JPH0248002B2 - KARUBOKISHIBINIRUHORIMAANOANMONIUMUENMATAHAAMINENNOSEIZOHOHO - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing ammonium salts and amine salts of carboxyvinyl polymers (hereinafter simply referred to as salts of carboxyvinyl polymers) that are non-toxic, highly safe, and have excellent thickening and dispersibility properties. Pertains to.

More specifically, the present invention relates to a method for producing a powdered ammonium salt or amine salt of a carboxyvinyl polymer, in which ammonia gas or amine gas is directly applied to the carboxyvinyl polymer powder.

Carboxyvinyl polymer salts dissolve or swell in water and water-soluble alcohols and glycols, and exhibit significant thickening properties, resulting in paints,
Color materials, adhesives, fibers, synthetic leather, ceramics, cosmetics,
It is well known that they are widely used as thickeners, dispersants, and stabilizers in various industries such as pharmaceuticals and agricultural chemicals.

Conventional methods for producing these salts include a method in which free carboxyvinyl polymer is suspended in a solvent in which the polymer is not dissolved and ammonia gas or amine gas is introduced to form salts (hereinafter simply referred to as the solvent method); Examples include a production method of polymerizing neutralized monomers (hereinafter simply referred to as polymerization method).

However, since the solvent method uses a large amount of organic solvent, there are dangers, health and safety issues, and problems with the recovery and processing equipment for the organic solvent.
The number of steps such as neutralization, deliquification, and drying increases, which is disadvantageous in terms of cost. Regarding the polymerization method, since the ammonium salt and amine salt of the monomer are water-soluble, there is a problem that when polymerization is carried out in an aqueous system, it is difficult to isolate the carboxyvinyl polymer salt in powder form.

In order to solve this problem, the present inventors have conducted intensive research on the method for producing salts of carboxyvinyl polymers, and have found that when ammonia gas or amine gas is directly applied to powdered carboxyvinyl polymers, the reaction efficiency is surprisingly high. The present inventors have discovered that carboxyvinyl polymer salts can be obtained in powder form, and have completed the present invention.

That is, the present invention allows ammonia gas or amine gas to act on carboxyvinyl polymer powder, and the carboxyvinyl polymer powder reacts with the ammonia gas or amine gas in powder form to give a powdered ammonium salt or amine salt of the carboxyvinyl polymer. This is a method for producing a powdered ammonium salt or amine salt of a carboxyvinyl polymer.

The present invention can be easily implemented, for example, as follows.

By introducing a predetermined amount of ammonium or amine gas into carboxyvinyl polymer powder while stirring and cooling, preferably at a temperature below 50°C, carboxyvinyl polymer salt can be obtained almost quantitatively in powder form. . The reaction proceeds rapidly with heat generation, and carboxyvinyl polymer salt is efficiently produced.

As the reaction apparatus, any general stirring reaction apparatus can be used without particular limitation as long as it has sufficient stirring and cooling ability to prevent the accumulation of neutralization heat in the powder.

Introducing ammonia gas or amine gas can be carried out by reacting while continuously introducing ammonia gas or amine gas, or by filling the ammonia gas or amine gas in a sealed environment after vacuum depressurization, and reacting, but the heat of neutralization In view of ease of control, it is preferable to carry out the reaction while continuously introducing ammonia gas or amine gas. In addition, since carboxyvinyl polymer immediately reacts with ammonia gas or amine gas to form a salt with high reaction efficiency, it is also easy to conduct a continuous reaction while supplying a certain amount of carboxyvinyl polymer and ammonia gas or amine gas. It can be implemented.

Furthermore, in order to proceed with the reaction in a safer state, an inert gas such as nitrogen gas may be introduced simultaneously with ammonia gas or amine gas without any problem to the present invention.

Here, carboxyvinyl polymers include those known per se, such as acrylic acid, methacrylic acid,
Polymers, copolymers, etc. of olefinic unsaturated carboxylic acids such as itaconic acid or derivatives thereof (chloroacrylic acid, cyanoacrylic acid, α-phenylacrylic acid, α-benzylacrylic acid, etc.) Examples include those obtained by crosslinking polymerization with a crosslinking agent and a crosslinking agent. As a crosslinking agent, polyallyl ethers of allyl sucrose, divinylbenzene, divinyldioxane, bentaerythritol or polyalkylene glycol, which are monomers having polyfunctional groups,
Examples include polyallyl esters of cyanuric acid, isocyanuric acid, phosphoric acid or phosphorous acid.

The carboxyvinyl polymer can be produced by a method known per se, for example, by using a monomer to be polymerized and a polymerization initiator (for example, peroxides such as lauroyl peroxide and tert-butyl peroxide, azobisisobutyronitrile, 2,2'-azobis( 2,
(4'-dimethylvaleronitrile) and other azo catalysts) are polymerized by heating in a solvent, and if the acid monomer is an ester, it is hydrolyzed after polymerization. It is usually manufactured by drying.

In addition, the amines used in carrying out the present invention include, without exception, commonly used organic amines that can become gaseous, such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine. , aliphatic amines such as propylamine, butylamine, isopropylamine, diisopropylamine, allylamine, diallylamine, alicyclic amines such as cyclopropylamine, cyclohexylamine, aromatic amines such as aniline, methylaniline, ethanolamine, diethanolamine, Examples include hydroxyalkylamines such as ethanolamine, cyclic amines such as morpholine and piperidine, and polyamines such as ethylenediamine.

In order to make these amines gaseous, it is usually sufficient to heat them to their boiling point.
This can be carried out according to a vaporization method known per se.

The thickening effect of carboxyvinyl polymer salts usually has no practical difference between pH 5 and 10, so when used as a thickening agent, no free carboxyl groups or alkaline components remain within that range. No problem. Usually for carboxyl group
30-90%, preferably 50-70% equivalent of ammonia gas or amine gas is used.

According to the present invention, since no organic solvent is used in the neutralization reaction, there are no safety and hygiene problems, and there is no need for equipment for recovering or treating organic solvents, and the process is simple. It has the following advantages. Furthermore, it has the advantage that it does not have the complexity and difficulty of the manufacturing process, which is seen in the manufacturing process of polymerizing ammonium salts or amine salts of monomers.

Examples of the present invention are shown below, but the present invention is not limited thereto. Incidentally, in the examples, parts indicating numbers are parts by weight, and % indicates weight %.

Example 1 Ammonia gas introduction pipe, thermometer, gas discharge pipe,
504 g of carboxyvinyl polymer (Wako Pure Chemical Industries Co., Ltd., trade name: Hibiswako 104) powder in a 5-separable flask equipped with a stirrer blade
Add 0.8 ml of ammonia gas under ice-water cooling and stir.
The ammonia was introduced at a rate of g/min, and the internal temperature was maintained at 15 to 30° C., and the introduction of ammonia was stopped after about 90 minutes to obtain 576 g of ammonium salt of carboxyvinyl polymer in the form of white fine powder.

By pouring the obtained ammonium salt into water and stirring, a thickened aqueous solution was easily obtained, and the 1% solution of the ammonium salt had a pH of 6.7 and a viscosity of 71,000 cps (B8H type rotational viscometer, 20 rpm).

Example 2 360 g of carboxyvinyl polymer (Wako Pure Chemical Industries, Ltd., trade name: Hibiswako 105) powder was placed in a flask similar to that used in Example 1, and a 30% trimethylamine aqueous solution was heated to reflux while stirring and cooling with ice water. The liberated trimethylamine gas was introduced at a flow rate of 2.8 g/min after dehumidification. Internal temperature is 25-35
The temperature was maintained at 0.degree. C., and the introduction of trimethylamine was stopped after about 1 hour, yielding 523 g of trimethylamine salt of carboxyvinyl polymer in the form of white fine powder.

As in Example 1, a thickened solution was easily obtained, and the pH of the 1% solution of trimethylamine salt was 6.0.
It showed a viscosity of 10200 cps (B8H type rotational viscometer 20 rpm).

Example 3 500 g of white fine powder polyacrylic acid was placed in a flask similar to that described in Example 1, and ammonia gas was introduced at a rate of 0.7 g/min under stirring and cooling.
The internal temperature is maintained at 20-30℃, and the introduction is stopped after about 120 minutes.
White fine powder polyacrylic acid ammonium salt
583g was obtained.

As in Example 1, a thickened aqueous solution was easily obtained, and the pH of a 1% solution of ammonium salt was 6.8 and 6500 cps.
(B8H type rotational viscometer 20 rpm) viscosity is shown.

Claims (1)

[Claims] 1. A method characterized in that ammonia gas or amine gas is applied to carboxyvinyl polymer powder, and the carboxyvinyl polymer powder reacts with the ammonia gas or amine gas in powder form to give a powdered ammonium salt or amine salt of carboxyvinyl polymer. A method for producing a powdered ammonium salt or amine salt of a carboxyvinyl polymer.