JPS5941661B2 - Water-soluble polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble polymer composition.

Specifically, the present invention relates to a water-soluble polymer composition with improved solubility in water.

Solid water-soluble polymers, such as solid polyacrylamide, are used as coagulation sedimentation agents, sludge dehydrating agents, soil conditioners, fiber treatment agents, and various additives in the paper industry after being dissolved in water. , it is desired to dissolve quickly and uniformly in water.

However, water-soluble polymers have the property of swelling in water and gradually dissolving in the bath, so if they contain a lot of fine powder or hydrophobic substances on the surface, they may form lumps that envelop air bubbles. , which tends to significantly reduce the rate of dissolution. To prevent this, methods of coating the surface with hydrophilic compounds or nonionic surfactants have been proposed, but they are not sufficiently effective or require a large amount of coating material, and water-soluble polymers are required. There was a problem that it affected the effectiveness for the purpose of use. The inventors of the present invention have conducted intensive studies on methods for improving the water solubility of solid water-soluble polymers, and found that by coating the surface of solid water-soluble polymers with a cationic surfactant The present invention has been achieved by discovering that the formation of lumps enclosing air bubbles can be extremely efficiently prevented.

That is, the gist of the present invention resides in a water-soluble polymer composition comprising a solid water-soluble polymer and a cationic surfactant.

When solid, especially powdered or granular, water-soluble polymers are dropped onto the water surface, if the individual particles are submerged in the water, no lumps will be formed, but if they float on the water surface due to surface tension, the particles will gather and form in the water. It swells to form a film, which then envelops the powder that has not been in contact with water, producing a bubbly mass. Such agglomerates do not come into optical contact with water, and the rate of disintegration is extremely slow. On the other hand, when the surface of a solid water-soluble polymer is coated with a trace amount of a cationic surfactant, individual particles have a greater affinity with water and are immediately submerged in water and rapidly dissolved.

Furthermore, even if a portion of the particles floats on the water surface, the particles exhibit the property of repelling each other on the water surface, and moreover, they sink into the water with the slightest impact, so no film is formed on the water surface. Therefore, no lumps enclosing air bubbles are generated. The reason why using a very small amount of cationic surfactant is effective is that the cationic surfactant spreads easily over the particle surface and coats it uniformly, and the cationic surfactant lowers the contact angle of water on the particle surface. It is presumed that this is due to the following reasons: Further, any solid water-soluble polymer whose optical solubility has been improved by coating with a cationic surfactant does not electrostatically adhere to resin containers. The present invention will be explained in more detail below.

Various well-known water-soluble polymers can be used as a component of the composition of the present invention, and specific examples include nonionic vinyl monomers such as acrylamide and methacrylamide; Neutralized salts such as dialkylaminoalkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylamide, and vinylpyridine, and cationic properties such as quaternary ammonium salt compounds, dialkyldiallylammonium salts, and trialkylvinylbenzylammonium salts using alkylating agents. Vinyl monomer;
Examples include water-soluble polymers obtained by homopolymerizing or copolymerizing anionic vinyl monomers such as sodium acrylate and sodium methacrylate.

The anionic water-soluble polymer forms a water-insoluble salt with the cationic surfactant, but since only a small amount of the cationic surfactant is used, the effect is small. However, the composition of the present invention exhibits particularly excellent effects when used with nonionic or cationic water-soluble polymers. The water-soluble polymer may have any shape as long as it is solid, but it is usually in the form of powder or particles.

The shape differs depending on the manufacturing method. For example, a crushed product obtained by drying and pulverizing a hydrous gel-like material produced by aqueous solution polymerization (usually the particle size is 50 to 2000μ); a fine powder product obtained by precipitation polymerization (the particle size C is usually 5 to 5μ);
00μ); Fine powder or granule product obtained by emulsion polymerization in a hydrophobic medium (usually the particle size is 10 to 1000μ)
; Bead-like products (usually having a particle size of 100 to 2000 μm) obtained by suspension polymerization using a dispersion stabilizer.
The dissolution promoting effect of adding a cationic surfactant is particularly remarkable for powders containing fine particles or water-soluble polymers in the form of beads. For example, this is remarkable for bead-shaped water-soluble polymers obtained by the following suspension polymerization method. In order to obtain a bead-shaped water-soluble polymer, it is necessary to carry out the polymerization in the presence of an organic solvent that does not dissolve the aqueous solution of the water-soluble vinyl monomer. The polymerization system at the start of polymerization is usually a water-in-oil type in which an aqueous solution is a dispersed phase and an organic solvent is a continuous phase. Hydrocarbons or halogenated aromatic hydrocarbons are used as the organic vehicle that does not dissolve the aqueous solution of the water-soluble vinyl monomer. As a hydrocarbon, carbon number is 6
-10 aromatic hydrocarbons, alicyclic hydrocarbons, or aliphatic hydrocarbons are preferred, and chlorinated benzene is preferred as the halogenated aromatic hydrocarbon. Particularly suitable organic solvents are benzene, toluene, xylene, isopropylbenzene, cyclohexane, methylcyclohexane, cyclooctane, decalin, n-hexane, n-hebutane, n-
These include otatane, n-decane, chlorobenzene, and dichlorobenzene. These organic solvents C are generally used in an amount of 0.5 to 10 times the weight of the aqueous solution of the water-soluble vinyl monomer. Examples of preferred dispersion stabilizers in such suspension polymerization include cellulose acetate butyrate,
Oil-soluble cellulose esters or ethers such as ethylcellulose and ethylhydroxyethylcellulose can be mentioned.

If an aqueous monomer solution is dispersed in the form of water droplets in a water-in-oil type and polymerized using this, a bead-like polymer having a particle size (100 to 1000 μm) can be obtained. When using an oil-soluble cellulose ester or ether as a dispersion stabilizer, the cellulose ester or ether is at room temperature (15 to 2
It is desirable to select an organic solvent that exhibits sparingly soluble or insoluble properties at 5°C) and becomes soluble at the polymerization temperature, and to conduct the polymerization at a temperature of 40°C or higher. The amount of dispersion stabilizer used is 0.05 to 10% by weight based on the organic solvent. , preferably 0.5-5? It is. During polymerization, the order of adding the dispersion stabilizer, organic solvent, monomer aqueous solution, and water-soluble radical polymerization initiator is not particularly limited, but the following method is particularly preferred. A dispersion stabilizer is dispersed or dissolved in an organic solvent, maintained at a predetermined temperature for polymerization, and deoxidized by passing nitrogen gas. A water-soluble polymerization initiator is added to the monomer aqueous solution and mixed uniformly. An aqueous monomer solution containing an initiator is quickly added to the dispersion medium while stirring. Stir while passing nitrogen gas and maintain at a predetermined temperature. The polymerization can be carried out at any temperature from 40°C to the Buddha point of the dispersion medium, but in order to obtain a polymer with a high molecular weight, it is preferable to carry out the polymerization at a temperature of 50 to 7°C. The monomer aqueous solution used includes
A polymerization inhibitor is added to prevent polymerization from starting before being dispersed in the dispersion medium. As a polymerization inhibitor,
Any commonly used polymerization inhibitor can be used, especially hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monobenzyl ether, 2-methylhydroquinone,
Hydroquinone derivatives such as 2,5-dimethylhydroquinone and 2,5-di-t-butylhydroquinone are preferred. The amount used is 20 to 10 per monomer aqueous solution.
000 ppm, preferably in the range of 100 to 2000 ppm. Monomer concentration 45-60 weight? The polymer obtained using the aqueous solution can be easily dehydrated by directly performing co-distillation of an organic solvent and water system, or by immersing it in a dehydrating solvent that does not dissolve the polymer, such as acetone or methanol. When using an aqueous solution with a monomer concentration of 60 to 75%, a similar dehydration method can be used, but it is sufficient to simply dry the product with ventilation after separation. Bead-shaped polymers can be obtained simply by separating the dispersion medium. Particularly when an oil-soluble cellulose ester or ether is used as a dispersion stabilizer, bead-shaped polymers containing no fine powder and having a particle size of 100 to 1000 μ can be obtained. Any well-known cationic surfactants can be used as the cationic surfactant blended to promote the solubility of the water-soluble polymer in the composition of the present invention, such as mono-, di-, tri-, and tetraalkyl amine salt types. Cationic surfactants of the ester, amide and ether type of mono-, di-, tri- and tetraalkylamine salts; Cationic surfactants of the polyoxyethylene alkylamine type; Heterocyclic cationic surfactants Examples include cationic surfactants that have antistatic properties for the water-soluble polymers used.

More specifically, laurylamine acetate, stearylamine acetate, lauryltrimethylammonium taloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, laurylbenzylmethylammonium chloride, methyldiethyloleylamide ethylammonium chloride, Examples include dodecyldimethyl-(2-phenooxyethyl)ammonium bromide, polyoxyethylene stearylamine, laurylpicolinium chloride, cetylpyridinium chloride, 1-hydroxyethyl-2-heptadecylglyoxalidine, and the like. The amount of cationic surfactant used is usually 0.005% of the water-soluble/surrounding polymer.
5 weight? It exhibits a light effect in the range of 0.02 to 1 weight, considering the amount required for uniform coating and economic efficiency. It is best to use within this range. The water-soluble polymer and cationic surfactant can be blended by mixing a solution or solid surfactant with the water-soluble polymer using light, or by melting the solid surfactant. Examples include a method in which a surfactant dissolved or suspended in a solvent is added to a water-soluble polymer and then dried.

When a cationic surfactant is blended into a water-soluble polymer by the method described above, the water-soluble polymer is usually coated with the cationic surfactant.

As a result, the surface properties of the solid water-soluble polymer are modified, so that the composition of the present invention has extremely high dispersibility in water. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. [Production of water-soluble polymer] Ethyl cellulose 39 was dissolved in cyclohexane 1009, and introduced into a 200CC four-tube separable flask equipped with a cooling tube, a nitrogen introduction tube, a dropping load, and a stirring blade made of fluororesin. The engineered cellulose was dissolved at 60°C.

80Z071< of 509 β-methacryloyloxyethyltrimethylammonium chloride during dropwise loading.
1. A 10% aqueous solution of the 2,2'-azobis-2-amidinopropane salt of 19 was introduced. After deoxidizing the reactor and dropping with nitrogen gas during loading, the reactor was heated at 100 rpm.
p. m. The aqueous monomer solution being added dropwise under stirring conditions is introduced into the reactor. 200~250r. ^M. The mixture was kept at 60° C. for 1 hour in a nitrogen atmosphere under stirring conditions.

After cooling, the product was taken from house to house, washed with ethyl acetate, and the solvent was dried to obtain a bead-like polymer having a particle size of 0.1 to 1 mm and containing no fine particles without requiring dehydration. This was sieved to obtain a polymer having a particle size of 0.4 to 0.6 mm. Example 1~
11 A cationic surfactant of the type and amount shown in Table 1 based on 100 parts by weight of polyβ-methacryloyloxyethyltrimethylammonium chloride in the form of beads with a particle size of 0.4 to 0.6 obtained by the above method. A shown below
-C method was used to obtain the composition of the present invention.

Diameter 8c7rL, height 20 (800 in a 7L cylindrical container)
Pour 1 ml of water and stir at 400 r.m. using a stirrer with stirring blades 7 in width and 2 CTfL in height. p. m. The composition 49 under stirring of
was added. Table 1 shows the presence or absence of lumps during dissolution and the time required for complete dissolution. In addition, after this composition was sealed in a polyethylene container and shaken, electrostatic adhesion to the container wall was observed, and the presence or absence of chargeability was examined and the results are also listed in Table 1. The following cationic surfactants were used.

Cortamine D86 (trademark); manufactured by Kao Atlas Co., Ltd., distearyldimethylammonium chloride c-T-A-Ct (trademark); manufactured by Tokyo Kasei Reagent Co., Ltd., cetyltrimethylammonium chloride Cortamine 86p Conc (trademark); manufactured by Kao Atlas Company, Stearyltrimethylammonium chloride ammonium 308 (trademark); manufactured by Kao Atlas Co., Ltd., polyoxyethylene alkylamine TexnOlR5 (trademark);
Nippon Nyukazai Co., Ltd., trialkylbenzylammonium chloride method A: 100 parts by weight of a solid water-soluble polymer is mixed with a predetermined amount of cationic surfactant dispersed in 40 parts by weight of cyclohexane.

Thereafter, the mixture is dried under ventilation under stirring until the cyclohexane is completely evaporated.

Method B: A predetermined amount of a solid cationic surfactant is added to a solid water-soluble polymer, the surfactant is heated and melted with stirring, and then cooled to room temperature while stirring.

Method C: Add a predetermined amount of cationic surfactant to a solid water-soluble polymer and shake vigorously for 5 minutes.

Examples 12 to 18 Compositions were produced in the same manner as in Example 1, except that the water-soluble polymers shown in Table 2 were used.

In the same way, measure the time until it completely dissolves in water.
Shown in the table. Table 2 also shows the time required for complete dissolution in water when no cationic surfactant is added. In addition, the water-soluble high molecular weight polymers ad are the polymers shown below.

Polymer a: 10 moles of β-methacryloyloxyethyltrimethylammonium taloride? and acrylamide 9
0 mole? Copolymer of Polymer b; methacrylamide propyltrimethylammonium chloride 10 moles ZO and acrylamide 90 moles? copolymer of polymer c; polyacrylamide

Claims (1)

[Scope of Claims] 1. A group consisting of neutralized salts of dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl (meth)acrylamides or quaternary ammonium salts prepared with alkylating agents, (meth)acrylamide, and (meth)acrylic acid. A water-soluble polymer obtained by polymerizing at least one monomer selected from Polymer composition. 2. The water-soluble polymer composition according to claim 1, wherein the solid particles are bead-shaped with a particle size of 100 to 2000 μm. 3. In the water-soluble polymer composition according to claim 1 or 2, the cationic surfactant is contained in an amount of 0.
A composition containing 01 to 5% by weight. 4. The water-soluble polymer composition according to any one of claims 1 to 3, wherein the cationic surfactant is a quaternary ammonium salt.