JPS59159825A - Production of aromatic polyketone - Google Patents

Abstract

PURPOSE:To facilitate the production of a high-polymerization degree aromatic polyketone excellent in heat resistance, strength, etc., by reacting an aromatic ether with an aromatic dicarboxylic acid dihalide in the presence of a Lewis acid in an aprotic organic solvent. CONSTITUTION:An aromatic ether of the formula (wherein n is 1-5), e.g., 1,4- diphenoxybenzene or 1,3-diphenoxybenzene, is reacted with an aromatic dicarboxylic acid dihalide, e.g., isophthaloyl or terephthaloyl dichloride, in the presence of a Lewis acid, e.g., aluminum chloride or tin tetrachloride, under stirring in an aprotic organic solvent, e.g., ethylene chloride or 1,1,2,2-tetrachloroethane. In this way, it becomes possible to eliminate the necessity of conducting the reaction at extremely low temperatures as is different from the case of conventional processes, and to obtain a high polymerization degree aromatic polyketone even when the reaction is conducted at a temperature of from about -10 deg.C to usually 50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic polyketones. 1,4
- It is known that the reaction between diphenoxybenzene and terephthalic acid chloride or/and isphthalic acid chloride is carried out in a hydrogen fluoride solvent in the presence of boron trifluoride, but this method requires very low temperatures (e.g. −
The reaction must be started at a temperature of 78° C.) and must be carried out using a special reactor, and recovery of the solvent requires very complicated operations.

In view of the above points, the present inventors conducted intensive studies and found that when the reaction is carried out in the presence of a Lewis acid using an aprotic organic solvent such as a halogenated hydrocarbon as a solvent, -10 to 35 It was discovered that a polymer with a high degree of polymerization can be obtained even at a high temperature of ℃. Since the present invention uses an aprotic organic solvent as a solvent, the polymer can be recovered very easily. The polymer obtained in the present invention can also be used as films, molded products, and fibers.
Its heat resistance is also high.

The gist of the present invention is to produce a polyketone by reacting an aromatic ether represented by the general formula [■] (in the formula [■], n is an integer of 1 to 5) and an aromatic dicarboxylic acid dihalide. , consists in a method for producing an aromatic polyketone in which the reaction is carried out in the presence of a Lewis acid using an aprotic organic solvent as a solvent.

To explain the present invention in more detail, the aromatic ethers represented by the general formula [1] used in the present invention include 1,4-diphenoxybenzene, bis(4-phenoxyphenyl) ether, 1, 3-diphenoxybenzene, bis(3-phenoxyphenyl)ether, 4,4'
-bis(4-phenoxyphenyl)diphenyl ether, (4-phenoxyphenyl)-4'-phenoxydiphenyl ether, etc., but are not limited to these. These may be used alone or as a mixture, and those with a 1,4- or 1,3-structure are preferred. Among these, it is most preferable to use 1,4-diphenoxybenzene.

Aromatic dicarboxylic acid dihalides used in the present invention include terephthalic acid dichloride, isophthalic acid dichloride, methoxyterephthalic acid dichloride, ethoxyterephthalic acid dichloride, isopropoxyterephthalic acid dichloride, fluoroterephthalic acid dichloride, chloroterephthalic acid dichloride, methylterephthalic acid dichloride , methyl inphthalic acid dichloride, methoxyisophthalic acid dichloride, diphenylmethane-4,4'-dicarboxylic acid dichloride, diphenylmethane-3,3'-dicarboxylic acid dichloride, diphenyl ether-4,4'-dicarboxylic acid dichloride, diphenyl-4,4 -dicarboxylic acid dichloride, isophthalic acid dipromide, terephthalic acid difluoride, terephthalic acid diiodide, naphthalene-2,6-dicarboxylic acid dichloride, naphthalene-1,
Examples include, but are not limited to, 5-dicarboxylic acid dichloride, naphthalene-2,6-dicarboxylic acid dibromide, and the like. Among these acid chlorides, terephthalic acid dichloride and isophthalic acid dichloride are preferred from the viewpoint of cost.

Examples of aprotic organic solvents used in the present invention include methylene chloride, ethylene chloride, 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, nitrobenzene, nitromethane, carbon disulfide, toluene, xylene,
Benzene, tetralin, decalin, hexane, ethyl ether, dibutyl ether, heptane, pentane, orthodichlorobenzene and the like are used, but are not necessarily limited thereto. Among these aprotic organic solvents, halogenated hydrocarbons are particularly preferred since polymers with a high degree of polymerization can be easily obtained. The amount of solvent used is preferably 1 to 500 times the amount (weight ratio) of the raw material acid dihalide.
~100 times the amount (weight ratio).

Lewis acids used in the present invention include aluminum trichloride, aluminum tribromide, boron trifluoride, ferric chloride, tin chloride, stannous chloride, titanium tetrachloride, boron trichloride, antimony pentachloride, Examples include, but are not limited to, zinc chloride, gallium trichloride, antimony hexachloride, phosphorus trichloride, phosphorus pentachloride, tellurium pentachloride, niobium pentachloride, and tungsten hexachloride.

Among these, aluminum chloride and tin tetrachloride are most preferred. The amount of these Lewis acids used is 0.5 to 5.0, preferably 0.9 to 2.0 in weight ratio to the acid dihalide.
It is.

Furthermore, the present invention can be carried out by adding a Lewis acid to a solution containing an ether represented by the general formula [■] and an aromatic dicarboxylic acid dihalide, or by adding an aromatic dicarboxylic acid dihalide having the general formula [■] in the presence of a solvent and a Lewis acid. Ethers represented by [■] may be added. In the method of the present invention, the reaction temperature is not particularly limited, but is -10°C or higher (usually 50°C or lower).
A high degree of polymerization can be obtained even at this temperature.

The aromatic polyketones obtained according to the invention have many advantages. In other words, mechanical properties such as tensile strength, bending strength, tensile modulus, and bending modulus, heat resistance, thermal decomposition onset temperature,
Excellent electrical properties and dimensional stability, low moisture absorption and water absorption rate.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 1,4-diphenoxybenzene 1 in a 300 ml reactor
0.3 g and 7.97 g of isophthalic acid dichloride are added, and 200 ml of dichloroethane previously dried with molecular sieve 4A is added.

Cool on ice to 5℃. Next, 13.5 g of aluminum chloride was added, and the mixture was cooled on ice for 2 hours while stirring, and then reacted for 16 hours at room temperature. After the reaction, dichloroethane is removed by filtration, and the polymer is washed twice with 200 ml of 0.1N hydrochloric acid aqueous solution and twice with 200 ml of demineralized water, and vacuum-dried at 150° C. overnight. The yield was 95%, and the ηinh (measured using 97% concentrated sulfuric acid at a concentration of 1.0 g/dl at 30°C) was 1.11 dl/g. This polymer had a glass transition temperature of 142°C and a melting point of 254°C.

When press molding was performed at 375°C, a tough film was obtained. The elastic modulus of this film (measured with a dynamic viscoelasticity measuring device manufactured by Toyo Baldwin) is 34,400 kg.
/cm3.

Example 2 The same reaction as in Example 1 was carried out except that terephthalic acid chloride was used instead of isophthalic acid dichloride, and the same post-treatment was performed. A polymer was obtained with a yield of 96%, and the same reaction as in Example 1 was carried out. ηinh = 1.02dl measured by the method of
/g.

Example 3 The same reaction as in Example 1 was carried out except that 1,3-diphenoxybenzene was used instead of 1,4-diphenoxybenzene, and the same post-treatment was performed, resulting in polymerization with a yield of 95%. A product was obtained, and ηin was measured in the same manner as in Example 1.
h=1.0 dl/g.

Example 4 The same reaction as in Example 1 was carried out except that 12.79 parts of bis(4-phenoxyphenyl) ether was used instead of 14-diphenoxybenzene, and the same post-treatment was performed, resulting in a yield of 94%. A polymer was obtained, and the ηinh measured in the same manner as in Example 1 was 1.12 dl/g.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hajime Hasegawa 1 other person

Claims (4)

[Claims] (1) When producing a polyketone by reacting an aromatic ether represented by the general formula [■] (in which n is an integer of 1 to 5) with an aromatic dicarboxylic acid dihalide, a Lewis acid A method for producing an aromatic polyketone, characterized by carrying out the reaction using an aprotic organic solvent as a solvent in the presence of (2) The manufacturing method according to claim 1, in which isophthalic acid dichloride and/or terephthalic acid dichloride is used as the aromatic dicarboxylic acid dihalide. (3) The manufacturing method according to claim 1, using a halogenated hydrocarbon as the aprotic organic solvent. (4) The manufacturing method according to claim 1, using diphenoxybenzene as the aromatic ether.