JP6833186B2 - Method for Producing Polyvinyl Carboxylic Acid Amide Crosslinked Polymer Particles - Google Patents

Description

The present invention relates to a method for producing polyvinylcarboxylic acid amide crosslinked polymer particles.

Polyvinylamine crosslinked polymer particles obtained by hydrolyzing polyvinylcarbic acid amide crosslinked polymer particles have been proposed for a wide range of uses such as gas adsorbents and anion exchange resins. As a method for producing the polyvinylamine crosslinked polymer particles, for example, divinylbenzene, (meth) acrylic acid ester or (meth) acrylamide-based crosslinkable monomer is copolymerized with N-vinylformamide (hereinafter abbreviated as NVF). A method has been proposed for obtaining a polyvinylamine crosslinked product in which the formamide group of the obtained polyvinylformamide crosslinked polymer is hydrolyzed to form an amino group (Patent Document 1). However, in this case, it is necessary to dry and pulverize the polymer after the completion of polymerization, and the obtained product has an indefinite shape. Further, a method of reverse phase suspension polymerization while stirring NVF and divinylbenzene in cyclohexane is disclosed (Patent Document 2). In this method, crosslinked polymer particles are generally obtained, but after the polymerization, cyclohexane needs to be removed, and operations such as distillation are required. Further, it is difficult to completely remove cyclohexane and the like, and there is a problem that they remain.
A method for obtaining polyvinylcarboxylic acid amide crosslinked polymer particles by suspension polymerization of N-vinylcarboxylic acid amide in salt water in the presence of a polyvinyl compound and a dispersant is disclosed (Patent Document 3). Although this method solves the above problems, the polymer particles may become agglomerates, and further improvement is desired.

Japanese Unexamined Patent Publication No. 61-51007 Japanese Unexamined Patent Publication No. 6-190235 International Publication 2016/042846

An object of the present invention is to efficiently produce agglutinated polyvinylcarboxylic acid amide crosslinked polymer particles by a simple operation. In many cases, agglomerates can be obtained by the conventional method, and particularly when the content of the polyvinyl compound is large, the agglutination tendency becomes strong, and a crosslinked copolymer without agglomerates has not been stably obtained.

As a result of diligent studies to solve the above problems, N-vinylcarboxylic acid amide and polyvinyl compound were suspended in salt water in the presence of a cationic polymer dispersant, an anionic compound and / or a nonionic surfactant. It has been found that by turbid polymerization, spherical polyvinylcarboxylic acid amide crosslinked polymer particles without aggregates can be obtained.

That is, in the present invention, N-vinylcarboxylic acid amide and polyvinyl compound are suspended-polymerized in salt water in the presence of a cationic polymer dispersant, an anionic compound and / or a nonionic surfactant, and polyvinylcarboxylic acid is used. The present invention relates to a method for producing an acid amide crosslinked polymer particle.

According to the present invention, spherical polyvinylcarboxylic acid amide crosslinked polymer particles without aggregates can be produced easily and efficiently.

Hereinafter, the present invention will be described in detail.

As a method for producing polyvinylcarboxylic acid amide crosslinked polymer particles in the present invention, first, generally used suspension polymerization is applied. That is, the suspension polymerization in salt water in the present invention includes an N-vinylcarboxylic acid amide, a polyvinyl compound, a monomer capable of copolymerizing with N-vinylcarboxylic acid amide if necessary, a polymerization initiator, and a cationic polymer. It can be carried out by suspending a dispersant, an anionic compound and / or a nonionic surfactant in salt water, stirring at an arbitrary strength to generate monomer droplets, and performing radical polymerization. The particle size of the monomer droplets is controlled by the dispersant and the stirring intensity, but is 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm.

Examples of the monomer of N-vinylcarboxylic acid amide used in the present invention include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, and N-vinylpropion. Examples thereof include amide, N-methyl-N-vinylpropionamide, N-vinylbutylamide, N-vinylisobutyramide and the like, and N-vinylformamide is preferable. In addition to the monomer of N-vinylcarboxylic acid amide, a monomer capable of copolymerizing with N-vinylcarboxylic acid amide may be used, and (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N'-dialkyl (meth) acrylamide, N, N'-dialkylaminoalkyl (meth) acrylamide, (meth) acrylamide Alkali metal salt or ammonium salt of alkane sulfonic acid, Alkali metal salt or ammonium salt of (meth) acrylic acid, Hydroxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acryloyloxyalkyl-trimethylammonyl salt, alkali metal or ammonium salt of (meth) acryloyloxyalkanosulfonic acid, N-vinylpyrrolidone, diallyl-dialkyl Examples thereof include ammonium salt, vinyl pyridine, vinyl imidazole, vinyl penzyltrialkylammonium salt, alkali metal salt or ammonium salt of vinylsulfonic acid, and one of these may be used, or two or more thereof may be combined. Is also good. Acrylonitrile is particularly preferable.

Examples of the polyvinyl compound include aromatic polyvinyl compounds such as divinylbenzene, trivinylbenzene and divinyltoluene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, and trimethylolpropane tri (meth). Poly (meth) acrylate such as acrylate, methylenebisacrylamide and the like can also be used. It is preferable to use an aromatic divinyl compound. The most preferred is divinylbenzene. The addition rate is in the range of 0.1 to 50% by mass with respect to the monomer, preferably in the range of 0.1 to 20% by mass. If it exceeds 5% by mass, it becomes difficult to obtain spherical particles only with N-vinylcarboxylic acid amide, so it is preferable to use a monomer copolymerizable with N-vinylcarboxylic acid amide. The addition rate of the copolymerizable monomer is used in the range of 50% by mass or less with respect to all the monomers. In particular, it is preferable to use acrylonitrile.

As the polymerization initiator, azo or peroxide-based polymerization initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvalero) Nitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis-2-amidinopropane hydrochloride, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis [2- (5-Methyl-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, etc., ammonium peroxobisulfate or potassium, excess Examples thereof include hydrogen oxide, benzoylperoxide, lauroylperoxide, octanoylperoxide, succinicperoxide, t-butylperoxy-2-ethylhexanoate and the like. Of these, oil-soluble initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferred. In addition, two or more initiators may be used in combination. The addition rate is usually 0.02 to 5% by mass, preferably 0.05 to 2% by mass, based on the monomer.

Examples of the salt include ammonium sulfate, sodium sulfate, ammonium chloride, sodium chloride, calcium chloride and the like, and among these, ammonium sulfate is particularly preferable. Further, these may be used alone or in combination. The addition rate is in the range of 50 to 100% by mass with respect to water, and if it is less than 50% by mass, the N-vinylcarboxylic acid amide does not separate into two phases, and if it is 100% by mass, the effect of the salt is sufficiently obtained. It is uneconomical to add more than 100% by mass. It is preferably 60 to 90% by mass.

The cationic polymer dispersant is obtained by polymerizing (meth) acryloyloxyethyltrimethylammonium chloride, dimethyldialylammonium chloride, etc., which are cationic monomers, and these cationic monomers and nonionic monomers are used. Copolymers can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N'-dimethylacrylamide, acrylonitrile, diacetoneacrylamide, 2-hydroxyethyl (meth) acrylate and the like. Can be mentioned. The weight average molecular weight of the cationic polymer dispersant is 5,000 to 2 million, preferably 50,000 to 1,000,000. The addition rate is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass with respect to water.

Examples of the anionic compound include 2,4-dimethylbenzene sulfonate such as sodium 2,4-dimethylbenzene sulfonate, toluene sulfonate such as sodium toluene sulfonate, xylene sulfonate such as sodium xylene sulfonate, and ethyl benzene. Ethylbenzene sulfonates such as sodium sulfonate, dodecyl sulphates such as sodium dodecyl sulphate, cyclohexane sulfonates such as sodium cyclohexane sulfonate, aliphatic sulfates, aromatic sulphates, benzoic acids such as benzoic acid or sodium benzoate. Salts, phthalates such as phthalates or sodium phthalates, p-tolulates such as p-tolurates, sodium p-tolulates, laurates such as lauric acid or sodium laurates, oleic acid, sodium oleate And other oleates, aliphatic carboxylic acid salts, aromatic carboxylic acid salts and the like. The addition ratio of the anionic compound is in the range of 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the monomers.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and poly. Polyoxyalkylene alkyl phenyl ether compounds such as oxyethylene nonylphenyl ether, polyoxyalkylene unit-containing ether compounds such as polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether; polyoxyethylene monolaurate, poly Polyoxyalkylene alkyl ester compounds such as oxyethylene monostearate, polyoxyethylene monooleate, and polyoxyethylene distearate; polyoxyalkylene alkylamine compounds such as polyoxyethylene alkylamine; sorbitan monolaurate, sorbitan monosteer Examples thereof include sorbitan compounds such as rate, sorbitan triolate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monoolate. Any of these HLB values is used, but the range of 8.0 to 17.0 is preferable. The addition rate of the nonionic surfactant is in the range of 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total amount of the monomers.

By using a cationic polymer dispersant and an anionic compound in combination, or by using a cationic polymer dispersant and a nonionic surfactant in combination, polyvinylcarboxylic acid amide crosslinked polymer particles without aggregates can be obtained. Can be done. This is because by adding an anionic compound, the anionic group of the anionic compound that is salted and exists on the monomer phase side and the cationic group of the cationic polymer dispersant that exists on the aqueous phase side interact with each other. As a result of the presence of these compounds at the interface of the monomer droplets, it is presumed that the stability of the monomer droplets is improved and a spherical polymer without agglomerates can be obtained. In addition, the nonionic surfactant has a hydrophobic group on the monomer phase side and a hydrophilic group on the aqueous phase side, and as a result, the dispersion stability of the monomer droplets is jointly with the dispersion stabilization effect of the cationic polymer dispersant. It is presumed that a spherical polymer without agglomerates can be obtained by improving the above. It is also possible that both the anionic compound and the nonionic surfactant are present in an arbitrary ratio.

The polymerization reaction is usually carried out at a temperature of 30 ° C. to 100 ° C. and a time of 1 hour to 15 hours.

After the polymerization, salts, cationic polymer dispersants, anionic compounds and / or nonionic surfactants, unreacted monomers and the like can be removed by washing with water.

The vinylcarboxylic acid amide crosslinked polymer particles obtained by the production method in the present invention can be hydrolyzed into vinylamine crosslinked polymer particles for gas treatment and general water treatment, as well as for semiconductor production. Production of pure water for nuclear power, thermal power generation, pharmaceuticals and cosmetics, process water, boiler water, reaction solution, desalting from fermented liquid, adsorption removal of acidic substances, formaldehydes, metal ions from waste water, etc. It is used for adsorption treatment of organic compounds and the like. Further, since the crosslinked polymer particles in the present invention are spherical, when used in a column as an adsorbent, the filling efficiency is high, the flow path is stable, the separation efficiency is increased, and general water treatment applications are used. There are also advantages such as increased adsorption capacity with the target substance and improved processing capacity.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

(Example 1)
146.4 g of desalted water, 96.0 g of ammonium sulfate, and 4.2 g of a polyacryloyloxyethyl trimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL four-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 50.1 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Jun 0.18 g of Yakuhin Kogyo Co., Ltd. and 0.5 g of sodium 2,4-dimethylbenzenesulfonate were mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 200 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 50 ° C. for 3 hours, followed by 60 ° C. for 2 hours. After the polymerization, it was filtered, washed with water, and filtered to obtain 133.2 g of polymer spherical particles having no aggregates in a water-containing state.

(Example 2)
980.3 g of desalted water, 640.4 g of ammonium sulfate, and 20.4 g of an aqueous polyacryloyloxyethyltrimethylammonium chloride solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 3000 mL four-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 332.0 g, divinylbenzene 28.0 g, acrylonitrile 40.0 g, sodium toluene sulfonate 10.0 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 1.2 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 90 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 4 hours, followed by 60 ° C. for 1 hour. After the polymerization, the polymer was filtered, washed with water, and filtered to obtain 858.7 g of polymer spherical particles having no aggregates in a water-containing state. The solid content was 40.3%.

(Example 3)
144.2 g of desalted water, 96.4 g of ammonium sulfate, and 6.0 g of a polyacryloyloxyethyl trimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL four-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 37.9 g, divinylbenzene 7.2 g, acrylonitrile 15.0 g, sodium toluene sulfonate 1.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2, 4-dimethylvaleronitrile) ) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 200 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1.5 hours. After the polymerization, it was filtered, washed with water, and filtered to obtain 88.4 g of polymer spherical particles having no agglomerates in a water-containing state. The solid content was 55.8%.

(Example 4)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, sodium laurate 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, the polymer was filtered, washed with water, and filtered to obtain 131.49 g of polymer spherical particles having no aggregates in a water-containing state. The solid content was 40.1%.

(Example 5)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, oleic acid 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ( 0.18 g of V-70 and Wako Pure Chemical Industries, Ltd. were mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 126.57 g of polymer spherical particles having no agglomerates in a water-containing state. The solid content was 40.9%.

(Example 6)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, sodium dodecyl sulfate 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, the polymer was filtered, washed with water, and filtered to obtain 127.63 g of polymer spherical particles without agglomerates in a water-containing state. The solid content was 40.4%.

(Example 7)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, sodium benzoate 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, the polymer was filtered, washed with water, and filtered to obtain 128.85 g of polymer spherical particles having no aggregates in a water-containing state. The solid content was 40.5%.

(Example 8)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, p-toluic acid 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 104.18 g of polymer spherical particles without agglomerates in a water-containing state. The solid content was 39.1%.

(Example 9)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, sodium ethylbenzene sulfonate 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 121.95 g of polymer spherical particles without agglomerates in a water-containing state. The solid content was 38.9%.

(Example 10)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyethylene sorbitan monolaurate (HLB16.7) 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy) -2,4-Dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 129.51 g of polymer spherical particles having no agglutinating state. The solid content was 39.6%.

(Example 11)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyethylene sorbitan monooleate (HLB15.0) 0.5 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-) 0.18 g of 2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 126.61 g of polymer spherical particles having no agglomerates in a water-containing state. The solid content was 42.1%.

(Example 12)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyalkylene alkyl ether (CL-70, HLB11.7, Sanyo Kasei Kogyo Co., Ltd.) 0.5 g, azo-based polymerization initiator 2, 0.18 g of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 133.24 g of polymer spherical particles having no agglomerates in a water-containing state. The solid content was 41.4%.

(Example 13)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyalkylene alkyl ether (CL-100, HLB13.3, Sanyo Kasei Kogyo Co., Ltd.) 0.5 g, azo-based polymerization initiator 2, 0.18 g of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 130.75 g of polymer spherical particles without agglomerates in a water-containing state. The solid content was 39.2%.

(Example 14)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyalkylene alkyl ether (ID-40, HLB8.0, Sanyo Kasei Kogyo Co., Ltd.) 0.5 g, azo-based polymerization initiator 2, 0.18 g of 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 143.59 g of polymer spherical particles having no agglutinating state. The solid content was 37.2%.

(Example 15)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, polyoxyethylene distearate (DO-400, HLB 8.4, Sanyo Kasei Kogyo Co., Ltd.) 0.5 g, azo-based polymerization initiator 2 , 2'-Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 60 ° C. for 1 hour. After the polymerization, it was filtered, washed with water, and filtered to obtain 137.46 g of polymer spherical particles without agglomerates in a water-containing state. The solid content was 38.2%.

(Comparative Example 1)
142 g of desalted water, 96.1 g of ammonium sulfate, and 8.1 g of polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL four-necked flask, and the mixture was stirred and dissolved. , A polymer bath. N-vinylformamide 49.9 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, azo-based polymerization initiator 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 0.18 g (manufactured by Yakuhin Kogyo Co., Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 250 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 2 hours, followed by 60 ° C. for 1 hour. After the polymerization, the polymer was filtered, washed with water, and filtered, and the obtained polymer contained a large number of aggregates of several hundred micrometers to several mm.

(Comparative Example 2)
1471 g of desalted water, 942.8 g of ammonium sulfate, and 30.2 g of a polyacryloyloxyethyl trimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 3000 mL four-necked flask, and the mixture was stirred and dissolved. , A polymer bath. N-vinylformamide 332.4 g, divinylbenzene 28.0 g, acrylonitrile 40.0 g, azo-based polymerization initiator 2, 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) 1.20 g (manufactured by Yakuhin Kogyo Co., Ltd.) was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 110 rpm. After 30 minutes, the temperature was raised, and polymerization was carried out at 45 ° C. for 3 hours, followed by 70 ° C. for 2 hours. After the polymerization, the polymer was filtered, washed with water, and filtered, and the obtained polymer contained many agglomerates of several mm.

(Comparative Example 3)
150.0 g of desalted water, 96.0 g of ammonium sulfate, and 4.0 g of a polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL three-necked flask, and the mixture was stirred. It was dissolved and used as a polymerization bath. N-vinylformamide 49.8 g, divinylbenzene 4.2 g, acrylonitrile 6.0 g, lauryltrimethylammonium chloride 0.5 g, azo-based polymerization initiator 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) 0.18 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 170 rpm. After 30 minutes, the temperature was raised and the reaction was started at 45 ° C., but aggregates were generated in the obtained polymer.

Claims (3)

N-vinylcarboxylic acid amide and polyvinyl compound in salt water with cationic polymer dispersant and as anionic compounds 2,4-dimethylbenzenesulfonate, toluenesulfonate, xylenesulfonate, ethylbenzenesulfonate , Dodecyl sulfate, cyclohexanesulfonate, benzoic acid or benzoate, phthalic acid or phthalate, p-toluic acid or p-toluic acid, lauric acid or laurate, oleic acid or oleate A method for producing polyvinylcarboxylic acid amide crosslinked polymer particles, which is obtained by suspension polymerization in the presence of one or more anionic compounds and / or nonionic surfactants. The method for producing a polyvinylcarboxylic acid amide crosslinked polymer particle according to claim 1, wherein the N-vinylcarboxylic acid amide is N-vinylformamide. The method for producing polyvinylcarboxylic acid amide crosslinked polymer particles according to claim 1, wherein the polyvinyl compound is divinylbenzene.