JPH05163352A - Production of polyether sulfone - Google Patents

Abstract

PURPOSE:To obtain the title compound excellent in molding stability, processability, etc., by reacting a dihalogenodiphenyl sulfone with a dihydric phenol compound in the presence of a specified phenol compound under specified conditions. CONSTITUTION:The title compound is produced by the reaction of a dihalogenodiphenyl sulfone (e.g. 4,4'-dichlorodiphenyl sulfone) with a dihydric bisphenol compound (e.g. 4,4'-dichlorodiphenyl sulfone) in the presence of an anhydrous alkali (hydrogen) carbonate (e.g. K2CO3) in an organic polar solvent (e.g. diphenyl sulfone), which reaction is conducted in the presence of a monophenol compound of the formula, wherein R is H, lower alkyl, alkoxyl, arylalkyl, cycloalkyl or an aromatic group; and n is 1-3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyether sulfone which is excellent in molding stability and processability in addition to heat resistance and mechanical strength.

[0002]

2. Description of the Related Art Polyether sulfone is used as a dihalogenodiphenyl sulfone by synthesizing an alkali metal disalt of a dihydric phenol compound in a reaction system or preliminarily synthesizing an alkali metal disalt of a divalent phenol compound. It is produced by reacting in an organic polar solvent, and at that time, a technique of blowing chloromethane into the reaction solution to terminate the terminal is known. For example, JP-A-53-12991 and JP-A-53-16098 disclose a technique of producing an aromatic polyether sulfone or ketone from a dihydric phenol compound and dihalogenodiphenyl sulfone and blowing chloromethane after the reaction is completed. Has been done.

[0003]

The polyether sulfone synthesized by the conventional technique has a high melt viscosity and is difficult to process as compared with other engineering plastics which can be extrusion-molded or injection-molded. .. That is, by increasing the heating time or processing at a higher processing temperature, the melt viscosity of the resin increases and the viscosity increases. It has been confirmed that the phenolic hydroxyl group remains at the terminal of the polyether sulfone synthesized by the conventional technique, and it is thought that it may react with the chlorine atom terminal by heating and cause an increase in the molecular weight. Has been.

JP-A-53-1991 and JP-A-53-1
As described in 6098, when a dihydric phenol compound is used in excess with respect to dihalogenodiphenyl sulfone and reacted, and chloromethane is blown into the reaction solution after completion of the reaction, the phenolic hydroxyl group reacts with a chlorine atom to terminate the terminal. To be done. However, since chloromethane is a gas at room temperature, it is difficult to control the amount of chloromethane incorporated into the reaction product, and it is difficult to accurately control the molecular weight.

[0005]

In order to solve these problems, the present inventors have used dihalogenodiphenylsulfone in excess with respect to the dihydric phenol compound or its alkali metal di-salt, and further use an excess of chlorine. It has been found that the addition of an equivalent amount or an equivalent amount or more of a monohydric phenol compound to the atomic end is effective in preventing an increase in the molecular weight due to the formation of an ether bond by heating the phenolic hydroxyl group and the chlorine atom end, The present invention has been completed.

That is, the present invention is used as a terminal terminating agent when producing a polyethersulfone by heating and stirring a dihalogenodiphenylsulfone and a dihydric phenol compound in an organic polar solvent in the presence of an anhydrous alkali metal compound. General formula (1)

[0007]

[Chemical 2]

[In the formula, R represents hydrogen, a lower alkyl group, an alkoxy group, an araalkyl group, a cycloalkyl group or an aromatic group, which may be the same or different, and n
Is an integer of 1 to 3. ] A method for producing a polyether sulfone, characterized by using a monohydric phenol compound represented by

Examples of the dihalogenodiphenyl sulfone used in the method of the present invention include 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4-chloro-4'-fluorodiphenyl sulfone, and , 4'-dibromodiphenyl sulfone, 1,4-
Bis (4-chlorobenzenesulfonyl) benzene, bis (4'-chlorogenzensulfonyl) ether, 1,
3-bis (4′-chlorobenzenesulfonyl) benzene, bis (3′-chlorobenzenesulfonyl) ether, 1,2-bis (4′-chlorobenzenesulfonyl)
Examples thereof include benzene, bis (2'-chlorobenzenesulfonyl) ether, and 4,4'-bis (4-chlorophenylsulfonyl) diphenyl.

Examples of the dihydric phenol compound used in the method of the present invention include 4,4'-dihydroxydiphenyl sulfone, 2,2'-bis (4'-hydroxyphenyl) propane and 2,2-bis (4). '-Hydroxy-
3 ', 5'-dimethylphenyl) propane, bis (4'
-Dihydroxyphenyl) propane, bis (4'-hydroxyphenyl) methane, bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2'-dihydroxydiphenyl, 4, 4'-dihydroxydiphenyl ether, 4,
4'-dihydroxydiphenyl sulfide, 4,4'-
Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxybenzophenone, 1,4-bis (4'-hydroxyphenoxy) benzene, 1,3-bis (4'-hydroxyphenoxy) benzene, 1,4-bis (4'-hydroxy Benzoyl) benzene, 1,3-bis (4'-
Hydroxybenzene sulfonyl) benzene etc. are mentioned.

Examples of the monohydric phenol compound represented by the general formula (1) used in the method of the present invention include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol and m-. Ethylphenol,
p-ethylphenol, 2,3-dimethylphenol,
2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, on-propylphenol, o-isopropylphenol, m-n-propylphenol, m-isopropylphenol, p-
n-propylphenol, p-isopropylphenol, o-n-butylphenol, o-sec-butylphenol, o-tert-butylphenol, m-n-
Butylphenol, m-sec-butylphenol, m
-Tert-butylphenol, pn-butylphenol, p-sec-butylphenol, p-tert-
Butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2,3,5
-Trimethylphenol, 2,3,6-trimethylphenol, 2,4,6-trimethylphenol, o-benzylphenol, m-benzylphenol, p-benzylphenol, o-butoxyphenol, m-butoxyphenol, p-butoxy Phenol, 6-tert-
Butyl-p-xylenol, 2-tert-butyl-p
-Xylenol, 2-tert-butyl-p-cresol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, 2,6
-Di-tert-butyl-p-cresol, 4,6-di-tert-butyl-4-hydroxymethylphenol, 2,4-dimethoxyphenol, 2,6-dimethoxyphenol, vanillin, cumylphenol and the like. .

In order to control the molecular weight of the polyethersulfone produced by the method of the present invention, dihalogenodiphenylsulfone is added to the dihydric phenol compound in an amount of 0.9 to 1.0.
Use equivalent amount. If dihalogenodiphenyl sulfone is used in an amount less than 0.9 equivalent to the dihydric phenol, it is not possible to obtain a high molecular weight polymerized pair having excellent properties as a polymer. In theory, the monohydric phenol compound may be used in an amount of 1.0 equivalent for reacting with an excess of chlorine atoms, but it is actually preferable to use a slight excess of about 1.5 equivalents.

This reaction mechanism for synthesizing polyether sulfone is that a phenolic hydroxyl group and an alkali metal carbonate react with each other to first produce an alkali metal di-salt of a divalent phenol compound, which reacts with dihalogenodiphenyl sulfone. Are known. Therefore, it is desirable to charge the monohydric phenol compound at the same time when the raw material monomers are charged, but if the alkali metal carbonate is used as the functional group equivalent, the alkali metal carbonate is always present in the reaction solution. There is no particular need to limit the time of entry.

Therefore, the monohydric phenol compound is charged at the same time as the raw material monomer and further reacted, the monohydric phenol compound is charged in a divided manner during the reaction, and after the raw material monomer is reacted for a fixed time, Any method of charging a monohydric phenol compound and further reacting may be used.

The polymerization temperature is preferably in the range of 250 to 300 ° C. At a temperature higher than this, the decomposition reaction of the product polymer proceeds, and at a temperature lower than this, a polymer pair having a sufficiently high molecular weight cannot be obtained. If the polymerization temperature is maintained, the polymerization time is about 2 to 4 hours, and a high molecular weight polymer can be obtained.

The organic polar solvent used as the reaction solvent is an aprotic polar solvent such as diphenyl sulfone,
Examples thereof include dimethyl sulfoxide, sulfolane, dimethyl sulfone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, diethyl sulfone, diethyl sulfoxide, and 1,4-dimethylbenzazolidinone.

[0017]

The present invention will be described in more detail below. Example 1 152.9 g of diphenyl sulfone as a solvent, 7.60 g of anhydrous potassium carbonate as a catalyst, and 14.36 g of 4,4′-dichlorodiphenyl sulfone as a raw material monomer.
(0.05 mol), 4,4'-dihydroxydiphenyl sulfone 12.01 g (0.048 mol), p-tert-butylphenol as a monovalent phenol compound 0.
61 g (0.004 mol) was charged into a 300 ml flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube, and heated under a nitrogen atmosphere on an oil bath. After diphenyl sulfone is dissolved, the reaction temperature is 300 ° C while stirring the reaction solution.
And the polymerization was started.

One hour after the start of the reaction, the viscosity of the reaction solution increased remarkably. The reaction was completed after a reaction time of 2 hours, the reaction solution was discharged into an acetone / methanol 1: 1 mixed solvent, and the precipitated solid was crushed, washed with water and dried at 130 ° C. to obtain polyether sulfone. The reduced viscosity of the obtained polyether sulfone and its intrinsic viscosity were measured. The results are shown in Table 1.
Shown in.

Example 2 Example 1 was repeated except that 0.91 g (0.004 mol) of cumylphenol was used instead of p-tert-butylphenol. One hour after the start of the reaction, the viscosity of the reaction solution remarkably increased. The reaction was completed after a reaction time of 2 hours. Table 1 shows the physical properties of the obtained polyether sulfone.

Example 3 152.9 g of diphenyl sulfone as a solvent, 7.60 g of anhydrous potassium carbonate as a catalyst, and 14.36 g of 4,4'-dichlorodiphenyl sulfone as a raw material monomer.
(0.05 mol), 4,4'-dihydroxydiphenyl sulfone 12.01 g (0.048 mol), a stirrer,
A 300 ml flask equipped with a nitrogen introduction tube, a thermometer, and a cooling tube was charged, and the mixture was heated on an oil bath under a nitrogen atmosphere. After the diphenyl sulfone was dissolved, the reaction temperature was raised to 300 ° C. while stirring the reaction solution to start the polymerization.

One hour after the start of the reaction, the viscosity of the reaction solution increased remarkably. Here, 0.61 g (0.004 mol) of p-tert-butylphenol was added, and the mixture was further reacted for 1 hour. The intrinsic viscosity of the obtained polyether sulfone and its melt viscosity were measured. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that p-tert-butylphenol was not added. One hour after the start of the reaction, the viscosity of the reaction solution remarkably increased. The reaction was completed after a reaction time of 2 hours. The properties of the obtained polyether sulfone are shown in Table 1.

Comparative Example 2 13.01 g of dihydroxydiphenyl sulfone (0.0
Example 1 was repeated except that 52 mol) was used and no p-tert-butylphenol was added. 2 hours after the start of the reaction, 0.024 liters of chloromethane (0.0
(1 mol). The properties of the obtained polyether sulfone are shown in Table 1. For the melt viscosity in Table 1, the polyether sulfone powders obtained in Examples and Comparative Examples were measured with a Koka type flow tester (manufactured by Shimadzu Corporation) while changing the residence time in the flow tester. Measurement temperature is 3
The temperature is 50 ° C. and the measurement pressure is 100 kg / cm ² .

[0024]

[Table 1]

[0025]

INDUSTRIAL APPLICABILITY In the present invention, the reactive end of polyether sulfone is terminated with a monohydric phenol compound, the molecular weight can be easily adjusted, and the increase in melt viscosity due to heating can be prevented. According to the present invention, the molding stability of the polyether sulfone can be improved and the processing can be easily performed, and the present invention has great significance.

Claims (1)

[Claims] 1. When producing a polyether sulfone by reacting a dihalogenodiphenyl sulfone and a dihydric phenol compound in an organic polar solvent in the presence of an anhydrous alkali metal carbonate and / or an anhydrous alkali metal hydrogen carbonate, General formula (1) [In the formula, R represents hydrogen, a lower alkyl group, an alkoxy group, an arylalkyl group, a cycloalkyl group, or an aromatic group, which may be the same or different, and n is 1 to 1;
It is an integer of 3. ] The manufacturing method of the polyether sulfone characterized by adding and reacting the monohydric phenol compound represented by these.