KR950011448B1 - Compositions of water-soluble cationic polymer and their preparation process - Google Patents

Abstract

The water soluble polymer of formula (1) is prepd. by polymerising 10-20 wt.% concentration of the water solution with dispersion stable agent and water soluble azo cpd. as a radical polymerization initiator. The water solution comprises : 0-50 wt.% of acryl amide of formula (2); 0-50 wt.% of dimethyl aminoethyl acrylate sulfate of formula (3); and 25-50 wt.% of acryloiloxyethyl dimethylsulfobenzyl ammonium chloride of formula (4); where a, b and c are an integer of more than 0 and are mole of the reactants. Pref. 0.5-5 wt.% of carboxymethyl celluose or celluose acetate as the dispersion stable agent is used w.r.t. pure water. The obtd. compsn. has good storage stable property.

Description

Water soluble cationic polymer composition and preparation method thereof

The present invention relates to a water-soluble polymer composition of the general formula (1)

In the above formula, a, b and c are integers greater than 0 and each depends on the number of moles of the reaction. As a conventional technique, Japanese Patent Laid-Open No. 62-15251 is a method for preparing a water-soluble polymer by dispersing a polymer by adding an acrylamide copolymer to an aqueous salt solution. However, this method is prepared by dispersing the solid polymer in an aqueous salt solution after complex grinding, drying, and product selection, and thus has low economical efficiency due to a long manufacturing process and a complicated process.

On the other hand, the method of USP No. 1319632 and Japanese Patent Laid-Open No. 56-74106 uses a nonionic emulsifier in an inert organic solvent to prepare an aqueous solution of monovinyl monomer (Monmer) in water-in-oil or water-in-oil. It is a method of emulsion and emulsion polymerization. This method also has the disadvantages of poor yield due to the use of organic solvents, complexity of the manufacturing process, economical deterioration, a long time is required when dissolving the polymer.

The present invention, in order to overcome the problems in the prior art as described above, the acrylamide and acryloyloxyethyldimethylsulfobenzyl ammonium salt using a dispersant to introduce sulfone groups into the ionic monomer, the product itself is fine Since it is dispersed so as to maximize the solubility in water, using a dispersant such as carboxymethyl cellulose has the advantage of maintaining a stable stability by dispersing a high concentration of polymer.

The present invention is 0-50% by weight of acrylamide of the general formula (2), 0-50% by weight of dimethyl aminoethyl acrylate sulfate of the general formula (3), and acryloyloxyethyl die of the general formula (4) 25 to 50% by weight of methylsulfobenzyl ammonium chloride was prepared to prepare an aqueous solution having a total concentration of 10 to 20% by weight, and then the dispersion stabilizer was polymerized using 0.5 to 5% by weight with respect to pure water and a radical polymerization initiator. The water-soluble polymer of Formula (1) is manufactured.

At this time, the compound of formula (4) is 4-8 atm using the formula (5) using 20 to 40% by weight of acryloxyethyldimethylbenzyl ammonium chloride and chlorosulfonic acid of the formula (6) with respect to the organic solvent. The mixture is prepared by reacting at a room temperature of 40 ° C., and 1000 to 300 ppm of methylhydroquinone and hydroquinone are added to the compound of the general formula (5) as a polymerization inhibitor. On the other hand, normal hexane or cyclohexane is preferable as the organic solvent.

The summary of the manufacturing method according to the present invention is as follows.

Raw material :

Formula (2): acrylamide

General formula (3): Dimethylaminoethyl acrylate sulfate

Formula (4): Acryloyloxyethyldimethylsulfobenzyl ammonium chloride

Reaction solvent: water (4 to 9 weight ratio of monomer: raw materials (2), (3) and (4) total concentration of 10-20% aqueous solution)

Dispersion Stabilizer: Carboxymethylcellulose, Cellulose Acetate (0.5 ~ 5% by weight of Reaction Solvent)

Catalyst: Sodium hydrogen sulfite (20-50 ppm), Copper sulfate (20-50 ppm)

Radical polymerization initiator: 2, 2-azobis (2-amidinopropane), hydrochloride (1000-2000 ppm)

Polymerization temperature: 10 ± 2 ℃

Polymerization Condition:

Mechanism of the process according to the invention is as follows.

(a) generating radicals

b). R ^*

Where a, b and c are integers greater than or equal to 0 depending on the number of moles of each of the reactants.

In addition, the restriction | limiting conditions of reaction in this invention are as follows. First, the total concentration of acrylamide (2), dimethylaminoethyl acrylate sulfate (3) and acryloyloxyethyldimethylsulfobenzyl ammonium chloride (4) is 10 to 20% by weight in aqueous solution. If it is less than%, it does not affect the product properties, but it is uneconomical due to an increase in the transportation cost of the product due to an increase in the molar content of the final product.

Second, when the dispersion stabilizer is less than 0.5% by weight, the dispersion stabilizer effect is reduced, so that it becomes hard to use due to its own core during storage. On the other hand, when more than 5% by weight, the dispersing effect is the same, but the economical efficiency is poor due to the excessive use of the dispersion stabilizer.

Thirdly, the total concentration of acryloyloxyethyldimethylmethylbenzine ammonium chloride (5) and chlorosulfonic acid (6) is 20 to 40% by weight with respect to the organic solvent, so when the concentration is higher than 40% by weight, high by-products are produced. Increases and the yield decreases when it is 20 weight% or less. At this time, by-products are produced when the temperature is 8 atm and 40 ° C. or higher, and when the pressure is 4 atm or lower, the reaction is significantly slowed.

Fourth, when the polymerization inhibitor is used in an amount of 3000 ppm or more with respect to acryloyloxyethyldimethylbenzyl ammonium chloride (5), the polymer viscosity is low when the polymer is produced, and the waste water treatment effect is low. Happens.

The type of water-soluble azo compound used as a radical polymerization initiator in the present invention is azobis (amino propane) hydrochloride, azobis (propanoic acid) acetate, azobis (N ₆ N ⁹ -dimethylisobutylimidine) hydrochloride or azobis ( Sodium anaborate).

As described above, the present invention polymerizes the reaction dye at a low temperature to obtain a high molecular weight polymer, and by introducing sulfone groups into the cationic monomer, it is excellent in solubility in water, and the product itself is finely dispersed, thus maximizing solubility. By using carboxymethyl cellulose, it has excellent advantages such as stably dispersing high concentration polymer and maintaining storage stability for a long time.

The present invention is illustrated below with comparative examples and examples.

Comparative Example 1

Japanese Patent Publication No. 62-15251

(1) After dissolving 32.9 g of acrylamide and 67.1 g of acryloxyethyldimethylbenzyl ammonium chloride in 100 g of pure water, the mixture was heated to 40 ° C and nitrogen-substituted.

(2) Next, 0.02 g of ammonium persulfate and 0.02 g of sodium hydrogen sulfite were added to polymerize to obtain a gel-like polymer (A).

(3) The polymer (A) was cut into thin slices with a knife and dried at 105 ° C., and then a powdery polymer having a diameter of 0.5 mm or less was obtained by a powder separator.

(4) 20 g of powdered polymer was dispersed in 80 g of 25% aqueous ammonium sulfate solution, and 0.4 g of mechaacryloyloxyethyltrimethyl ammonium chloride polymer was added to dissolve it to prepare a dispersion.

Comparative Example 2

Japanese Patent Laid-Open No. 56-74106

(1) 280 g of a 345% by weight aqueous monomer solution containing 350 g of cyclohexane, 9 g of polyoxyethylene nonylphenyl ether as a surfactant, 103 g of methacryloyloxyethyltrimethyl ammonium chloride, and 23 g of acrylamide were charged into the reactor.

(2) The inside of the tube was stirred to form a stable emulsion of oil-in-water type, and then deoxygenated with nitrogen gas.

(3) The temperature was raised to 50 ° C, 0.378 g of 2,2'-azobis (2-aminophorophane) lead trichloride was added as a polymerization initiator, and polymerization was carried out at a temperature in the range of 60 to 70 ° C for 5 hours.

(4) The temperature was raised to 80 ° C. to azeotropic cyclohexane and water to remove water.

(5) After azeotropic dehydration, the polymer was filtered and dried at 90 ° C. for 1 hour to obtain a polymer having a particle diameter of 0.2 to 2.2 mm.

Comparative Example 3

USP 1,319,632

(1) To 400 g of toluene, 4 ml of polyoxynonylphenyl ether (eight moles of ethylene oxide added), 4 g of ethylene cellulose, 140 g of 70% methacryloyl trmethyl ammonium chloride, 43 g of 50% acrylamide, and 10% tertiary butyl 3 ml of hydroperoxide was added to form an emulsion.

(2) The emulsion was sublimed to reflux temperature and then polymerized for 2 hours.

(3) After water was azeotropically dehydrated, a polymer having an incident size of 0.3 to 0.6 mm was obtained.

Example 1

Process for the preparation of cationic monomers. Pressure reactor equipped with thermometer, air inlet pipe and cooler

(A) 100 g of acryloyloxyethyldimethylbenzyl ammonium chloride, 500 g of normal hexane, and 0.1 g of methylhydroquinone were added thereto.

(B) 21.5 g of chlorosulfonic acid was added dropwise for 30 minutes while stirring well at room temperature (25 ° C.), and then heated to 365 ° C. and reacted for 2 hours while maintaining the air pressure at 5 kg. 120 g of oxyethyldimethylsulfobenzyl ammonium chloride was obtained (yield 90.5%).

Element Analysis

Theoretic Value: C: 48.08%, H: 5.72%, N: 4.00%, S: 9.16%, Cl: 10.15%

Found: C: 48.10%, H: 5.42%, 0: 23.1%, N: 4.10%, S: 9.12%, Cl: 10.25%

Example 2

Method of Making Cationic Polymer

In a five-necked flask with thermometer, nitrogen introduction tube and cooler

(A) 300 g of pure water and 3 g of carboxymethyl cellulose were added thereto, and then heated to 60 ° C. while being aerated with nitrogen, followed by stirring well at rpm 400 for 30 minutes, followed by cooling to 10 ° C. and stirring.

(B) 40 g of the cationic monomer prepared in Example 1 and 75 g of 50% acrylamide were added to the reactor with good stirring, followed by aeration with nitrogen for 30 minutes.

(C) Add 0.1cc of 10% copper sulfate, 0.15cc of 10% sodium bisulfate and 10% of 2%, 2'-azobis (2-amidinopropane) and hydrochloride at 10 ± 2 ℃ After aeration for 5 minutes, the mixture was stirred at 250 rpm.

(D) After aging for 2 hours at the time of reaching 60 ° C, a finely polymerized polymer (0.5 mm or less in diameter) was obtained.

Example 3

Cationic water-soluble polymers were prepared in the same manner as in Example 2, using 45 g of 80% dimetalaminoethylacrylate sulfate instead of acrylamide.

Example 4

Cationic water-soluble polymers were prepared in the same manner as in Example 2, using 25 g of acrylamide, 4 g of 98% acryloyloxyethyldamethylsulfobenzyl ammonium chloride, and 25 g of 80% dimethylaminoethyl acrylate sulfate.

Example 5

In the same manner as in Example 2, a polymer was obtained using 250 g of pure water instead of 300 g of pure water and 50 g of acetic acid and 4 g of cellulose acetate instead of carboxymethylcellulose.

Table 1 below provides a comparative example and an example.

TABLE 1

* Reduced viscosity ( sp / c) measured 0.1% by weight of a polymer solution in 1N prescribed saline at 25 ° C. using a Canon-Penske viscometer (t ₀ = 121 seconds).

* Polymer solubility was based on when the polymer concentration was adjusted to 0.2% in a 500 ml beaker, dissolved at rpm 300, filtered through an 80 mesh sieve, and the insoluble content was 3 g or less.

As a result, it can be seen that the polymer of the present invention has extremely excellent solubility in water and excellent reducing viscosity.

Claims (5)

A method for producing a cationic water-soluble polymer by polymerizing acrylamide, dimethylaminoethylacrylate sulfate and acryloyloxyethyldimethylsulfobenzylammonium chloride aqueous solution, acrylamide of formula (2) 0 to 50 The total concentration is 0 to 50% by weight, dimethylaminoethyl acrylate sulfate of formula (3) and 25 to 50% by weight of acryloyloxyethyldimethylsulfobenzyl ammonium chloride of formula (4) A method of producing a water-soluble polymer of the general formula (1), characterized in that the aqueous solution of 10 to 20% by weight is polymerized using a water-soluble azo compound as a dispersion stabilizer and a radical polymerization initiator. Where a, b and c are integers greater than or equal to 0 depending on the number of moles of each of the reactants. The method of claim 1, wherein the carboxymethyl cellulose or cellulose acetate is used as a dispersion stabilizer using 0.5 to 5% by weight of pure water. The method of claim 1, wherein the water-soluble azo compound is azobis (amidinopropane) hydrochloride, azobis (propanoate), acetate, azobis (N, N ⁶ - dimethyl-isobutyl already Din) hydrochloride or azobis (cyano Nova Lane Sodium acid) formula (1) is a method for producing a water-soluble polymer. The method of claim 1, wherein the compound of formula (4) is reacted 1: 1 with acryloyloxyethyldimethylbenzyl ammonium chloride of formula (5) and chlorosulfonic acid of formula (6) in molar ratio. The manufacturing method of the water-soluble polymer of General formula (1) characterized by the above-mentioned. Water-soluble polymer composition consisting of 0 to 50% by weight of the general formula acrylamide and 25 to 50% by weight of acryloylethyldimethylsulfobenzyl ammonium chloride of the general formula (4) below.