JPH02294305A - Method for sulfonating aromatic polymer - Google Patents

Abstract

PURPOSE:To obtain a sulfonated polymer, having a high sulfonation degree and useful as an antistatic agent, dispersing agent for pigments, concrete water reducing agent, etc., by separately feeding an aromatic polymer solution and a sulfonating agent from nozzles to a reactor under a specific discharging pressure. CONSTITUTION:An aromatic polymer solution, such as PS, and a sulfonating agent (preferably sulfuric anhydride) are separately discharged from nozzles under conditions of >=100kg/cm<2>.G, preferably 150-300kg/cm<2>.G discharging pressure and fed to a reactor to sulfonate the aromatic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present laBA relates to a method for sulfonating aromatic polymers.

[Prior art] Polystyrene sulfone is produced by continuously feeding a polystyrene solution and a sulfonating agent separately at a rate that satisfies specific conditions into a sulfonation reactor equipped with a high shear force stirrer. methods are known (for example, Japanese Patent Application Laid-Open No.
72703).

[Problems to be Solved by the Invention] However, when the average molecular weight of polysticine used as a raw material becomes high, the viscosity of the reaction solution becomes high.

This poses a problem in that handling becomes difficult and the yield of water-soluble sulfonated polystyrene is extremely reduced. Additionally, the complicated structure of the stirrer makes it difficult to clean. be.

[! l! Means for Solving the Problem] The present inventors have arrived at the present invention as a result of intensive studies on a method for sulfonating aromatic polymers that is capable of sulfonating aromatic polymers such as high molecular weight polystyrene and is easy to clean.

That is, in the present invention, when an aromatic polymer is continuously supplied to a sulfonation reactor for sulfonation, the aromatic polymer solution and the sulfonation agent are separately discharged from a nozzle at a pressure of 100 kg/am'・G or more. This is a method for sulfonating an aromatic polymer, which is characterized in that the aromatic polymer is supplied to a reactor with

The aromatic polymer in the present invention may be any polymer having aromatic removal in its main chain or side chain, and examples thereof include vinyl aromatic polymers, aromatic polyesters, aromatic polyesters, and the like.

Examples of the vinyl aromatic polymer include styrene polymers or copolymers, α-methylstyrene polymers or copolymers, and the like. Examples of the styrene copolymer or α-methylstyrene copolymer include styrene or α-methylstyrene copolymer.
Methylstyrene and alkyl (meth)acrylates [methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, etc.], Fatty acid vinyl [such as vinyl acetate, aromatic hydrocarbon monomers [vinylnaphthalene, vinyltoluene, p-methylstyrene, etc.], unsaturated carboxylic acids or their anhydrides [(meth)acrylic acid, maleic anhydride,
itaconic anhydride], (chlorinated) olefins (α-
Examples include copolymers with olefins, isoprene, imbutylene, diisobutylene, butadiene, piperylene, chloroprene, etc.), and copolymers with 2}IJ group-containing monomers [(meth)acrylonitrile, etc.].

Examples of the aromatic polyether include poly(2,6-dimethylphenylene ether).

Examples of the aromatic polyester include polyethylene terephthalate, polyethylene isophthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and polyethylene-2.6-naphthalate.

The aromatic nucleus content in the aromatic polymer is usually 10% or more, preferably 20% or more, based on the number of polymers in the polymer. For example, in the case of a styrene copolymer, the styrene monomer unit poisoning in the styrene copolymer is usually 15% or more, preferably 30% or more, based on the polymerization of the copolymer. In the case of aromatic polyesters, the aromatic nucleus content in the aromatic polyester is usually at least IO%, preferably at least 20%, based on the weight of the polymer.

The molecular weight of the aromatic polymer is usually t,ooo to 2,00
0,000, preferably 2. 000-1,000
,000. In the case of styrene polymers or copolymers, the molecular weight is usually between t,ooo and 2,00
0,000, preferably 2,000 to 1,000.
It is 000. In the case of aromatic polyethers, the molecular weight is usually i,ooo to 1,000,00G,
Preferably it is 2,000 to 500,000. In the case of aromatic polyester, the molecular weight is usually from 1,000 to
1,000,000, preferably 2,000-50
It is 0,000.

In the present invention, the aromatic polymer is sulfonated in solution. Examples of the solvent for making the solution include those that are inert to the sulfonating agent, such as aliphatic halogenated hydrocarbons having 1 to 2 carbon atoms and nitrated aliphatic hydrocarbons having 1 to 3 carbon atoms. . As aliphatic halogenated hydrocarbons,
l,2-dichloroethane, methylene dichloride, ethyl chloride, carbon tetrachloride,! , 1-dichloroethane, 1,1,
Examples include 2.2-tetrachloroethane, chloroform, and ethylene dibromide. Examples of nitrated aliphatic hydrocarbons include nitromethane, nitroethane, l-nitropropane, and 2-nitropropane. Preferred solvents are aliphatic halogenated hydrocarbons.

The dissolution of the aromatic polymer depends on the molecular weight of the polymer, but the aromatic polymer is usually dissolved in an amount of 1-
100 parts by weight, preferably 5 to 50 parts by weight, are dissolved.

Sulfuric anhydride is preferably used as the sulfonating agent. Liquid sulfuric anhydride, liquid sulfuric anhydride, nitrogen gas, sulfonating agent such as dry air, inert gas, and 1,2-dichloroethane,
Anhydrous sulfuric acid diluted with a solvent inert to the sulfonating agent such as an aliphatic halogenated hydrocarbon having a few to 2 carbon atoms such as ethyl chloride can also be used. The concentration of sulfuric anhydride diluted with inert gas is normal! -15% by volume, preferably 3 to 5% by volume.

The concentration of anhydrous sulfuric acid diluted with an inert solvent is usually 1 to 50% by weight, preferably 5 to 20% by weight.

Moreover, a complex of sulfuric anhydride and Lewis base can also be used. Examples of Lewis bases include trialkyl phosphates (triethyl phosphate, trimethyl phosphate, etc.), fatty acid alkyl esters (ethyl acetate, ethyl valmitate, etc.), ethers or thioethers (dioxane, thioxane, diethyl ether, etc.). Preferred Lewis bases are trialkyl phosphates and fatty acid alkyl esters.

In the present invention, the amount of the sulfonating agent used is usually 0.4 to 2 mol, preferably 0.5 to 1.5 mol, per 1 mol of aromatic nucleus units in the aromatic polymer. be.

If the amount of the sulfonating agent is less than 0.4 mol, the dispersibility of the sulfonated reaction product in water will be poor. Furthermore, if the amount of sulfonating agent is large, by-products such as sulfur sulfate will 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.
1 molar amount, preferably 0.02 to O. S mol m.

In the present invention, the sulfonation reactor (or mixing head) is one in which a polymer solution and a sulfonation agent are separately jetted from a nozzle at high pressure and mixed by the jetting force of the liquid.

The nozzles are typically opposed and allow the blower solution and sulfonating agent to collide.

The spacing between the nozzle tips is usually 5 to 50 fill, preferably IO to 20 fill! It is l. The discharge pressure from the nozzle is 100Kg/am'・G or more, preferably 150
〜300Kg/c■2・G. Discharge pressure is IQ OK
In the g/cs'·G structure, mixing is insufficient and a large amount of water-insoluble sulfonated polymer is present, resulting in an extremely low yield of water-soluble sulfonated polymer.

The diameter of the nozzle is usually from 0.1 to 0.0mII+2, preferably from 0.2 to 0.5+u+", and can be adjusted by 21 dollars or the like to change the discharge pressure.

Raw materials such as an aromatic polymer solution and a sulfonating agent are supplied to the reactor using normal means. For example, the raw materials are placed in a raw material tank and fed into the reactor using a pump such as a plunger type bomb, a turbo blower, etc., and the injection nozzle of the reactor is used. The mixture is mixed by injection. The flow rate of polymer solution and sulfonating agent into the reactor is typically 100-500 ml/sea.

The polymer solution and sulfonating agent instantaneously mixed by collision are usually stored in a large capacity reservoir to complete the sulfonation reaction.

The reaction temperature for sulfonation is usually 0 to 80°C, preferably 10 to 50°C. The reaction is carried out under anhydrous conditions.

The obtained sulfonation reaction product can be used as it is or in the form of hydroxides, carbonates, or ammonia of alkali metals, alkaline earth metals, etc., amines (alkylamines such as triethylamine, dimethynoleamine, laurylamine, stearylamine, etc.), and alkanols. For example, amines
After adding a neutralizing agent such as ethanolamine, etc., the reactant is gradually added to the water or the above neutralizing agent aqueous solution while stirring, and the sulfonated reactant is dissolved or dispersed in the water by stirring thoroughly. do.

Although the amount of water can be varied depending on the molecular weight of the aromatic polymer, it is usually 0.00% per part by weight of the aromatic polymer.
5 to 20 parts by weight, preferably 1 to 10 parts by weight.

Thereafter, the solvent is removed by distillation, branching, etc. In order to reduce the solvent content in the sulfonated polymer aqueous liquid, 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.

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

Examples 1-4 Polystyrene with an average molecular weight of 1,000 or 200,000 was dissolved in 1,2-dichloroethane to prepare a 15% by weight polymer solution. Also as a sulfonating agent! , 10% by weight liquid sulfuric anhydride diluted with 2-dichloroethane was used. These were separately supplied to a sulfonation reactor under the conditions shown in Table 1 to carry out a sulfonation reaction. The reactor has an inner diameter of 12 mm and a length of 100 mm.
Maximum nozzle diameter o. The smms were placed facing each other as shown in FIG. 1. The discharge pressure was adjusted at $21.

The polymer reaction solution mixed and sulfonated in the reactor was immediately stored in a storage tank, and the sulfonation reaction was completed at a temperature of 20°C. Next, the sulfonation reaction solution was dissolved in water, and 30% Na
It was neutralized by adding an OH aqueous solution.

Furthermore, 1,2-dichloroethane was separated by distillation to obtain an aqueous solution of sodium polystyrene sulfonate. The results are summarized in Table-1. In the table, the yield of water-soluble sodium polystyrene sulfonate was calculated from the water-soluble and water-insoluble parts. The sulfonation rate is the rate of introduction of sulfonic acid groups per styrene monomer unit constituting polystyrene.

As a comparative example, the polymer solution and the sulfonating agent were separately supplied to the reactor in the same manner as in Examples 1 to 4, and only the discharge pressure was changed. The results are shown in Table-2.

[Effects of the Invention] According to the present invention, by employing simple means, not only aromatic polymers such as low molecular weight polystyrene but also high molecular weight aromatic polymers can be sulfonated. Polymers can be produced in high yield.

Furthermore, the method of the present invention allows easy cleaning of the reactor and is extremely excellent as an industrial production process.

Because of the above effects, the sulfonated aromatic polymer obtained in the present invention is useful for applications such as antistatic agents for paper or resins, dispersants for inorganic and spinal pigments, and water reducers for concrete.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of the reactor, and FIG. 2 is a flow sheet. l: injection nozzle, 2: liquid inlet, 3: mixing chamber, 4:
Mixing chamber outlet, 5: reactor, 8: storage tank, 7: valve, 8:
Polymer solution tank, 9 = sulfonating agent tank,
10,ll: Infusion pump table-1 table-2

Claims (1)

[Claims] 1. When continuously feeding the aromatic polymer to the sulfonation reactor for sulfonation, the aromatic polymer solution and the sulfonation agent are separately discharged from the nozzle at a pressure of 100 kg/c.
A method for sulfonating an aromatic polymer, the method comprising supplying the aromatic polymer to a reactor under conditions of m^2.G or higher.