JPH02258802A - Production of sulfonated aromatic polymer aqueous liquid - Google Patents

Abstract

PURPOSE:To obtain the water soluble and water dispersible title polymer aqueous liquid having small solvent content, high concentration and suitable as antistatic agent for resin by sulfonating an aromatic polymer in a solvent, adding the reaction product to water and separating the reaction product from the solvent. CONSTITUTION:An aromatic polymer [e.g. styrene (co)polymer] is sulfonated in a solvent (preferably halogenated hydrocarbon) and the sulfonated reaction product is added to water and separated from the solvent to provide the aimed polymer aqueous liquid. Furthermore, an amount of water added is preferably 0.5-20 pts.wt. based on 1 pt.wt. aromatic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an aqueous sulfonated aromatic polymer liquid. Specifically, the present invention relates to a method of separating a sulfonation reaction product and a solvent under specific conditions to obtain a highly concentrated water-soluble or water-dispersible sulfonated aromatic polymer aqueous liquid with a low solvent content.

[Prior Art] As a method for obtaining a sulfonated aromatic polymer aqueous liquid by sulfonating an aromatic polymer in a solvent, for example, a method of adding water to a sulfonation reaction product and then separating the solvent (e.g. JP-A No. 63-189404) is exemplified.

[Problems to be Solved by the Invention] However, when water is added to the sulfonated reactant and stirred, large lumps of the sulfonated reactant swell with water are formed, making stirring difficult. The higher the molecular weight, the greater the tendency, especially for high molecular weight polystyrene with an average molecular weight of 10,000 or more,
In the case of polydimethylphenylene ether, stirring is virtually impossible. As a result, even if the solvent is separated statically,
The sulfonation reaction product contains a considerable amount of solvent, and it is also difficult to distill the solvent. Also, even if the molecular weight is low, when the concentration of the sulfonated reactant in the solvent increases,
A similar mass of sulfonated reactants is produced and is virtually unstirrable. Therefore, in order to stir, it is necessary to increase the amount of water added.

As a result, in order to obtain a highly concentrated aqueous solution of the sulfonated reaction product, water must be removed by distillation or the like, which is not economical.

[Means for Solving the Problems] The present inventor has arrived at the present invention as a result of intensive research into a method for producing a highly concentrated sulfonated aromatic polymer aqueous liquid with a small solvent content.

That is, the present invention is a method for producing an aqueous sulfonated aromatic polymer liquid, which comprises sulfonating an aromatic polymer in a solvent, and then adding the sulfonation reaction product to water to separate it from the solvent. be.

The present invention will be explained in more detail below.

The aromatic polymer in the present invention may be any polymer having an aromatic nucleus in its main chain or side chain. For example, vinyl aromatic polymers such as styrene polymers, styrene copolymers, α-methylstyrene polymers, α-methylstyrene copolymers, aromatic polyethers such as polydimethylphenylene ether, polyethylene terephthalate, polyethylene isophthalate, polypropylene Examples include aromatic polyesters such as terephthalate.

As styrene or α-methylstyrene copolymer,
For example, styrene or α-methylstyrene and (meth)
Methyl acrylate, ethyl (meth)acrylate, (
(meth)acrylic acid alkyl esters such as butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, fatty acid vinyl such as vinyl acetate, vinylnaphthalene, vinyltoluene,
Aromatic hydrocarbon monomers such as p-methylstyrene (
Unsaturated carboxylic acids or their anhydrides such as meth)acrylic acid, maleic anhydride, and itaconic anhydride, α-olefins, olefins such as isoprene, imbutylene, diisobutylene, butadiene, piperylene, and chloroprene, (meth)acrylonitrile, etc. Examples include copolymers of a nitrile base with monomers, etc.

As the aromatic polyether in the present invention, poly(2
, 8-dimethylphenylene ether).

Examples of the aromatic polyester in the present invention include:
Examples include polyethylene terephthalate, polyethylene phthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and polyethylene-2°6-naphthalate.

The aromatic nucleus content in the aromatic polymer is usually at least 10%, preferably at least 20%, based on the weight of the polymer.

For example, in the case of styrene copolymers, the styrene monomer unit content in the styrene copolymer is usually at least 159A, preferably at least 30%, based on the weight of the copolymer.

In the case of aromatic polyesters, the aromatic nucleus content in the aromatic polyester is typically 10
% or more, preferably 20@A or more.

The molecular weight of aromatic polymers is usually 1000 to 2000.
0001 Preferably it is 2000-1000000.

For example, in the case of styrene polymers or styrene copolymers, the molecular weight is usually between 1000 and 200 o o o o
, preferably 2,000 to 1,000,000.

In the case of aromatic polyethers, the molecular weight is usually 100
0~1000000. Preferably 200-5000
It is 00.

In the case of aromatic polyesters, the molecular weight is usually 100
0~1000000. Preferably 200-5000
It is 00.

In the present invention, after the aromatic polymer is dissolved in a solvent, the aromatic polymer is sulfonated by various methods.

As the solvent, those inert to the sulfonating agent are usually used, such as aliphatic halogenated hydrocarbons having 1 to 2 carbon atoms and nitrated hydrocarbons having 1 to 3 carbon atoms. Specific examples of halogenated hydrocarbons include 1.2-dichloroethane, methylene dichloride, ethyl chloride, carbon tetrachloride, 1.1-dichloroethane, 1. 1. 2. Examples include 2-tetrachloroethane, chloroform, and ethylene dipromide. Examples of nitrated aliphatic hydrocarbons include nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. Preferably it is a halogenated hydrocarbon.

Dissolution of the aromatic polymer depends on the molecular weight of the polymer, but the aromatic polymer is usually dissolved in the amount of 1 part by weight per 100 parts by weight of the solvent.
~100 parts by weight, preferably 5 to 50 parts by weight, are added and dissolved.

Sulfuric anhydride is preferably used as the sulfonating agent. Liquid sulfuric anhydride, liquid sulfuric anhydride with an inert gas such as nitrogen or dry air and 1. Sulfuric anhydride diluted with an aliphatic halogenated hydrocarbon having 1 to 2 carbon atoms such as 2-dichloroethane and ethyl chloride can also be used.

A complex of sulfuric anhydride and Lewis base can also be used and is preferred. Lewis bases include triethyl phosphate,
Examples include trialkyl phosphates such as trimethyl phosphate, fatty acid alkyl esters such as ethyl acetate and ethyl palmitate, and ethers or thioethers such as dioxane, thioxane and diethyl ether. Preferred Lewis bases are trialkyl phosphates and fatty acid alkyl esters.

In the present invention, the amount of the sulfonating agent used is usually 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of aromatic nucleus units in the aromatic polymer. It is better to carry out the sulfonation using a small amount. When the amount of sulfonating agent increases, by-products such as sulfur sulfate increase.

When using a complex of sulfuric anhydride and Lewis base, the amount of Lewis base used is usually 0.01 to 1 mole of aromatic nuclear units constituting the total aromatic polymer used in the reaction.
The amount is 1 molar, preferably 0.02 to 0.5 molar.

The sulfonation reaction is usually carried out at 0 to 80°C, preferably at 1
It is carried out at 0-50°C and in anhydrous conditions.

The method of sulfonating the aromatic polymer of the present invention will be illustrated.

The aromatic polymer is dissolved in the aliphatic halogenated hydrocarbon such that the concentration of the polymer in the solvent is typically in the range of 5 to 50% by weight. A solvent for the aliphatic halogenated hydrocarbon and optionally a Lewis base are added to the sulfonation reactor.

Next, equal amounts of the polymer solution and sulfuric anhydride are added simultaneously to the reactor, usually over a period of 2 to 20 hours.

The reaction temperature is usually kept at 10-50°C. As the reaction progresses, the sulfonated reactant precipitates as a solvent-insoluble substance.

In the present invention, the sulfonation reaction product obtained as described above can be used as it is or in the form of hydroxides or carbonates of alkali metals or alkaline earth metals, or ammonia, amines such as triethylamine, dimethylamine, laurylamine, etc. After adding a neutralizing agent such as an alkylamine such as stearylamine, or an alkanolamine such as ethanolamine, the reactant is gradually added to water or the above neutralizing agent aqueous solution while stirring, and the mixture is thoroughly stirred. Dissolve or disperse the sulfonation reactant in water.

The amount of water varies depending on the molecular weight of the aromatic polymer, but is usually 0.5 to 20 parts by weight per 1 part by weight of the aromatic polymer.
Preferably it is 1 to 10 parts by weight.

Thereafter, the solvent is removed by distillation, liquid separation, etc. In order to reduce the amount of solvent contained in the sulfonated polymer aqueous solution, a method of distilling the solvent is preferred.

In the case of solvent separation by distillation, the sulfonated polymer aqueous liquid is heated while stirring and mixing, and the solvent is distilled out under normal pressure or reduced pressure.

[Example] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 As a sulfonation reactor, 1,2-dichloroethane 1 was placed in a 3 L four-necked flask equipped with a stirrer and a thermometer.
040g yohylic acid)! 7! Chi/l'9゜1g (0,
05 mol) was added. Further, 104 g of polystyrene (molecular weight 200,000) (1.0 mol as an aromatic nucleus unit constituting polystyrene) was dissolved in 936 g of 1,2-dichloroethane in advance to obtain a solution A.

The temperature in the reactor was maintained at 20-25° C., and 4 g (0.05 mol) of liquid sulfuric anhydride was gradually added dropwise.

Next, 1040 g of solution A and 80 g of liquid sulfuric anhydride (1
, 0 mol) were added dropwise at the same time. The dropping speed is such that solution A is
The ratio of 418 g/waiting time sulfuric anhydride was adjusted to 32 g/hour. During the dropping process, cool the temperature to 18
It was kept at ~22°C.

The sulfonated polystyrene precipitated as it formed. After the sulfonation was completed, the dispersion slurry of sulfonated polystyrene was gradually added to 481 g of an aqueous solution containing 44 g of sodium hydroxide at a temperature of 30° C. while stirring the solution.

Heat the neutralized mixture and add the sulfonated reactants to the aqueous solution.
, under normal pressure until the odor of 2-dichloroethane disappears.
The temperature was raised to 105°C, and 1,2-dichloroethane was distilled off. After finely adjusting the pH to 8 with an aqueous sodium hydroxide solution, water was added to obtain a 30% aqueous sodium salt solution of sulfonated polystyrene. The 1,2-dichloroethane content of the aqueous solution was determined by gas chromatography and was found to be 0.05% by weight.

Example 2 As a sulfonation reactor, 1,2-dichloroethane 6 was added to a 3 L four-necked flask equipped with a stirrer and a thermometer.
93 g and triethyl phosphate 18°2 (0.1 mol)
added. In addition, in advance, polystyrene (molecule llk500
0) 208g (2.0 mol as an aromatic unit constituting polystyrene) to 1179 1゜2-dichloroethane
A solution A was obtained by dissolving it in g.

The temperature in the reactor was maintained at 20 to 25°C, and 8 g (0.1 mol) of liquid sulfuric anhydride was gradually added dropwise.

Next, 1387 g of solution A and 160 g of liquid sulfuric anhydride (
2.0 mol) was added dropwise at the same time. The dropping rate was adjusted so that the rate of solution A was 98 g/hour, and the rate of sulfuric anhydride was 23 g/hour. During the dropping process, cool the temperature to 18
It was kept at ~22°C.

The sulfonated polystyrene precipitated as it formed. After the sulfonation was completed, the dispersion slurry of sulfonated polystyrene was added to 471 g of water at a temperature of 30° C. with stirring.

Furthermore, add 320 g of 30% sodium hydroxide aqueous solution,
Neutralized. The neutralized mixture was heated, and 1,2-dichloroethane was distilled off under normal pressure until the odor of 1,2-dichloroethane in the aqueous solution of the sulfonated reaction product disappeared. After adjusting the pH to 8 with an aqueous sodium hydroxide solution, water was added to obtain a 40% aqueous sodium salt solution of sulfonated polystyrene. 1 of the aqueous solution. When the 2-dichloroethane content was determined by gas chromatography,
It was 0.05% by weight.

Example 3 As a sulfonation reactor, 1,2-dichloroethane 1 was added to a 3 L four-necked flask equipped with a stirrer and a thermometer.
0.040 g and 9.1 g (0.05 mol) of triethyl phosphate were added. Further, in advance, 120 g of polydimethylphenylene ether (150,000 asci) (1.0 mol as an aromatic nucleus unit constituting the polymer) was dissolved in 920 g of 1,2-dichloroethane to obtain a solution A.

The temperature in the reactor was maintained at 35-40° C., and 4 g (0.05 mol) of liquid sulfuric anhydride was gradually added dropwise.

Next, 1040 g of solution A and 80 g of liquid sulfuric anhydride (1
, 0 mol) were added dropwise at the same time. The dropping speed is such that solution A is
418 g/hour, sulfuric anhydride was adjusted to a rate of 32 g/hour. During the dripping process, cool the temperature to 35~35℃.
It was kept at 40°C.

The sulfonated polymer precipitated as it formed. After the sulfonation was completed, the dispersion slurry of sulfonated polystyrene was gradually added to 471 g of water at a temperature of 30° C. with stirring. Further, 147 g of a 30% aqueous sodium hydroxide solution was added to neutralize the mixture. The neutralized mixture was heated, and 1,2-dichloroethane was distilled off under normal pressure until the odor of 1,2-dichloroethane in the aqueous solution of the sulfonated reaction product disappeared. After finely adjusting the pH to 8 with an aqueous sodium hydroxide solution, water was added to obtain a 25% concentration water-soluble sodium salt of sulfonated polydimethylphenylene ether. When the 1°2-dichloroethane content of the aqueous solution was determined by gas chromatography, it was found that O,
OS was % by weight.

Comparative Example 1 471 gt of water was added to sulfonated polystyrene and sulfonated polydimethylphenylene ether obtained by carrying out the sulfonation process in the same manner as in Examples 1 to 3, and stirring was attempted, but after a few minutes, a large gel-like mixture formed. The experiment could not proceed because lumps formed and stirring was impossible.

[Effects of the Invention] According to the present invention, a highly concentrated aqueous sulfonated aromatic polymer liquid with a low solvent content can be obtained. For applications that require high concentrations such as antistatic agents for resins,
suitable.

Claims (1)

[Claims] 1. Production of an aqueous sulfonated aromatic polymer liquid, which comprises sulfonating an aromatic polymer in a solvent and then adding the sulfonation reaction product to water to separate it from the solvent. Method. 2. The amount of water is 0.5 to 20 per part by weight of aromatic polymer.
The manufacturing method according to claim 1, wherein the amount is parts by weight.