.

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

In the twelfth aspect of the present invention, the polyvalent alcohol is ethylene glycol, propylene glycol, glycerin, pentaerythritolyl, sorbitol or polyoxyalkylene of these polyvalent alcohols. 10. The method for producing a water-soluble polymer dispersion according to claim 9, wherein the water-soluble polymer dispersion is one or more selected from the group consisting of a hydroxyl group at the terminal of the polymer.

In the thirteenth aspect of the present invention, the polyvalent alcohol is polyethylene glycol and / or propylene glycol, and the production of the water-soluble polymer dispersion according to the ninth aspect is carried out. Is the way.

The invention of claim 14 is the method for producing a water-soluble polymer dispersion according to claim 9, characterized in that the salt constituting the aqueous salt solution contains at least one polyvalent anion salt. .

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION One or more water-soluble polymer dispersions selected from the group consisting of cationic, nonionic and amphoteric of the present invention comprises a polycondensation polymer which is soluble in an aqueous salt solution. It is composed of polymer particles having a particle size of 100 μm or less, which are produced by a dispersion polymerization method in the coexistence of a alcohol. 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, or in the case of a nonionic water-soluble polymer, acrylamide is added and dissolved, and a polycondensation polymer and a polyhydric alcohol as a dispersant are allowed to coexist before polymerization. The pH at this time is set to 2-6. After uniformly dissolving the mixture, oxygen in the reaction system is removed by nitrogen substitution and a radical polymerizable initiator is added to initiate polymerization, and the polymer can be produced with stirring. Further, coexistence of a chain transfer agent, a cross-linking agent and the like before the initiation 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 ammonia, an aliphatic monovalent amine or an aliphatic polyamine, or may be a product obtained by reacting epihalohydrin by mixing two or more kinds thereof, or in the first step of the reaction 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 terms of management to combine with three kinds or four kinds, and preferably one kind or two kinds are used in combination.

On the other hand, polyvalent alcohol is ethylene glycol.
, Propylene glycol, glycerin, mono- to tripolyoxyethylenated terminal hydroxide of glycerin, pentaerythritol, pentaerythritol mono to tetrapolyoxyethylenated terminal hydroxide, sorbitol, Examples thereof include sorbitol mono- or multi-polyoxyethylenated terminal hydroxides, polyethylene glycol and polypropylene glycol. Of these, polyethylene glycol,
Polypropylene glycol is particularly preferred.

The compounding ratio of these polycondensation type polymer and polyvalent alcohol is 8: 1 to 1: 3, preferably 5: 1 to 1: 2.
Is appropriately selected according to the monomer to be polymerized. In particular, when carrying out the copolymerization in which the ratio of the cationic monomer is low, it is effective to increase the ratio of the heavy ionic polymer having high ionicity. On the contrary, when the copolymerization ratio of the ionic monomer is low,
It is effective to lower the ratio of heavy-duty polymer and increase the ratio of polyoxyethylenated terminal hydroxide of pentaerythritol, glycerin or sorbitol among polyvalent alcohols. . The dispersant of the present invention is not limited to the use of two or more kinds of each of the condensation polymer and the polyvalent alcohol, but the combination of two kinds, three kinds and four kinds is very complicated in terms of management. However, it is more efficient and effective to select one of the natural type and the synthetic type and determine the optimum mixing ratio.

The fact that the polycondensation polymer and the polyhydric alcohol are used in combination in the present invention is effective, and many theoretically unknown parts cannot be clarified. 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. Viscosity also increases,
The dissolved polymer and precipitated particles coexist. After this,
The ratio of the precipitated polymer increases, the viscosity of the polymer gradually decreases, and the polymer changes to 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. . On the other hand, the alkyl go in the polyhydric alcohol molecule is hydrophobic go, and adsorbs toward the surface of the deposited particles, and the hydroxy go is hydrophilic go and faces the outside of the deposited particles. To prevent agglomeration, agglomeration due to its influence, and particle coarsening. The polycondensation polymer used at the same time has a high ability to protect particles of ionic go itself, which has strong hydrophilicity, but since ionic go exists in the chain, it does not have an orientation like a surfactant. poor. Hydrophilicity of hydroxygo itself is smaller and weaker than that of ionic go. Therefore, it is considered that the combined use of both properties is the effect of the combined use. It is presumed that these relationships reduce the viscosity around the particles, improve the slippage between the precipitated particles and the dissolved gelled polymer, and achieve a smooth phase change.

Among the cationic monomers used when polymerizing one or more water-soluble polymers selected from cationic, nonionic and amphoteric, the cationic monomer represented by the general formula (1) As an example of the above, 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,
Examples thereof include (meth) acryloyloxy 2-hydroxypropyldimethylbenzylammonium chloride and (meth) acryloylaminopropyldimethylbenzylammonium chloride. Examples of the cationic monomer represented by the general formula (2) include diallylmethylamine,
Examples include diallylbenzylamine and dimethyldiallylammonium chloride diallylmethylbenzylammonium chloride.

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.

The molar ratio of the cationic monomer in the case of producing the dispersion of the cationic water-soluble polymer is 1 to 100 mol%, preferably 5 to 100 mol%, and more preferably 10 to 10. It is 100 mol%. When producing a dispersion liquid of an amphoteric water-soluble polymer, the cationic monomer 10 to
It is 90 mol%, preferably 20 to 90 mol%. Further, the anionic monomer is preferably 5 to 50 mol%,
More preferably, it is 5 to 40 mol%. Acrylamide is 0 to 95 mol%, preferably 0 to 85 mol%
Is. Acrylamide is used when preparing a dispersion of a nonionic water-soluble polymer.

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,
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 composed of the polymer dispersion of the present invention is used for dehydration of pulp sludge in the paper industry, treatment of wastewater in other food industries, metal and petroleum refining, and treatment of gravel washing wastewater for building materials. It can be applied to mixed sludge including 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 to be added varies depending on the type of drainage, the concentration of suspended matter, etc.
It is about ppm. Moreover, it is 0.1 to 3 weight% with respect to sludge ss.

[0036]

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) In 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 added to the flask. 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 polymer N
0. -1. The results are shown in Table 2.

(Synthesis Example 2) Polymer N was prepared in the same manner as in Synthesis Example 4.
0. -2 to N0. -5 was synthesized. The results are shown in Table 2.

[0039]

[Table 1] DA: dimethylamine, HA: pentaethylenehexamine, AM: ammonia, TMA: trimethylamine, D
PA: dimethylaminopropylamine, EPI: epichlorohydrin

[0040]

[Table 2] (Polyhydric alcohol) The following were used as the polyhydric alcohol.

[0041]

Example 1 A polycondensation polymer NO. 1 prepared in Synthesis Example 1 was placed in a five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. 1 (50% aqueous solution), 10.
5 g (5.0% of monomer), polyhydric alcohol NO. 1
0, 3.2 g (3.0% of monomer), ion-exchanged water 16
0.0 g, 115.0 g of ammonium sulfate, and 250 g of 50% aqueous acrylamide solution were charged and completely dissolved. Keep the internal temperature at 29-33 ° C, replace with nitrogen for 30 minutes,
2,2'-azobis [2- (5-methyl-
2-Imidazolin-2-yl) propane] 1.1 g of a 1% aqueous solution of dihydrochloride was added to start polymerization. After 2 hours and 15 minutes from the start, a slight increase in the viscosity of the reaction product was observed, and this state was maintained for 40 minutes, but then it settled and transferred to the dispersion liquid. After 8 hours from the start, 0.6 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The concentration of the swelling monomer in the obtained dispersion was 21.
0%, the polymer particle size was 10 μm or less, and the viscosity of the dispersion liquid was 120 mPa · s. This sample is referred to as prototype-1. The results are shown in Table 4.

[0042]

Examples 2 to 4 By the same operation as in Example 1, a polycondensation polymer in Table 1 and a dispersant system in which Table 2 and a polyhydric alcohol were combined were used. Prototypes 2 to 4 were synthesized according to the composition. The results are shown in Table 4.

[0043]

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. Polycondensation polymer NO. 5 (40% aqueous solution) 11.5 g (4.0% of monomer), polyhydric alcohol NO. 8, 4.6g
(4.0% of monomer), ion-exchanged water 159.0 g, ammonium sulfate 115.0 g, and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 1
00.6 g was charged and completely dissolved. Internal temperature is 33 ~
Keep the temperature at 35 ° C and replace with nitrogen for 30 minutes.
2.3 g of 1% aqueous solution of 2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (0.020%) was added to initiate polymerization. It was Two hours after the start of the reaction, a slight increase in the viscosity of the reaction product was observed, but this state continued for 30 minutes, after which it settled and transferred to the dispersion liquid. After 8 hours from the start, 1.1 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The resulting dispersion has a loading monomer content of 23%, a polymer particle size in the range of 1 to 10 μm, and a dispersion viscosity of 200.
It was mPa · s. The results are shown in Table 4.

[0044]

Examples 6 to 12 Using the same operation as in Example 5, using a dispersant system in which the polycondensation polymer of Table 1 and the polyhydric alcohol of Table 2 were combined, the addition amount and the monomer shown in Table 3 were used. Prototype-6 to Prototype-12 were synthesized according to the composition. The results are shown in Table 4.

[0045]

Example 13 A polycondensation polymer NO. Was placed in a five-neck separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. 3 (50% aqueous solution), 10.0 g (4.0% of monomer), polyhydric alcohol NO. 9, 3.8 g (3.0% of monomer), 186.0 g of ion-exchanged water, 115.0 g of ammonium sulfate, 50% aqueous solution of acrylamide 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 thereafter, it was settled and transferred to the dispersion liquid. After 8 hours from the start, 0.9 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The resulting dispersion has a swelling monomer concentration of 25.0% and a polymer particle size of 10
The viscosity of the dispersion was 200 mPa · s or less.
In addition, a molecular weight measuring device by a static light scattering method (Otsuka Electronics D
The weight average molecular weight was measured by LS-7000).
This sample is referred to as prototype-1. The results are shown in Table 4.

[0046]

Examples 14 to 17 Table 1 is prepared by the same procedure as in Example 1.
Prototypes -14 to -17 were synthesized using the polycondensation polymer of No. 1 and a dispersant system in which Table 2 and a polyhydric alcohol were combined and the addition amount and the monomer composition shown in Table 3 were used. The results are shown in Table 4.

[0047]

[Comparative Example 1] In a five-neck 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. Polycondensation polymer NO. 5 (40% aqueous solution) 11.5 g (4.0% of monomer), ion-exchanged water 163.4 g, ammonium sulfate 115.0 g, and acryloyloxyethyltrimethylammonium chloride, 80% aqueous solution 100.
6 g was charged and completely dissolved. Internal temperature 33-35 ℃
And nitrogen purge for 30 minutes, then 2,2'-as an initiator
Azobis [2- (5-methyl-2-imidazoline-2-
2.3 g of a 1% aqueous solution of (yl) propane] dihydrochloride
Polymerization was started by adding (0.020% to the amount of monomer) g.
After 1 hour and 30 minutes from the start, a vigorous increase in the viscosity of the reaction product was observed, but the reaction continued as it was, and the state was maintained for 50 minutes, but then it settled and transferred to the dispersion liquid.
After 8 hours from the start, 1.1 g of the above initiator solution was added, and polymerization was further performed for 8 hours. The viscosity of the dispersion is 310 mPa · s
Met. The results are shown in Table 4.

[0048]

Comparative Examples 2 to 6 By the same operation as in Comparative Example 1, the polymerized polymer alone or the polycondensed polymer alone in Table 1 or 2 was used as a dispersant, and the addition amount and the monomer composition shown in Table 3 were used. Comparative-2 to Comparative-6 were synthesized by. The results are shown in Table 4.

[0049]

[Table 3] DMQ: Acryloyloxyethyltrimethylammonium chloride DMC: Methacryloyloxyethyltrimethylammonium chloride ABC: Acryloyloxyethylbenzylbenzyldimethylammonium chloride DMPQ: Acryloylaminopropyltrimethylammonium chloride AAC: Acrylic acid, IA: Itaconic acid, AAM: Acrylamide

[0050]

[Table 4] Addition amount: mass% of monomer, dispersion viscosity: mPa · s, molecular weight: 10,000

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Claims (14)

[Claims] 1. A salt aqueous solution having one or more fine particles of a water-soluble polymer selected from cationic, nonionic and amphoteric particles having a particle size of 100 μm or less, and a polycondensation system soluble as a dispersant in the salt aqueous solution. A water-soluble polymer dispersion liquid in which at least one or more of a molecule and a polyvalent alcohol coexist. 2. One or more water-soluble polymer fine particles selected from cationic, nonionic and amphoteric are a polycondensation polymer soluble in the salt aqueous solution as a dispersant and a polyvalent alcohol. Of these, at least one kind is allowed to coexist, and monomers 0 to 1 represented by the following general formulas (1) and / or (2) are used.
00 mol%, the monomer represented by (3) 0 to 50 mol%,
A monomer (mixture) consisting of 0 to 100 mol% of acrylamide and 0 to 30 mol% of another copolymerizable nonionic monomer is produced by dispersion polymerization under stirring in an aqueous salt solution. The water-soluble polymer dispersion according to claim 1. [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, and the same or different. But, A is oxygen or NH,
B represents 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) 2CH
2SO3, C6H4COO or COO, R9 is 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 according to claim 3, wherein the polycondensation polymer has an ion equivalent value of 2.0 to 8.0 meq / g. 5. The polyvalent alcohol is ethylene glycol, propylene glycol glycerin, pentaerythritolyl, sorbitol or a polyvalent alcohol thereof.
2. The water-soluble polymer dispersion according to claim 1, which is one or more selected from the group of polyoxyalkylenated terminal hydroxylated compounds of 6. The water-soluble polymer dispersion according to claim 1, wherein the polyhydric alcohol is polyethylene glycol and / or polypropylene glycol. 7. The weight average molecular weight of the water-soluble polymer selected from the cationic, nonionic and amphoteric components that constitute the polymer dispersion is from 2,000,000 to 20,000,000. 1. The polymer dispersion liquid according to 1. 8. The water-soluble polymer dispersion according to claim 1, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt. 9. In a salt aqueous solution, at least one or more of a polycondensation polymer soluble in the salt aqueous solution and a polyvalent alcohol are made to coexist as a dispersant, and 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 method for producing a water-soluble polymer dispersion comprising fine particles having a particle diameter of 100 μm or less, which is characterized by performing dispersion polymerization under stirring. 10. The polycondensation polymer is ammonia,
The method for producing a water-soluble polymer dispersion according to claim 9, which is a polycondensation product of one or more amines selected from aliphatic monoamines and aliphatic polyamines with epihalohydrin. 11. The method for producing a water-soluble polymer dispersion according to claim 10, wherein the polycondensation polymer has an ion equivalent value of 2.0 to 8.0 meq / g. 12. The polyhydric alcohol is ethylene glycol, propylene glycol, glycerin, pentaerythritolyl, sorbitol, or a polyoxyalkylenated terminal hydroxylated product of these polyhydric alcohols. The method for producing a water-soluble polymer dispersion according to claim 9, which is one or more selected from the group. 13. The method for producing a water-soluble polymer dispersion according to claim 9, wherein the polyhydric alcohol is polyethylene glycol and / or polypropylene glycol. 14. The method for producing a water-soluble polymer dispersion according to claim 9, wherein the salt constituting the aqueous salt solution contains at least one polyvalent anion salt.