JPS63316A - Production of aromatic poly(thio)ether-ketone - Google Patents

Abstract

PURPOSE:To produce the title polymer of excellent heat stability, by reducing an aromatic poly(thio)ether-ketone in the presence of a specified compound. CONSTITUTION:An aromatic (thio)ether (A) of formula I (wherein R<1-12> are each H, halogen, hydrocarbon or alkoxy, X is a direct bond, O or S and lis 0-2) is reacted with an aromatic dicarboxylic acid dihalide of formula II (wherein R<13-20> are each R<1>, Y is a halogen and m is 0-3) or phosgene at -10-100 deg.C in an aprotic organic solvent (e.g., CCl4) in the presence of 0.1-10.0mol, per mol of component A, of a Lewis acid (e.g., AlCl3) to obtain an aromatic poly(thio)ether-ketone. The product is reduced at room temperature in the presence of a compound of formula IV [wherein A<1-3> are each (cyclo) alkyl or aryl which may be substituted provided that all of a<1-3> are not H atoms at the same time] and there is a large excess of a carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for post-polymerization treatment of crystalline thermoplastic aromatic poly(thio)etherketones.

[Conventional technology]

General formula [1N] ...... (11 ([■] In the formula, R1, ..., RH represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and X represents a direct bond, an acid purple or represents a sulfur atom, t represents an integer from θ to co, m represents an integer from θ to 3, and n is 0 or l), especially an aromatic poly(thio)etherketone having the structure [ Aromatic poly←尭≠4etherketones with structures of V]HHHH and (VIE have high melting points ([V], Tm −, ? 6 s c ; [VIE
, Tm-JJ Hiro℃) and high glass transition temperature ([■], T
g-i s lIc ; (Vl), Tg −/Gda 0)
has.

It is known to have excellent heat resistance, mechanical properties, electrical properties, and dimensional stability, as well as low water absorption, making it an extremely physically excellent polymer. or.

It is a polymer that is insoluble in solvents other than concentrated sulfuric acid and has excellent chemical resistance.

On the other hand, the manufacturing method of these polymers is
<z, lI'-difluoropenzophenone 1III
A method of reacting an alkali metal salt of ′-dihydroxybenzophenone or hashihydroquinone in diphenyl sulfone is known, but the reaction temperature must be raised to 300°C or higher, and ψ, ri′-difluorobenzophenone is expensive. However, there are many drawbacks to the manufacturing method.

In view of the above points, the present inventors conducted intensive studies and obtained the following formula [
The polyetherketone found in [2] can be synthesized by the reaction of an aromatic ether or thioether with an aromatic carboxylic acid civalide.
We have found a method for producing it under mild conditions around room temperature in the presence of a Lewis acid in an aprotic organic solvent and at a significantly low cost.

However, after the aromatic poly(thio)etherketone produced by this method is washed to deactivate the catalyst and further remove it, the dried polymer is heated to melt, resulting in gelation. It had the drawback of being unstable.

[Purpose of the invention]

The present inventors aimed to improve the above points, and as a result of further intensive studies, the following general formula [
The present invention was based on the discovery that mature woman quality was significantly improved by treatment in the presence of a silane compound represented by [1v].

(In the formula, Person 1, A2, and AS are an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, or a hydrogen atom that may have a substituent.

However, this excludes the case where A1, A2, and A3 are all hydrogen atoms. ) That is, the gist of the present invention is the general formula ([]...[
I] ([■] In the formula, R1-82° represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, oxygen, or a sulfur atom, and t is an integer of O-1. The purpose of the present invention is to improve the thermal stability of a polymer by embedding K to produce an aromatic poly(thio)etherketone (where m is an integer from O to 3, and n is O or l).

[Structure of the invention]

In the detailed description of the present invention, the polymerization of such an aromatic poly(thio)etherketone is carried out by the general formula ([I] in which R
'-RI2 represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, and t is an integer of O-1 ) ether and general formula (II
) ([In formula 13, R13 to R20 represent a hydrogen atom, a hydrogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom, or a sulfur atom, Y represents a halogen atom, m is an integer of 0 to 3) with the aromatic dicarboxylic acid civalide or phosgene represented by the formula CIV in the post-treatment step after polymerization reaction in an aprotic organic solvent in the presence of a Lewis acid.
) (In the formula, A1, A2, and AF groups are alkyl groups, aryl groups, cycloalkyl groups, and aralkyl groups that may have substituents, or hydrogen atoms, provided that all of A', A'', and A3 are This is achieved by reduction treatment with a silane compound represented by (excluding cases where it is a hydrogen atom).

The above-mentioned post-treatment with the general formula [IV] is carried out in the presence of an acid as a solvent, particularly a carboxylic acid, and the carboxylic acid is used in large excess relative to the polymer, or in a mixture of the carboxylic acid and another solvent. It will be held in

Specific examples of the silane compounds used include triethylsilane, tri-n-propylsilane, tri-n-octylsilane, diethylsilane, triphenylsilane, diphenylsilane, phenylsilane, diethylphenylsilane, diphenylethylsilane, and tri-p-methoxy. Examples include, but are not limited to, phenylsilane, and general formula C
Any silane compound represented by IVI can be used. Furthermore, triethylsilane is most preferred as the silane compound. The amount of the silane compound to be used is 1 molar or more based on the number of moles of ether bonds in the polymer, preferably io
More than molti can be used. As the common acid, carboxylic acids are preferable, and specific examples include Iri acetic acid, trifluoroacetic acid, dichloroacetic acid, monochloroacetic acid, 10-pionic acid, and butyric acid. Among them, dichloroacetic acid, dichloroacetic acid, Particularly preferred is trifluoroacetic acid. Two or more types of carboxylic acids may be used as a mixture, or they may be used in combination with other solvents.

The reaction was carried out at room temperature (YuO-co 5r2). Although the reaction temperature is not particularly limited, the reaction may be carried out under heating or under pressure.

Although the reaction time varies depending on the reaction conditions, it is generally carried out for 5 minutes or more.

Further, the aromatic group (thio)ether represented by the general formula [I] used in the present invention includes diphenyl ether, /, 9-diphenoxybenzene, biphenyl, bis(terphenoxyphenyl) ether, ≠, ll' -bis(tI-phenoxyphenyl)diphenyl ether,
3. ．． 3'-simefk phenyl ether, /, coubis(3-methylphenoxy)benzene, 3.3'-dimethoxyphenyl ether, /, LA-bis(3-methoxyphenoxy)benzene, /, 4'-bis(2- chlorophenoxy)benzene, diphenyl sulfide,
q-phenoxydiphenyl sulfide, /, 4(-
His-(phenylmercapto)benzene, terphenyl, lI-phenoxybiphenyl%II, 4('-diphenoxybiphenyl, etc.)
Any of those represented by can be used, and the invention is not necessarily limited to these. Further, these aromatic (thio)ethers may be used alone or in combination.

Further, the aromatic dicarboxylic acid cybaride represented by the general formula [11] used in the present invention includes terephthalic acid dichloride, isophthalic acid cyclolite, cyphenyletheruda, ≠'-dicarboxylic acid dichloride, /
, 4'-bis<41-chloroformylphenyl)benzene 1,2. ! Examples include -dimethylterephthalic acid dichloride, diphenylsulfide-p,II'-dicarboxylic acid dichloride, lI,ll'-diphenic acid dichloride, and 6-naphthalenedicarboxylic acid dichloride, but those represented by the general formula [1] Any of these can be used, and the invention is not necessarily limited to these.

Further, these aromatic dicarboxylic acid cybarides may be used alone or in combination. Further, these aromatic dicarboxylic acid cybarides may be used in combination with phosgene.

Examples of aprotic organic solvents used in the present invention include methylene chloride, ethylene chloride, /, U-dichloroethane, i, i, co-cochtrachloroethane, chloroform, carbon tetrachloride, nitrobenzene, nitromethane, carbon disulfide, ethyl ether, dibutyl ether, pentane,
Hexane.

Heptane, orthodichlorobenzene, etc. are used, but are not necessarily limited to these. The amount of solvent used is /-! of the diphenyl ether used. ;00 times amount (weight ratio) preferably! -100 times the amount (weight ratio).

The Lewis acids used in the present invention include anhydrous aluminum trichloride and anhydrous aluminum tribromide.

Anhydrous trichloride, boron trifluoride ethyl ether complex, stannic chloride, tin chloride, ferric chloride, titanium tetrachloride, boron trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, Tellurium pentachloride, niobium pentachloride, tungsunide hexachloride, and especially aluminum chloride are preferred. The amount of these Lewis acids used is o, oi to 100, preferably Q, in a 1 molar ratio to the aromatic (thio)ether.
/ -70,0. Also, if necessary, LICI
Inorganic bases such as amides, amines, organic bases such as ether compounds, and those that generally form complexes with Lewis acids (excluding monomers) may be added to the reaction system.

The polymerization temperature is not particularly limited, but is -10'C or higher (generally
It is carried out under mild conditions (below Q/o 0°C). The reaction may also be carried out under pressure.

〔Example〕

Hereinafter, the present invention will be explained in more detail using embodiments.

In addition, one evaluation of thermal stability after melting and heating was carried out using a Shimadzu Koka type flow tester CFT-3001.
The extrudability of the extruded strands, the appearance of the extrudates and the concentration of polymer against sulfuric acid
Solubility when dissolved at 17 tu concentration and 7
It was determined based on measurements of =.

Example/Diphenyl ether? ,/y-(0,O171 mol)
, anhydrous aluminum trichloride/7.9 p (0,/
3) 1 mol) and lithium chloride t f (0,OII
2 mol) in 2-dichloroethane qs- under water cooling.

Phosgenda p,ry was introduced. The reaction mixture was stirred at room temperature for several hours. The reaction mixture was separated into a solution part and a capillary part. The solution part was removed by decantation, and the gel part was poured into 100% methyl alcohol to isolate the precipitated polymer.

The isolated polymer was soaked in methyl alcohol at a temperature of 0.1
．． It was 3 dl/f.

Next, the above polymer S1 was dissolved in /10- dichloroacetic acid, triethyl 7- was added, and after reacting for 1 hour at room temperature under nitrogen, the polymer solution was precipitated in water and washed with water using JOO.
The mixture was heated twice with 300 ml of acetone under reflux, and dried overnight under reduced pressure at /20C. The polymer was melt-heated for 5 minutes using a Koka type flow tester (Shimadzu Corporation CFT-s00'), and the extruded strand was easily extruded, and the extruded sample was Dissolved in 9t% sulfuric acid at 9 degrees /f/dt? Met.

Comparative Example 1 A sample that was polymerized in the same manner as in Example 1, but not subjected to post-processing, was melt-heated for 5 minutes at ttooc using a Koka type flow tester in the same manner as in Example 1ψ, and the extrudability was poor. As described above, according to the present invention, the thermal stability of the product is improved by adding qts sulfuric acid to the extruded sample at a concentration of /ji'/tit. There is no.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - 1 other person

Claims (5)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] ([I] In the formula, R^1 to R^1^2 represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, and l is 0 is an integer between ~2) and the general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the [II] formula, R ^1^3 to R^2^0 represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, and
represents a direct bond, an oxygen atom or a sulfur atom, Y represents a halogen atom, and m is an integer of 0 to 3) or phosgene, in the presence of a Lewis acid, By reacting in an aprotic organic solvent, the general formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・[III] (In the [III] formula, R^1 ~ R^2^ 0 represents a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond, an oxygen atom or a sulfur atom, represents an integer of 0 to 2, and m represents an integer of 0 to 3. , n is 0 or 1) In the method for producing an aromatic poly(thio)etherketone having repeating units of
thio)etherketone with the general formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[IV] (In the formula, A^1, A^2, A^3 groups are an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, or a hydrogen atom that may have a substituent. However, A^ 1. A method for producing an aromatic poly(thio)etherketone, which is characterized in that it is post-treated in the presence of a compound represented by 1, except when A^2 and A^3 are all hydrogen atoms. (2) The production method according to claim 1, wherein the post-treatment is carried out in the presence of general formula [IV] and a carboxylic acid. (3) The manufacturing method according to claim 1, characterized in that the compound represented by the general formula [IV] is used in an amount of 1 mol % or more based on the number of moles of ether bonds in the polymer. (4) The manufacturing method according to claim 1, in which a solid Group III halide of the periodic table is used as the Lewis acid. (5) Claim 1 in which anhydrous aluminum halide or anhydrous gallium halide is used as the Lewis acid.
Manufacturing method described in section.