JPS6063204A - Production of quaternarized polystyrene - Google Patents

Abstract

PURPOSE:To obtain a colorless, odorless and transparent quaternarized polystyrene containing little impurities, by dissolving a specific chloromethylated polystyrene polymer in a water-soluble solvent, adding an aqueous solution of trialkylamine or trialkylamine and water separately to the solution, and separating the objective polymer from the aqueous phase after the reaction. CONSTITUTION:A chloromethylated polystyrene polymer having an average molecular weight of >=500 and containing >=10(wt)% chloromethylated styrene and/or >=10% chloromethylated alpha-methylstyrene as monomers, is dissolved in a water-soluble solvent (e.g. acetone), and is made to react with a trialkylamine (e.g. trimethylamine) by adding the trialkylamine in the form of aqueous solution or adding trialkylamine and water separately to the above polymer solution. Trialkylammonium group is introduced into the chloromethyl group by the reaction, and the reaction mixture is left at rest to separate into the aqueous phase and the solvent phase. The objective quaternarized polystyrene is separated from the aqueous phase. USE:Agent for processing paper or synthetic paper.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing quaternized polystyrenes.

More specifically, the present invention relates to a method for producing quaternized polystyrene that is colorless, odorless, transparent, and has few impurities.

Traditionally, low molecular weight surfactants, nonionic polymers, anionic polymers, and cationic polymers have been used as processing agents for paper and synthetic paper for the purpose of increasing paper strength, preventing static electricity, and imparting electrical conductivity. In particular, quaternary ammonium polymers are known to be excellent as conductive agents, and are described in U, S, Pat, 3011.
918, Japanese Patent Publication No. 50-1154 monomer, or a copolymer of monomers, and has drawbacks such as low monomer yield, poor stability, and high production cost.

The latter is a polymer containing at least 30% by weight of styrene units having quaternary ammonium salt-substituted methyl groups; The desired product is prepared by introducing a salt-substituted methyl group, or the production by polymerization of monomers is performed using the above-mentioned No.U, S, Pat, 3.
011918 (!: A production method that has the same drawback and introduces a quaternary ammonium salt-substituted methyl group into a polymer having styrene units is to directly add a tertiary amine such as trimethylamine to the solid content of chloromethylated polystyrene. After the reaction, the excess amine is distilled off, so the reaction does not proceed uniformly, and the reaction time is long, so the target product tends to be colored, and there are many problems with the product properties due to the contamination of contaminants. As a result, the transparency and printability are not sufficient for the purpose of use.

The present inventors focused on such problems, and as a result of intensive studies, they discovered a method for producing quaternized polystyrene that has excellent transparency, is not colored, and has little odor due to the reaction raw materials, The invention has been completed.

In other words, the present invention provides an aqueous solution of at least 10% by weight of chloromethylstyrene or/and at least a 10-fold alkylamine as a monomer unit in a polymer having an average molecular weight of 500 or more, or a combination thereof with water. After adding them separately and conducting a reaction to introduce a trialkylammonium group into a chloromethyl group, the reaction system is separated into two layers: an aqueous layer and a solvent layer, and the solvent layer containing unreacted trialkylamine is further separated. , is a method for producing quaternized polystyrene as an aqueous solution in a one-stage reaction that does not contain unreacted raw materials.

The aqueous solution of quaternized polystyrene thus obtained solves the above problems and is extremely excellent.

Regarding the raw materials and manufacturing method used in the method of the present invention, the polystyrene of the present invention is a polymer of simple styrene, a polymer of simple α-methylstyrene, or a copolymer of styrene and α-methylstyrene. can be mentioned.

Or + methylated polystyrenes, at least 1
A polymer with an average molecular weight of 500 or more consisting of 0% by weight of chloromethylated styrene and/or a small amount (both 10% by weight of chloromethylated α-methylstyrene and the balance of styrene and/or α-methylstyrene). The latter method is inexpensive and common, either by polymerizing methylstyrene or chloromethyl α-methylstyrene or by chloromethylating the polystyrenes.As a known method for chloromethylating polystyrenes, The process involves reacting a commonly used chloromethylating agent in the presence of a Friedelkraff catalyst, e.g. chloromethyl ether in the presence of aluminum trichloride or zinc chloride, in the presence of a solvent. There is also a way to react.

To the chloromethylated polystyrene obtained as described above, a water-soluble stimulant in an amount of 1 to 10 times by weight is added and dissolved. Add trialkylamine in an amount of 1 to 1.3 times in molar ratio to the chloromethyl group introduced into the chloride and chloromethylated polystyrene as an aqueous solution or separately with water and heat at 10 to 60°C. The reaction is carried out for 1 to 10 hours to introduce a trialkylammonium group. I
- Examples of realkylamines include trimethylamine and toluethylamine.

Aqueous solutions that dissolve chloromethylated polystyrenes may be used alone or in combination of two or more.

In the initial reaction of introducing the above-mentioned trialkylammonium chloride group, the reaction system is homogeneous, or as the reaction progresses, unreacted raw materials are transferred to the solvent layer used to dissolve the chloromethylated polystyrene. The target quaternized polystyrene migrates to the aqueous layer, and when the reaction is left standing after the reaction is completed, it separates into two layers: a solvent layer and an aqueous layer. After standing, the solvent is separated and removed to obtain a quaternized polystyrene containing no unreacted raw materials as an aqueous solution. If necessary, trace amounts of solvent contained in the aqueous solution can be removed by l.knopping or steam distillation.

The aqueous solution of quaternized polystyrene obtained in this manner is highly transparent, has no coloration, has little odor, and has excellent long-term storage stability.

When the aqueous solution of quaternized polystyrene of the present invention is used as a processing agent for paper or synthetic paper, the resulting aqueous solution can be applied as is, or diluted with water and applied directly or by dipping, and no reaction occurs at the time of application. Work environment is good as there is no smell of amine etc.
2. It is preferable that the amount of impurities is small, so that a coated surface with excellent printability without uneven coating can be obtained.

Hereinafter, the present method will be described in detail with reference to examples, but the present method is not limited to these examples.

Example 1 Polyvinylhensyl homopolymer (average molecular weight approximately 200
00.100% chloromethylated product) 98.59 was dissolved in 975 g of dimethylpolamide, and 383.59 of a 10% aqueous solution of trimethylamine was gradually added at a temperature of 30°C. After the addition was completed, the reaction was carried out at the same temperature for 5 hours, and when the mixture was cooled to room temperature and stirring was stopped, the reaction mixture was separated into two layers: an aqueous layer and a solvent layer. The solvent layer was separated to obtain a colorless and transparent aqueous solution with little odor and containing 284% polyvinylhenosyltrimedyl ammonium chloride.

50% chloromethylated product 944y of mer (average molecule ffl 10000) was dissolved in 472 g of dioxane, 247.69 g of water was further added, and 38.9'j of triethylamine was gradually added at a temperature of 35°C. The temperature was raised to 50° C. 2 hours after the addition was completed, the reaction was continued at the same temperature for 4 hours, and then the mixture was cooled to room temperature and separated into two layers. The solvent layer was separated to obtain a colorless, transparent, and odorless aqueous solution of the quaternized polymer. The solid content concentration was 344%.

Example 3 Polystyrene with a chloromethylation rate of 10% (average molecular weight approximately 1000) 108.79 g was dissolved in 109 g of acetonate, and water was further added 108.7 g! and 30% at a temperature of 40℃.
256 g of a trimethylamine aqueous solution was gradually added, and the reaction was carried out at the same temperature for 3 hours. When the mixture was cooled to room temperature and stirring was stopped, the mixture was separated into two layers. The solvent layer was separated to obtain a colorless, odorless, slightly cloudy aqueous solution of the quaternized polymer. The solid content concentration was 475%.

Example 4 Polystyrene 118.39 (average molecular weight approximately 2500) with a chloromethylation rate of 30% was dissolved in 354.89 tetrahydrofuran, and 203.9 f/8% 7% triethylamine aqueous solution was gradually added at a temperature of 45°C. After the addition was completed, the reaction was continued at the same temperature for 3 hours, and then cooled to room temperature and separated into two layers. The solvent layer is separated and a clear, colorless and odorless quaternized polymer aqueous solution (solid content concentration 40%) is obtained.
) was obtained.

Comparative Example 1 Polystyrene with a chloromethylation rate of 30% (average molecular weight about 2500) 118.39 was dissolved in 354.89 of tetrahydrofuran, and 203.99 of an 88'7% triedylamine aqueous solution was added and the same procedure as in Example 4 was carried out. The reaction was carried out. After the reaction is complete, remove the solvent with an evaporator,
Furthermore, 539 pure water was added to adjust the solid content concentration to 40% to obtain a turbid yellow quaternized polymer aqueous solution with a strange odor.

The quaternized boristinones produced in the Examples and Comparative Examples were coated on bi-quality paper using a roll at a coating amount of 2 g/m2, and the surface resistance values were measured. The results are shown in Table-1. The surface resistance value was measured at 25° C. and 30% relative humidity using an electrometer manufactured by Takeda Riken (Haki →).

Table-1

Claims (1)

[Scope of Claims] At least 10% by weight of chloromethylated styrene or/and at least 10% by weight of chloromethylated α-methylstyrene as a monomer unit in a polymer having an average molecular weight of 500 or more A chloromethylated polystyrene polymer containing chloromethyl is dissolved in a water-soluble solvent, a trialkylamine is added in an aqueous solution, or it and water separately to perform a reaction. After introducing a trialkylammonium group into a chloromethyl group, the reaction system is separated into an aqueous layer. A method for producing quaternized polystyrene, which comprises separating into two layers, a solvent layer and a solvent layer, and obtaining a reaction product as an aqueous solution.