JPH05140311A - Aromatic polyetherketone sulfone and its production - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to provide a novel aromatic polyether ketone sulfone having excellent heat resistance, a high glass transition temperature, and excellent chemical resistance. [Structure] General formula [I] The repeating unit represented by or at least one of the phenylene groups in the repeating unit is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 1 carbon atoms.
Essentially consisting of repeating units nuclear-substituted with an aryl group of 2 and using a p-chlorophenol solvent at 0.2 g /
The reduced viscosity measured at 60 ° C. at a concentration of dl is 0.1 dl /
An aromatic polyether ketone sulfone having a weight of at least g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polyether ketone sulfone excellent in heat resistance, which is preferably used as a material in the aerospace industry, precision machinery field, electric / electronic / OA field, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the use of engineering plastics has expanded with the progress of technology, and polymers having excellent heat resistance have been demanded. As a method of improving the heat resistance of a polymer, there is a method of introducing a sulfone group or a carbonyl group into the polymer chain. For example, JP-A-2-4829 discloses a polyaryl comprising a repeating unit represented by the following formula [II]. Ether has been proposed. However, even this polyaryl ether could not be said to have sufficient heat resistance.

[Chemical 2]

[0003]

An object of the present invention is to provide a polymer having excellent heat resistance, a high glass transition temperature and chemical resistance. The present invention also aims to provide a production method suitable for producing this polymer.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a polymer composed of a specific repeating unit having an ether group, a carbonyl group and a sulfone group in a specific order. They have found that they have excellent heat resistance and chemical resistance, and have completed the present invention based on this finding.

That is, the present invention has the general formula [I]

[Chemical 3] The repeating unit represented by or at least one of the phenylene groups in the repeating unit is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 1 carbon atoms.
Essentially consisting of repeating units nuclear-substituted with the aryl group of 2 and using a p-chlorophenol solvent at 0.2 g /
The reduced viscosity measured at 60 ° C. at a concentration of dl is 0.1 dl /
It provides an aromatic polyether ketone sulfone characterized by being g or more. When the reduced viscosity of the aromatic polyether ketone sulfone of the present invention is less than 0.1 dl / g, it cannot be said that the heat resistance and the mechanical strength are practically sufficient. The preferred range of reduced viscosity is 0.2 to 20.
dl / g.

The aromatic polyether ketone sulfone of the present invention is, for example, 4,4'-sulfonyldibenzoyl chloride or at least one of the phenylene groups therein is an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. At least one of diphenyl ethers or a phenylene group therein, or a substituent having a nucleus substituted with a group (hereinafter, may be referred to as 4,4′-sulfonylbenzoyl chlorides) or an alkoxy group having 1 to 6 carbon atoms, or It can be obtained by electrophilic reaction polycondensation with a nucleus-substituted product (hereinafter, also referred to as diphenyl ethers) that is nuclear-substituted with an aryl group having 6 to 12 carbon atoms.

The electrophilic polycondensation is carried out by reacting 4,4'-sulfonyldibenzoyl chlorides and diphenyl ethers in a solvent, preferably in the presence of Friedel-Crafts catalyst. The ratio of 4,4'-sulfonyldibenzoyl chlorides to diphenyl ethers is usually 0 in order to form a polymer having a sufficiently high molecular weight. .9
It is 7 to 1.02, preferably 1.00 to 1.01.

As the Friedel-Crafts catalyst, Lewis acids such as aluminum trichloride, aluminum tribromide, boron trichloride, iron trichloride, zinc dichloride, tin tetrachloride, titanium tetrachloride, boron trifluoride, etc. are used. Be done. Particularly, aluminum trichloride is preferably used. Since 4,4'-sulfonyldibenzoyl chlorides have a basic sulfone group, the amount of Lewis acid used is usually 4 to 10 moles per 1 mole of 4,4'-sulfonyldibenzoyl chlorides. It is preferably 4.2 to 6 mol.

In the polycondensation reaction of the present invention, a Lewis base is added to the reaction system in addition to the above Lewis acid to obtain a Lewis acid-
It is preferable to form a Lewis base complex and carry out the reaction using this as a catalyst. Examples of the Lewis base include N, N
-Dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethyl sulfone and the like. Particularly, dimethyl sulfone is preferable. The amount of the Lewis acid-Lewis base complex used is usually 2 to 1 mol of 4,4′-sulfonyldibenzoyl chlorides.
It is 10 times equivalent, preferably 3 to 6 times equivalent. When the amount of the complex used is large, the polymerization rate becomes slow, and when the amount is small, the system may be precipitated and the polymer may not be obtained. Lewis acid
A preferred combination of Lewis bases is the aluminum trichloride-dimethyl sulfone combination.

The reaction temperature of the polycondensation reaction is usually -20 to 10
0 ° C, preferably 0 to 70 ° C, more preferably 10 to 5
The reaction time is usually 0.5 to 50 hours, preferably 1 to 20 hours, more preferably 2 to 10 hours. The reaction is preferably performed in an atmosphere of an inert gas such as argon.

The reaction is carried out in the presence of a solvent, and as the solvent, halogenated hydrocarbons such as dichloromethane, 1,2-dichloromethane, carbon tetrachloride and 1,1,2,2-tetrachloroethane are preferably used. A particularly preferred solvent is 1,2-dichloroethane. It is preferable to use these solvents after drying.

The order of charging the reaction raw materials is not particularly limited, but the initial reaction is preferably carried out under ice cooling in order to suppress side reactions in the initial stage of polymerization. After the completion of the polymerization reaction, the reaction solution is put in ice-cooled hydrochloric acid, washed with methanol, hot water and the like and dried to obtain the target polymer.

[0013]

EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto. Example 1 A 300 ml separable flask equipped with a stirrer, an argon gas introduction tube, and a calcium chloride tube was charged with 33.714 g (0.253 mol) of aluminum trichloride and 100 ml of 1,2-dichloroethane, and the mixture was cooled to 5 ° C in an ice bath. Cooled to. Next, 7.531 g (80.0 mmol) of dimethyl sulfone was gradually added, and further diphenyl ether 3.
404 g (20.0 mmol) was added. Finally 4,
4'-sulfonyldibenzoyl chloride 6.864 g
(20.0 mmol) was added.

When the temperature was raised to 20 ° C. and the reaction was carried out at this temperature for 6 hours, a viscous reaction solution was obtained. The reaction solution was poured into hydrochloric acid containing ice, and the obtained polymer was washed 5 times with hot water and once with methanol. After drying at 130 ° C. overnight, 8.29 g of white polymer (yield 93.7%) was obtained. The glass transition temperature (Tg) of the obtained polymer is 21.
0.9 ° C, thermal decomposition start temperature (5% weight loss in air) is 4
It was 84.7 ° C. 0.2 g of p-chlorophenol
The reduced viscosity of the polymer solution having a concentration of / dl measured at 60 ° C. was 0.39 dl / g. IR of the obtained polymer
The chart is shown in FIG.

As a result of elemental analysis, theoretical values and calculated values were in agreement, and as a result of IR analysis, it was confirmed that the polymer was composed of repeating units represented by the following formula.

[0016]

[Chemical 4]

[0017]

Industrial Applicability According to the present invention, it is possible to obtain a polymer having a high glass transition point, which is composed of repeating units having a sulfonyl group, a carbonyl group and an ether group in a specific order and which has excellent heat resistance.

[Brief description of drawings]

FIG. 1 is a chart of infrared absorption spectrum of the polymer obtained in Example 1.

Claims (2)

[Claims] 1. A compound represented by the general formula [I]: The repeating unit represented by or at least one of the phenylene groups in the repeating unit is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 1 carbon atoms.
Essentially consisting of repeating units nuclear-substituted with the aryl group of 2 and using a p-chlorophenol solvent at 0.2 g /
The reduced viscosity measured at 60 ° C. at a concentration of dl is 0.1 dl /
An aromatic polyetherketone sulfone, characterized in that it is at least g. 2. At least one of 4,4′-sulfonyldibenzoyl chloride or a phenylene group therein is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. And at least one of the phenylene group therein and the diphenyl ether or the phenylene group therein is nuclear-substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. The method for producing an aromatic polyetherketone sulfone according to claim 1, wherein the polynuclear compound is subjected to electrophilic polycondensation.