JPH0598007A - Production of highly heat-resistant aromatic copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer of a low content of ionic impurities by polymerizing an alkali thiolate-terminated prepolymer with a dihaloaromatic compound. CONSTITUTION:The purpose copolymer is obtained by polymerizing a prepolymer containing an alkali thiolate group at at least one end and obtained by depolymerizing a polyarylene thioether comprising repeating units of formula I by treatment with an alkali metal sulfide in a polar organic solvent with a dihaloaromatic compound of formula II and optionally an alkali metal sulfide in a polar organic solvent. In the formulas, R is 1-6 C alkyl; k is 0 or 1-4; m is 0 or 1-100; and X is halogen.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic copolymer having a bis (benzoyl) benzophenone structural unit. More specifically, polyarylene thioether (hereinafter abbreviated as PATE) is depolymerized to produce a prepolymer having an alkali thiolate group at the terminal,
Then, the present invention relates to a method for producing a highly heat-resistant aromatic copolymer containing a small amount of ionic impurities by reacting this prepolymer with a specific dihalogen-substituted aromatic compound to polymerize.

According to the present invention, an arylene thioetherketone-based copolymer copolymerized with good uniformity of composition can be obtained by using two or more kinds of dihalogenated aromatic compounds having different stability and reactivity in the polymerization reaction system as starting materials. it can.

[0003]

2. Description of the Related Art In recent years, in the fields of electronics and electricity, SMT (surface mounting) can be supported in order to reduce the size and weight of parts, and moreover, ionic impurities such as chlorine ions that cause corrosion of metal elements. There is a need for a high heat-resistant polymer with a low content.

Polyphenylene sulfide (hereinafter abbreviated as PPS), which is a typical polymer belonging to PATE, has a crystal melting point of about 285 ° C., and it is difficult to say that it has sufficient heat resistance for SMT, and the current industrial production method. In
There is a problem in that a large amount of ionic impurities are contained because sodium chloride in the same amount or more as PPS is produced as a by-product.
As a method of increasing the crystal melting point of PATE, an arylene thioether unit and an arylene thioether ketone unit represented by Chemical Formula 4 are used.

[0005]

[Chemical 4] A copolymer in which is randomly introduced has been proposed (Japanese Patent Publication No. 59-5100).

However, in the method of reacting dihalobenzene, which is a raw material of the copolymer, and a dihaloaromatic compound activated by a ketone group together with an alkali metal sulfide in a polar organic solvent, reactivity and polymerization Because of different chemical stability in the system, even if an attempt is made to copolymerize, a polymer having satisfactory composition uniformity, heat resistance or melt stability cannot be obtained. That is, the obtained random copolymer has an amount of 90 mol% as the arylene thioether unit decreases.
When it is less than the above range, the crystallinity is lowered and the heat resistance and mechanical properties are deteriorated.

Aromatic thioethers and phosgene or aromatic dicarboxylic acid dihalides are reacted in the presence of a Lewis acid in an aprotic solvent to give structural formulas [IV] and [V].

[0008]

[Chemical 5]

[0009]

[Chemical 6] A method of obtaining a polymer having is proposed. (JP-A-60-104126, JP-A-60-120720
issue). However, the obtained copolymer has a problem that it has a low degree of polymerization, poor melt stability, and immediately gels. The present inventors have proposed a dihalobenzene represented by Chemical formula 7 and a dihaloaromatic compound activated by a ketone group represented by Chemical formula 8 or 9

[0010]

[Chemical 7]

[0011]

[Chemical 8]

[0012]

[Chemical 9] In order to improve the above-mentioned problems in the copolymerization with the above, a method for preparing a prepolymer in advance and reacting these prepolymers with each other to produce a copolymer was previously proposed (JP-A-2-225527, Japanese Patent Application No. 225527/1990). Flat 1-3429
No. 68) has a problem that the by-produced alkali metal halide cannot be sufficiently removed.

On the other hand, as another method for producing an arylene thioether polymer, there has been proposed a method of reacting a dihalogen-substituted aromatic compound with an aromatic dithiol or an alkali metal salt (alkali thiolate) thereof (Japanese Patent Publication No. 45-19713). Issue, Japanese Patent Publication No. 46-4398
No. 6/197634 / 61-200
127, JP-A-62-529, JP-A-62-530.
JP-A-62-91530, JP-A-62-2053
No. 0).

In these production methods, the reactivity is good, but the aromatic dithiols and alkali thiolates of the raw materials are easily oxidized, so that their purification and handling are difficult,
There is a problem that manufacturing cost becomes high and industrial implementation is difficult.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a highly heat-resistant aromatic copolymer containing few ionic impurities. The inventors of the present invention have conducted extensive studies to overcome the above-mentioned problems of the prior art. When an alkali metal sulfide is allowed to act on PATE, the main chain of PATE is cut and depolymerized, and both terminals are depolymerized. It was found that a compound (prepolymer) having an alkali thiolate group can be easily obtained.

It was found that the prepolymer having an alkali thiolate group at its terminal was polymerized again when reacted with various dihalogen-substituted aromatic compounds in a polar organic solvent to obtain a copolymer having a high degree of polymerization. It was
Moreover, this prepolymer was found to have excellent stability in the polymerization reaction system. That is, it is possible to take advantage of only the advantage of the method for producing PATE using the aromatic dithiol or alkali thiolate having good reactivity described above as a raw material.

According to this method, a prepolymer having an alkali thiolate group at at least one terminal is prepared, and the prepolymer and the dihalogen-substituted aromatic compound activated by the ketone group are treated under relatively mild conditions. Thus, a copolymer having a high degree of polymerization and excellent melt stability can be produced by reacting smoothly. Further, according to this method, the repeating unit (VI)

[0018]

[Chemical 10] Since the effect of imparting heat resistance to (1) is great, it is possible to easily design a copolymer having desired heat resistance by incorporating the repeating unit in a small amount of PATE chain. As a result PAT
It has an advantage that the solvent resistance and water absorption resistance, which are excellent characteristics of E, can be sufficiently retained. Further, according to this method, it is possible to reduce the amount of salt produced in the reaction system,
The content of ionic impurities in the resulting copolymer can be reduced. The present invention has been completed based on these findings.

[0019]

Thus, according to the present invention, the repeating unit [I] is used in a polar organic solvent.

[0020]

[Chemical 11] [Wherein R represents an alkyl group having 1 to 6 carbon atoms, k
Represents 0 or an integer of 1 to 4. A prepolymer (B) having an alkali thiolate group at at least one terminal, which is obtained by depolymerizing a polyarylene thioether (A) having an alkali metal sulfide.

[0021]

[Chemical formula 12] (However, m is 0 or an integer of 1 to 100, and X is
Represents a halogen atom. And a dihalogen-substituted aromatic compound represented by the formula (1) is polymerized in a polar organic solvent together with an alkali metal sulfide, if necessary, to provide a highly heat-resistant aromatic copolymer (C). .. Hereinafter, the present invention will be described in detail.

[Raw Material PATE (A)] In the present invention,
The raw material PATE (A) used for depolymerization is a repeating unit [I].

[0023]

[Chemical 13] [Wherein R represents an alkyl group having 1 to 6 carbon atoms, k
Represents 0 or an integer of 1 to 4. ] It is polyarylene thioether (A).

Here, the polyarylene thioether (A) contains 50 units of the repeating unit [I] in the polymer.
It means that it contains at least 70% by weight, preferably at least 70% by weight, more preferably at least 80% by weight.

The PAT used as a raw material in the present invention
E (A) includes a polymer having a high degree of polymerization to an oligomer having a low degree of polymerization having several repeating units, preferably about several tens of repeating units. In addition, off-spec products, molding waste, and waste plastic can be used.

Such a raw material PATE (A) is not particularly limited, but is usually obtained by a reaction of a dihalogen-substituted aromatic compound and an alkali metal sulfide. For example,
U.S. Pat. No. 3,919,177, U.S. Pat. No. 4,64
As disclosed in Japanese Patent No. 5,826, it can be obtained by heating and polymerizing an alkali metal sulfide and a dihalogen-substituted aromatic compound in a polar organic solvent such as N-methylpyrrolidone. .. Furthermore, in the present invention, the compound of the general formula [VII] is used for 1 mol of the alkali metal sulfide.

[0027]

[Chemical 14] [However, X represents a halogen atom, R represents an alkyl group having 1 to 6 carbon atoms, and k represents 0 or an integer of 1 to 4. ] A dihalogen-substituted aromatic compound whose main component is represented by 0.9 to 1.1 mol, preferably 0.9
5 to 1.05 mol, more preferably 0.97 to 1.0
PATE obtained by carrying out a polymerization reaction of 3 mol in a water-containing polar organic solvent can be preferably used as a raw material.

Examples of the compound represented by the above general formula [VII] include p-dichlorobenzene, m-dichlorobenzene, 2,6-dichlorotoluene, 2,5-dichlorotoluene and p-dibromo. Dihalogen-substituted aromatic compounds such as benzene can be mentioned. Also, 2, 6
-Dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 3,5-
Dichlorobenzoic acid, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorodiphenyl sulfone, 4,
4'-dichlorodiphenyl sulfoxide, 4,4'-
Other dihalogen-substituted aromatic compounds such as dichlorodiphenyl ketone can be used as a minor component of 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less.

The PATE thus obtained may be used by separating it from the reaction mixture, or the reaction mixture may be directly subjected to depolymerization. In particular, when reducing ionic impurities, the raw material PATE (A) is preferably one obtained by separating the polymer from the polymerization mixture and purifying it by washing or the like.

The polar organic solvent and water contained in the reaction solution can be used as they are as a part of the components of the depolymerization step. In addition, PATE may be obtained by cooling the reaction solution to cause precipitation.

[Alkali Metal Sulfide] Examples of the alkali metal sulfide used for depolymerization of PATE (A) include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. it can. Further, an alkali metal sulfide prepared in situ from an alkali hydrosulfide and an alkali hydroxide can be used.

[Bis (benzoyl) benzophenone-containing dihalogen-substituted aromatic compound] Bis (benzoyl) benzophenone reacted with a prepolymer (B) having an alkali thiolate group at at least one terminal obtained by depolymerizing PATE (A) The contained dihalogen-substituted aromatic compound has the general formula [II]

[0033]

[Chemical 15] (However, m is 0 or an integer of 1 to 100, and X is
Represents a halogen atom. ) At least 1
Compound of species.

The halogen atom X is selected from fluorine, chlorine, bromine or iodine and may be the same or different from each other. Particularly, those selected from chlorine or bromine are preferable. As such a dihalogen-substituted aromatic compound, when m = 0, a compound represented by the general formula [VIII]

[0035]

[Chemical 16] (However, X represents a halogen atom.)

Examples of the compound represented by the general formula [VIII] are preferably 4,4'-bis (4-chlorobenzoyl) benzophenone and 3,3'-bis (4-
Chlorobenzoyl) benzophenone, 3,4'-bis (4-chlorobenzoyl) benzophenone, 4,4'-
Bis (4-bromobenzoyl) benzophenone, 3,
3'-bis (4-bromobenzoyl) benzophenone,
3,4′-bis (4-bromobenzoyl) benzophenone and the like and mixtures of two or more thereof are used. Among these compounds, general formula [III]

[0037]

[Chemical 17] Compounds represented by are preferred.

Further, an oligomer or polymer formed by the reaction of the compound represented by the general formula [VIII] with a small amount of an alkali metal sulfide and having a halogen atom at its terminal can also be used ( In the general formula [II], m = 1 to 100). In this case, m
Is preferably an integer of 1 to 20, more preferably 1 to 8. If m exceeds 100, the reactivity may be insufficient.

(Polar organic solvent) As the polar organic solvent,
For example, N-alkylpyrrolidone such as N-methylpyrrolidone, 1,3-dialkyl-2-imidazolidinone,
Aprotic organic amide solvents represented by tetraalkylurea, hexaalkylphosphoric acid triamide and the like are preferable because the stability of the reaction system is high and a high molecular weight polymer can be obtained.

(Production Method) In the production method of the highly heat-resistant aromatic copolymer (C) of the present invention, an alkali metal sulfide is allowed to act on PATE (A) to depolymerize it, so that at least one terminal has an alkali thiolate group. To obtain a prepolymer (B) having (a depolymerization step or an alkali thiolation step) and a step of causing a polymerization reaction again by reacting the produced prepolymer (B) with various dihalogen-substituted aromatic compounds (polymerization step) Alternatively, a repolymerization step) is included.

Depolymerization Step The prepolymer (B) having an alkali thiolate group at at least one end is usually (a) polar organic solvent 1k.
a water-containing polar organic solvent containing up to 20 mol of water per gram,
(B) PATE (A) for 1 kg of polar organic solvent
0.1 to 5 basic moles, and (c) 1 to 1 basic mole of PATE (A), a mixture containing 0.01 to 1 mole of an alkali metal sulfide at 200 to 300 ° C. for 0.1 to 30 moles.
It can be suitably obtained by carrying out a depolymerization reaction for a time.

The reaction temperature is usually 200 to 300 ° C., preferably 220 to 280 ° C., more preferably 235 to 2 ° C.
It is 80 ° C. If the temperature is lower than 200 ° C, depolymerization and alkali thiolation will be insufficient, or the reaction time will be too long. If the temperature exceeds 300 ° C, a decomposition reaction will easily occur, which is not preferable.

The reaction time is usually 0.1 to 30 hours, more preferably 0.5 to 20 hours. If it is less than 0.1 hours, the reaction may be insufficient, and if it exceeds 30 hours, it is economically disadvantageous.

The coexisting amount of water in the depolymerization step is up to 20 mol, preferably 0.1 to 20 mol, per 1 kg of the polar organic solvent.
The molar range is more preferably 0.2 to 10 mol. If it exceeds 20 mol, an undesirable side reaction may occur.

The amount of PATE (A) used for depolymerization is in the range of 0.1 to 5 basic moles, preferably 0.2 to 4 basic moles per kg of the polar organic solvent. If it is less than 0.1 basic moles, the productivity will be reduced, and if it exceeds 5 basic moles, the viscosity of the reaction system will be high, which is not preferable. The "basic mole" number in the present invention means PATE
Is the number of moles calculated with the total of the atomic weights constituting the repeating unit [I] as 1 gram molecule.

The amount of alkali metal sulfide is PATE
(A) 0.01 to 1 mol, preferably 0.02 to 0.9 mol, and more preferably 0.05 to 1 mol per 1 basic mol.
A range of 0.8 mol is desirable. If it is less than 0.01 mol,
Alkali thiolation may be insufficient, and conversely, if it exceeds 1 mol, the composition uniformity and melt stability of the copolymer (C) obtained in the polymerization step may be adversely affected.

The mixture containing the water-containing polar organic solvent, the polyarylene thioether (A) and the alkali metal sulfide has a pH value of 9 or more, preferably 10 or more, which is obtained by diluting the mixture with 10 times (weight ratio) of water. It is desirable to be alkaline so that If the pH value is less than 9,
Depolymerization and alkali thiolation may be insufficient.

In order to bring the mixture to the desired alkalinity,
0.001 to 1 mol per 1 mol of PATE (A),
Preferably 0.01 to 0.5 mol of the basic compound can be added. As such a basic compound,
At least one compound selected from hydroxides, oxides, and carbonates of alkali metals or alkaline earth metals can be given.

Thus, the prepolymer (B) having an alkali thiolate group at at least one terminal is obtained. It is considered that such a prepolymer (B) is usually mainly one having an alkali thiolate group at both ends.

The degree of polymerization of the prepolymer (B) varies depending on the reaction conditions such as the degree of polymerization of the raw material PATE (A) and the amount of alkali metal sulfide used for depolymerization, and one repeating unit [I] is used. From a few oligomers to those having a relatively high degree of polymerization, those used in the present invention can be used without particular limitation, and any degree of polymerization, or a mixture of these. Good.

The prepolymer (B) having an alkali thiolate group at at least one terminal is used as a component of the next polymerization step with good stability as a reaction mixture (reaction solution) containing the prepolymer (B). be able to.
Further, if necessary, the prepolymer (B) can be once separated from the reaction solution under a condition that it is not oxidized and used as a component for the next polymerization step.

Prepolymer (B) having an alkali thiolate group at the end by depolymerization with an alkali metal sulfide
It is not necessary that the reaction system be strongly alkaline after the formation of. Rather, strong alkalinity may hinder the polymerization reaction.

Therefore, after the alkali thiolation reaction, when the produced prepolymer (B) is used as it is in the next polymerization reaction without being separated from the reaction solution, it can be partially neutralized with an acidic substance. However, if the reaction solution is made acidic, the alkali thiolate group is easily decomposed, which is not preferable.

As the neutralizing agent, a salt of a protic acid and / or a strong acid and a weak base is used, and a salt of a strong acid and a weak base is particularly preferable. Specific examples include ammonium halides, dilute mineral acids, organic carboxylic acids, and the like.

Polymerization Step The polymerization reaction of the prepolymer (B) having an alkali thiolate group at at least one terminal with at least one dihalogen-substituted aromatic compound represented by the general formula [II] is usually carried out by (a) ) Water-containing polar organic solvent containing up to 30 mol of water per kg of polar organic solvent, (b) 0.05-5 basic prepolymer (B) having an alkali thiolate group at least at one end with respect to 1 kg of polar organic solvent 80 moles of the mixture containing at least one dihalogen-substituted aromatic compound represented by the general formula [II], and (c) 1 mole of the prepolymer (B). It can be suitably carried out by carrying out a polymerization reaction at ˜300 ° C. for 0.1 to 30 hours.

The polymerization reaction temperature is usually 80 to 300 ° C.,
More preferably, it is 100 to 280 ° C. Reaction temperature is 8
If the temperature is lower than 0 ° C, the polymerization reaction may be insufficient,
On the contrary, if the temperature exceeds 300 ° C, a decomposition reaction may occur.

The polymerization time is usually 0.1 to 30 hours, more preferably 0.5 to 20 hours. The reaction time is 0.
If it is less than 1 hour, the polymerization reaction may be insufficient, and conversely, if it exceeds 30 hours, the productivity will be poor.

Further, by carrying out the polymerization reaction by raising the temperature in multiple stages of two or more, it is easy to obtain a higher molecular weight copolymer in a shorter time. For example, there is a method in which the first-stage polymerization is performed at a temperature up to 235 ° C., and then the second-stage polymerization is performed by raising the temperature to 245 ° C. or higher.

The amount of water in the reaction system in this polymerization step is
Up to 30 mol, preferably 1 per kg of polar organic solvent
The range of ˜25 mol, more preferably 5˜20 mol is desirable. A part of this water may be added during the polymerization reaction. In particular, in the latter half of this polymerization step, when the temperature is raised to 245 ° C. or higher to carry out the polymerization reaction, adding water before and after this temperature raising step results in a copolymer (C having a higher molecular weight and more excellent melt stability). ) Is easy to obtain. If the amount of water exceeds 30 moles, undesirable side reactions are likely to occur, and it becomes difficult to obtain a high molecular weight copolymer.

The amount of the prepolymer (B) is 0.05 to 5 basic mol, preferably 0.1 per 1 kg of the polar organic solvent.
A range of up to 4 basic moles is desirable. If it is less than 0.05 basic mole, it is disadvantageous in terms of productivity, and if it is more than 5 basic moles,
The viscosity of the reaction system becomes high, which is not preferable. However, the basic number of moles of the prepolymer (B) means the number of moles calculated as the sum of the atomic weights constituting the repeating unit [I] as 1 gram molecule.

The amount of the dihalogen-substituted aromatic compound is preferably 0.7 to 1.3 mol, more preferably 0.9 to 1.1 mol, per mol of the prepolymer (B). 0.
If it is less than 7 mol or more than 1.3 mol, it is difficult to obtain a high molecular weight copolymer.

Here, the number of moles of the prepolymer (B) is
It is defined as the number of moles of the alkali metal sulfide obtained by subtracting the amount of the alkali metal sulfide remaining after the depolymerization reaction from the amount of the alkali metal sulfide added when producing the prepolymer (B).

In the present invention, if necessary, an alkali metal sulfide can be used in the step of polymerizing the prepolymer (B) and the dihalogen-substituted aromatic compound. 60 mol% relative to the sum of prepolymer (B) and alkali metal sulfide
It can be used in the following range, preferably in a range of less than 50 mol%, more preferably in a range of 30 mol% or less. The amount of the alkali metal sulfide used in this case is added to the number of moles of the prepolymer (B) defined above when defining the amount of the dihalogen-substituted aromatic compound, and this total amount is added to the mole of the prepolymer (B). Let it be a number.

Other Polymerization Conditions In the production method of the present invention, as a reaction device, at least a portion which is in direct contact with the reaction solution is composed of an inert corrosion-resistant material which does not react with the reaction solution such as titanium material. It is preferably one.

In the method for producing the copolymer, a halogen compound such as bis (halobenzoyl) benzophenone, bis (halobenzoyl) benzene, dihalobenzophenone, dihalodiphenylsulfone, monohalobenzophenone is used as a reaction system at the end of the reaction. A copolymer having further improved melt stability can be obtained by adding to and reacting with.

The copolymer of the present invention has a repeating unit [V
I]

[0067]

[Chemical 18] At least one polyarylene thioether ketone ketone ketone (PTKKK) segment (X)
And repeating unit [I]

[0068]

[Chemical 19] Is a copolymer containing at least one PATE segment (Y) having

When the copolymer of the present invention is to be obtained as a granular material, the weight ratio of the total amount of the segment (Y) to the total amount of the segment (X) is preferably 0.5 to 9. , More preferably 1.0 to 5, and even more preferably 1.5 to 4.

[0070]

EXAMPLES The present invention will be specifically described below with reference to reference examples, examples and comparative examples, but the present invention is not limited to these examples.

The method for measuring the physical properties of the polymer is as follows. <Measurement of Physical Properties> Melting point (Tm), glass transition temperature (Tg) Melting point (Tm) and glass transition temperature (Tg) are about 0.
It was formed into a sheet of 5 mm, and the temperature was raised from room temperature to 10 ° C./minute in a nitrogen atmosphere and measured using a differential scanning calorimeter (DSC). The Tm of the granular polymer (polymer after polymerization) was measured under the same conditions without performing sheet forming by hot pressing.

The composition ratio of the polymer was calculated from the elemental analysis value of sulfur.

Amount of Sodium Ions The amount of sodium ions was quantified by ion chromatography after decomposing the polymer in heated concentrated sulfuric acid, treating with hydrogen peroxide water to prepare a sample solution.

A polymer sample was loaded into a capillograph (manufactured by Toyo Seiki Co., Ltd.) equipped with a nozzle having a melt viscosity inner diameter of 1 mmφ and L / D = 10/1, preheated at a temperature higher than the melting point Tm of the polymer for 5 minutes, and then sheared. It was measured at a specific temperature of 1,200 / sec.

Measurement of number average molecular weight A sample reaction solution (including an alkali thiolate compound) was sampled, treated with a large excess amount of dilute hydrochloric acid water, washed sufficiently with water, and vacuum dried to prepare a sample sample. The raw material PATE polymer was directly used as a sample sample. The number average molecular weight was determined by gel permeation chromatography (GPC method). The measurement conditions are as follows. Column: SHODEX AT80M / S Two in series Solvent: α-Chlornaphthalene Flow rate: 0.7 ml / min Temperature: 220 ° C. Sample concentration: 0.05 wt% Injection amount: 200 μl Detector: Hydrogen flame ionization detector (FID) Molecular weight Calibration: Standard polystyrene and

[0076]

[Chemical 20] Data processing: Chromatopack C-RAX (Shimadzu)

[Synthesis Example] [Synthesis of 4,4′-bis (4-chlorobenzoyl) benzophenone] Aluminum chloride 25 was added to a 500 ml four-necked flask equipped with a stirrer, a dropping device, a thermometer, and a reflux condenser. .60 g (0.192 mol), 1,1,2,2
-Tetrachloroethane (100 ml) was added, and the mixture was stirred until the aluminum chloride mass disappeared, and then 44.14 g (0.192 mol) of 4-chlorobenzotrichloride was added at 5 ° C. Further at this temperature diphenylmethane 13.45
g (0.08 mol) was appropriately added, and the mixture was reacted with stirring for 2 hours.
After the reaction was completed, 100 ml of water was added to the reaction mixture, the liquid temperature was raised to 100 ° C., and the mixture was vigorously stirred for 3 hours to hydrolyze 4,4′-bis (4-chlorophenyldichloromethyl) diphenylmethane produced in the above reaction. Decomposition yielded 4,4'-bis (4-chlorobenzoyl) diphenylmethane.

After the completion of hydrolysis, the reaction solution was cooled, 200 ml of chloroform was added to dissolve the organic matter, the chloroform layer was separated, washed with water, and then distilled. Toluene was added to the residue obtained by distilling off chloroform and 1,1,2,2-tetrachloroethane by distillation to recrystallize,
28.0 g of off-white needle crystals of 4,4′-bis (4-chlorobenzoyl) diphenylmethane were obtained.

Next, in a 200 ml titanium autoclave equipped with a stirrer, a reflux condenser and an air blowing tube, 4,4'-bis (4-chlorobenzoyl) diphenylmethane 20.00 g, acetic acid 90 g, water 10 g, cobalt acetate were added. Tetrahydrate 0.5 g, manganese acetate tetrahydrate 1.0 g,
Add 1.00 g of ammonium bromide and add 10 kg / nitrogen.
After pressurizing to cm ² G, the temperature was raised. After the temperature of the reaction system reached 180 ° C., while maintaining the pressure of 11 kg / cm ² G at this temperature, 24 liters / hour of air was flowed under stirring for reaction for 7 hours.

After the reaction was completed, the reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration and washed with acetic acid. The crystals obtained were recrystallized from 1-methyl-2-pyrrolidinone to give 17.53 g of 4,4'-bis (4-chlorobenzoyl) benzophenone.
Got The purity analyzed by a differential scanning calorimeter manufactured by METTLER CORPORATION was 99.90%. The yield was 84.9%.

Its structure is a compound represented by the following structural formula 21 by mass spectrometry (Mass), infrared spectrum spectrometry (IR) and elemental analysis.

[0082]

[Chemical 21]

The analysis values are shown below. Molecular weight (Mass): 458 IR: 1645 cm ^-1 (C = O) Elemental analysis: [Experimental value] [Theoretical value] C: 70.6 wt% 70.61 wt% H: 3.5 wt% 3.51 wt % Cl: 15.4 wt% 15.44 wt% Melting point: 310.5-311 ° C

Further, the required amount of 4,4'-bis (4-chlorobenzoyl) benzophenone (hereinafter abbreviated as BCBB) used in the following Examples and Comparative Examples was synthesized by the above-mentioned method.

[Reference Example 1] <Preparation of starting material PATE (A)> N-methylpyrrolidone (NMP) 7.0 kg, hydrous sodium sulfide 3.03 k
g (18.02 mol, water content 53.6% by weight) was charged into a titanium-lined autoclave, and after substitution with nitrogen gas,
While gradually raising the temperature to 200 ° C., 2.02 kg of an NMP solution containing 1.32 kg of water and 0.41 mol of hydrogen sulfide were distilled out.

Then, p-dichlorobenzene 2.65 k
g (18.03 mol), 0.24 kg (13.32 mol) of water and 3.70 kg of NMP were fed as a mixed solution, and 2
After reacting at 20 ° C for 5 hours, 0.72 kg of water is further added.
(40.00 mol) was injected under pressure, and the temperature was raised to 255 ° C. to react for 3 hours.

The obtained reaction mixture was sieved with a screen to separate the granular polymer, washed three times with acetone and three times with water, dehydrated and dried at 100 ° C. to obtain white granular PATE (A- 1) was obtained.

The physical properties of PATE (A-1) were as follows. Tm = 281 ° C. Tg = 86 ° C. η ^* = 2200 poise (310 ° C.) Number average molecular weight = 11000 Sodium ion = 450 ppm

Example 1 <Depolymerization and Alkali Thiolation Reaction> 108 g of PATE (A-1) prepared in Reference Example 1 in a titanium polymerization can.
A mixture of (1.0 basic mol), 500 g of NMP, 23.07 g of hydrous sodium sulfide (water content 53.88 wt%), and 1.0 g of sodium hydroxide was stirred to prepare a mixed solution. The pH value of the aqueous solution obtained by diluting a part of this mixed solution with 10 times (weight ratio) water was 12.

After substituting this mixture with nitrogen, stirring the mixture,
By heating at 240 ° C. for 2 hours, depolymerization and alkali thiolation reaction were carried out to obtain a reaction solution (a-1). Residual sodium sulfide in this reaction solution was quantified by an ion chromatography method and found to be 2.5%.

<Analysis of Alkali Thiolated Compound> The reaction solution (a-1) was diluted with 10 times amount of water, adjusted to pH 3 with hydrochloric acid, sufficiently washed with water, and vacuum dried at room temperature to obtain thiol compound. Got

The thiol compound had a thiophenol odor. In addition, the infrared absorption spectrum shows that the raw material P
2560 derived from thiol group not found in ATE
Weak absorption was observed near cm ^-1 . The sulfur content of the thiol compound increased to 31.6 wt% compared to the theoretical PATE value of 29.60 wt%. The melt viscosity of this thiol product was 50 poise or less (310 ° C.), which was much smaller than 2200 poise of the raw material PATE.

<Copolymerization reaction> The above reaction solution (a-1) 3
88.7 g [containing 0.082 mol of prepolymer (B) and 0.0021 mol of sodium sulfide] and BCBB38.5
8 g (0.084 mol) NMP 336 g and water 85.
1 g of titanium was charged into a polymerization can made of titanium, and after nitrogen substitution, the temperature was raised to 2
The reaction was carried out at 70 ° C for 30 minutes.

After the temperature of this reaction mixture was lowered to 240 ° C., the final stage of the reaction was carried out. End-of-reaction treatment is 6.3 g of 4,4'dichlorobenzophenone (hereinafter abbreviated as DCBP)
A mixed solution of 60 g of NMP and NMP was injected under pressure and reacted at 240 ° C. for 30 minutes.

The reaction mixture thus obtained was opened to 150 μm.
After sieving with a (100 mesh) screen, the granular polymer was separated, washed three times with acetone and three times with water, and then dehydrated. After drying at 100 ° C., a copolymer (polymer C1) was obtained in a yield of 72%.

<Physical Properties of Polymer> Obtained Polymer C1
The physical properties of were as follows. Tm = 336 ° C. (Tm of the copolymer after polymerization was 345 ° C.) Tg = 114 ° C. Melt viscosity = 150 poise (370 ° C.) Sodium ion content = 60 ppm

Example 2 <Depolymerization and Alkali Thiolation Reaction> Water-containing PATE (A-1) 166.1 g before drying prepared in Reference Example 1
(1.0 basic mole, water content 36.6% by weight), NMP7
00g, hydrous sodium sulfide (water content 53.88% by weight)
A mixture of 18.8 g and 1.0 g of sodium hydroxide was stirred to prepare a mixed liquid. The pH value of the aqueous solution obtained by diluting a part of this mixed solution with 10 times (weight ratio) water was 12.

After substituting this mixture with nitrogen,
The mixture was heated at 240 ° C. for 1 hour to carry out depolymerization and alkali thiolation reaction to obtain a reaction solution (a-2). Residual sodium sulfide in this reaction solution was quantified by an ion chromatography method and found to be 3.4%.

<Copolymerization reaction> The above reaction solution (a-2) 5
00 g [containing 0.0783 mol of prepolymer (B) and 0.0028 mol of sodium sulfide] and BCBB36.84
g (0.0802 mol) was charged in a titanium polymerization can, and after nitrogen substitution, the temperature was raised and the reaction was carried out at 270 ° C. for 30 minutes.

After the temperature of this reaction mixture was lowered to 240 ° C., the final stage of reaction was carried out. DCBP for the final treatment of the reaction
A mixture of 6.3 g and 60 g of NMP was press-fitted, and the mixture was mixed at 240 ° C for 3
The reaction was carried out for 0 minutes. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain a copolymer (polymer C2) with a recovery rate of 88%.

<Physical Properties of Polymer> The physical properties of the copolymer C2 were as follows. Tm = 306 ° C. (Tm of the copolymer after polymerization was 318 ° C.) Tg = 108 ° C. Melt viscosity = 200 poise (370 ° C.) Sodium ion content = 40 ppm

Example 3 <Depolymerization and Alkali Thiolation Reaction> 108 g (1.0 basic mole) of PATE (registered trademark FORTRON # W300, manufactured by Kureha Chemical Industry Co., Ltd.) in a titanium polymerization vessel,
NMP500g, hydrous sodium sulfide (water content 53.88
A mixture of 18.8 g (wt%) and 1.0 g of sodium hydroxide was stirred to prepare a mixed solution. The pH value of an aqueous solution obtained by diluting a part of this mixed solution with 10 times (weight ratio) water is 1
It was 2.

After substituting the mixture with nitrogen, stirring the mixture,
After heating at 240 ° C. for 1 hour, depolymerization and alkali thiolation reaction were performed to obtain a reaction solution (a-3). The residual sodium sulfide in the reaction solution was quantified by an ion chromatography method and found to be 0.3%.

<Synthesis of PTKKK oligomer> BCBB
80 g (0.174 mol), hydrous sodium sulfide (water content 53.88% by weight) 10.34 g, NMP 400 g and water 30.4 g were charged into a titanium polymerization vessel, and after nitrogen replacement, the temperature was raised to 220 ° C. for 2 hours by heating. React, PTK
A reaction solution KS1 containing the KK oligomer K1 was obtained.

<Copolymerization reaction> The above reaction solution (a-3) 2
82.5 g [containing 0.0499 mol of prepolymer (B) and 0.0002 mol of sodium sulfide], 230.1 g of reaction liquid slurry KS1 and 37.4 g of water were charged into a titanium polymerization can, and after nitrogen replacement, the temperature was raised. Then, the reaction was carried out at 270 ° C. for 30 minutes.

After the temperature of this reaction mixture was lowered to 240 ° C., the final stage of reaction was carried out. DCBP for the final treatment of the reaction
A mixture of 6.3 g and 60 g of NMP was press-fitted, and the mixture was mixed at 240 ° C for 3
The reaction was carried out for 0 minutes. A polymer was recovered from the obtained reaction liquid slurry using a paper filter (type 5 A), sufficiently washed with acetone and water, and dried to obtain a copolymer (polymer C3) with a recovery rate of 93%.

<Physical Properties of Polymer> The physical properties of the copolymer C3 were as follows. Tm = 340 ° C. (Tm of the copolymer after polymerization was 355 ° C.) Tg = 111 ° C. Melt viscosity = 50 poise (370 ° C.) Sodium ion content = 110 ppm

Comparative Example 1 <Synthesis of homopolymer> BCBB 28.7 g, hydrous sodium sulfide (water content 53.88% by weight) 10.58 g, N
500 g of MP and 38.4 g of water were charged into a titanium polymerization vessel, and after nitrogen substitution, the temperature was raised by heating and the reaction was carried out at 220 ° C. for 2 hours.

The reaction solution slurry was put into acetone to allow the polymer to settle, and then the polymer was recovered using a paper filter (5 type A), thoroughly washed with acetone and water, and dried to obtain a fine powder polymer. R1 was obtained. The average particle size of the polymer R1 was 20 μm or less, and the melting point of the polymer after polymerization was 436 ° C.

[0110]

INDUSTRIAL APPLICABILITY According to the present invention, two or more kinds of dihalogen-substituted aromatic compounds having different stability and reactivity in the polymerization reaction system are used as starting materials, and the amount of ionic impurities is small and the heat resistance is wide and the heat resistance is wide. Aromatic copolymers of

Further, according to the present invention, by-product oligomers in the PATE manufacturing process, off-spec products, molding waste of PATE and used waste plastics can be recycled, which contributes to effective use of resources.

The copolymer of the present invention is useful alone as a resin for molding, but if necessary, a stabilizer, another thermoplastic resin, a fibrous filler and / or an inorganic filler may be added to the copolymer. It can be used as a composition.

Claims (4)

[Claims] 1. A repeating unit [I] embedded image in a polar organic solvent. [Wherein R represents an alkyl group having 1 to 6 carbon atoms, k
Represents 0 or an integer of 1 to 4. A polyarylene thioether (A) having the following formula (A) is reacted with an alkali metal sulfide to depolymerize, and a prepolymer (B) having an alkali thiolate group at at least one terminal and a compound represented by the general formula [II] 2] (However, m is 0 or an integer of 1 to 100, and X is
Represents a halogen atom. ) A dihalogen-substituted aromatic compound represented by the formula (2) is polymerized in a polar organic solvent if necessary with an alkali metal sulfide to produce a highly heat-resistant aromatic copolymer (C). 2. A prepolymer (B) having an alkali thiolate group on at least one terminal is (a) a water-containing polar organic solvent containing up to 20 mol of water per 1 kg of a polar organic solvent, and (b) in 1 kg of a polar organic solvent. In contrast, 0.1 to 5 basic moles of polyarylene thioether (A) (provided that the basic mole number is the number of moles calculated by summing the atomic weights constituting the repeating unit [I] as 1 gram molecule), and (c ) Obtained by depolymerizing a mixture containing 0.01 to 1 mol of an alkali metal sulfide with respect to 1 basic mol of polyarylene thioether (A) at 200 to 300 ° C for 0.1 to 30 hours. The manufacturing method according to claim 1, which is a product. 3. A polymerization reaction between a prepolymer (B) having an alkali thiolate group at at least one terminal and at least one dihalogen-substituted aromatic compound represented by the general formula [II] is carried out by (a) polar organic compound. Water-containing polar organic solvent containing up to 30 moles of water per kg of solvent, (b) 0.05 to 5 basic moles of a prepolymer (B) having an alkali thiolate group at at least one end with respect to 1 kg of polar organic solvent, and (C) 80 to 80 parts of a mixture containing 0.7 to 1.3 mol of at least one dihalogen-substituted aromatic compound represented by the general formula [II] per 1 mol of the prepolymer (B).
The production method according to claim 1 or 2, wherein the polymerization reaction is performed at 300 ° C for 0.1 to 30 hours. 4. A dihalogen-substituted aromatic compound is represented by the general formula [III]: The method according to claim 1, wherein the compound is a compound represented by the formula (wherein X represents a halogen atom).