JPH02225527A - Polyarylene thioether block copolymer and its production - Google Patents

Abstract

PURPOSE:To produce the title crystalline copolymer excellent in heat resistance, processability, etc., by heating a liquid mixture of a reaction solution containing a polyarylene thioether prepolymer with a specified dihaloaromatic compound, an alkali metal sulfide, an organic amide solution and water. CONSTITUTION:An organic amide solution containing a dihalobenzene-based dihaloaromatic compound and an alkali metal sulfide is heated in the presence of water to form a reaction solution containing a polyarylene thioether prepolymer mainly consisting of repeating units of formula I and having reactive terminal groups (step 1). The reaction solution from step 1 is mixed with a 4,4'-dihalobenzophenone-based dihaloaromatic compound, an alkali metal sulfide, an organic amide solvent and water, and the combined solution is heated to form a polyarylene thioether ketone block mainly consisting of formula II (wherein CO and S in the benzene ring are bonded para to each other) (step 2). By performing the reactions in the above steps under specified conditions, the title copolymer containing polyarylene thioether ketone blocks and the polyarylene thioether blocks can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention has excellent melt stability, processability, and handleability, and
Regarding crystalline polyarylene thioether block copolymers, for more details, please refer to polyarylene thioether ketone block and polyarylene thioether block copolymer.
The present invention relates to a novel block copolymer containing blocks and a method for producing the same.

The present invention also relates to a molded article using the block copolymer. Furthermore, the present invention relates to the stabilized block copolymers.

[Conventional technology] In recent years, in the electronics/electrical industry and the automobile/aircraft/space industry, materials with heat resistance with a melting point of approximately 300°C or higher,
Furthermore, there is a strong demand for crystalline thermoplastic resins that are easy to melt process.

Recently, polyarylene thioether ketone (hereinafter referred to as PT)
(abbreviated as K) has attracted attention for its high melting point and is being studied.

For example, JP-A-60-58435, West German Publication DE-3405523A1, JP-A-60-1041.
No. 26, JP-A-47-13347, Magazine In
dian J, Chem, 2IA (May, 198
2) pp, 501-502, JP-A-151-2212
No. 29, U.S. Patent No. 4,716,212,
US Patent No. 4,690,972, European Patent No. 0
．． 270,955 A2 Publication, European Patent No. 0.27
4.754 A2 Publication and European Patent No. 0.28
0,325 Disclosures regarding PTK can be found in A2 Publications and other publications.

However, with respect to the PTK described in the above-mentioned document, molding by the Funatsuri melt processing method has not been successful so far.In the present invention I, "-The Funatsuri melt processing method"
means conventional melt processing methods for thermoplastic resins such as extrusion molding, injection molding, and melt spinning.

Successful molding of PTK using general melt processing method
The reason for the absence of C is that PTK according to the prior art has poor thermal stability, and is therefore prone to loss of crystallinity during melt processing, or a crosslinking reaction or carbonization reaction accompanied by an increase in melt viscosity.

Therefore, the present inventors investigated a method for economically producing PTK that has sufficient thermal stability during melting to be able to apply the Funatsuri melt processing method. As a result of investigation, it was discovered that PTK with dramatically improved thermal stability during melting could be obtained (hereinafter referred to as r-thermal stability PTKJ) (Japanese Patent Application Laid-Open No. 64-54031).

Furthermore, by adding basic compounds such as hydroxides and oxides of metals from Group IA or Group NA of the periodic table to this thermally stable PTK, the thermal stability during melt processing can be improved.
- It was found that the layer could be improved (Patent application 1427-1983)
No. 72).

The thermostable PTK thus obtained has a high melting point, and in particular, the homopolymer has an extremely high melting point of about 360°C.

However, this increases the melt processing temperature and requires melt processing equipment for high temperature processing. Additionally, strict temperature control is required to perform melt processing without thermal denaturation.

Moreover, since thermostable PTK is usually obtained as a fine powder with a particle size of about 5 to 20 um, it is easy to handle (operate) during the polymer recovery process after sintering, especially filtration, washing, drying, and transportation. There are also problems in polymer production such as poor handling (or handling), poor meterability during melt processing, and occurrence of blocking when using a popper.

[Problems to be Solved by the Invention] The object of the present invention is to improve the heat resistance of the thermostable PTK,
The object of the present invention is to provide a polymer with improved processability and handling while maintaining excellent characteristics such as crystallinity as much as possible.

The present inventors first attempted to lower the processing temperature by randomly copolymerizing thermostable PTK with a different type of monomer to improve the processability of the thermostable PTK. That is, random copolymerization was carried out by combining 4,4'-dihalobenzophenone and dihalobenzene, which is a different kind of dihaloaromatic compound, as a dihaloaromatic compound.

However, the obtained random copolymer showed a tendency that as the proportion of dihalobenzene increased, the crystallinity and heat resistance decreased, and the thermal stability during melting also deteriorated.

In addition, dihalobenzophenones such as 4,4'-dihalobenzophenone are activated by ketone groups and have much higher reactivity than dihalobenzene, so their copolymerizability with dihalobenzene is extremely poor.

Therefore, the present inventors developed a polyarylene thioether (hereinafter referred to as "polyarylene thioether") having a thermostable PTK in the chain.

PTK- that incorporates PATH (abbreviated as PATH) as a block.
An attempt was made to produce a PATH block copolymer. As a result, in an organic amide solvent, P A and T E having a specific average degree of polymerization and a terminal thiolate group and/or thiol group as reactive end groups were made into prepolymers, and this PATE prepolymer and 4.4' It has been discovered that a polyarylene thioether block copolymer with excellent processability and high crystallinity can be obtained by reacting -dihalobenzophenone and an alkali metal sulfide under specific conditions.

Moreover, it has been found that the block copolymer can be obtained as a granular material with extremely good handling properties by a conventional recovery method from the polymerization system.

It has also been found that the block copolymer has high thermal stability when melted, and that various molded products can be easily obtained from the block copolymer alone or from its composition by a general melt processing method.

Furthermore, it has been found that by adding a specific basic compound to the block copolymer, optionally together with an antioxidant, a block copolymer with improved melt stability and reduced crystallinity can be obtained.

The present invention has been completed based on these findings.

[Means to solve the problem] That is, the gist of the present invention is as follows.

[In the formula, the -〇〇- group and the -S- group are bonded to the para position via a benzene ring] A polyarylene thioether whose main constituent is a polyarylene thioether ketone block (A)・Block (B) and
A polyarylene thioether block copolymer alternately containing at least one or more of each of the following: (a) blocks (B) relative to the total amount of blocks (A);
(b) the average degree of polymerization of the block (Bl) is 10 or more, and (c) the melt viscosity (at 350°C and a shear rate of 1200/sec) Polyarylene thioether block copolymer (2) defined by a measurement) of 2 to 100,000 voids (2) ■Organic amide solvent containing a dihaloaromatic compound mainly composed of dihalobenzene and an alkali metal sulfide in the coexistence of water. a first step of heating to form a reaction solution containing a polyarylene thioether prepolymer having a reactive end group as a main component; (1) a reaction solution obtained in the first step; A dihalo aromatic compound mainly composed of dihalobenzophenone consisting of '-dichlorobenzophenone and/or 4,4'-dibromobenzophenone, an alkanometal sulfide, an organic amide solvent and water are mixed, and the mixture is heated. a second step of producing a polyarylene thioetherketone block having as a main component [wherein the -〇〇- group and -8- group are bonded to the rose position via a benzene ring]; The polyarylene thioether ketone block (A) and the polyarylene thioether
A method for producing a polyarylene thioether block copolymer containing block (B).

(a) In the first step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0. .8 to 1.05 (mol 1 mol), and polymerization is carried out until the average degree of polymerization of the polyarylene thioether prepolymer becomes 10 or more.

(b) In the second step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg).

(C) In the second step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (total amount of alkali metal sulfides charged in the first step and second step) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0.95 to 1.2.
(1 mole).

(d) The ratio of the charged amount of the dihalo aromatic compound whose main component is dihalobenzophenone to the charged amount of the dihalo aromatic compound whose main component is dihalobenzene is in the range of 0.1 to 10 (1 mol). to do.

(e) Conducting the reaction in the second step at a temperature range of 150 to 300°C. However, the reaction time at 210°C or higher is 10
Within hours.

(f) Melt viscosity of the block copolymer produced in the second step (measured at 350°C and a shear rate of 1200/sec)
The reaction should be carried out until the number is 2 to 100,000 voids.

(3) ■ In the coexistence of water, a dihaloaromatic compound containing dihalobenzene as the main component and an organic amide solvent containing an alkali metal sulfide are heated to form a polyarylene thioether containing as the main component and having reactive end groups.・The first step of forming a reaction solution containing a prepolymer; By heating an organic amide solvent containing an aromatic compound and an alkali metal sulfide, [wherein the -〇〇- group and the -S- group are bonded to the rose position via the benzene ring] as the main constituent, a second step of forming a reaction solution containing a polyarylene thioether ketone prepolymer having a reactive end group;
It consists of at least three steps: a third step of mixing and reacting a reaction solution containing a prepolymer and a reaction solution containing a polyarylene thioetherketone prepolymer.

A polyarylene thioether block comprising a polyarylene thioether ketone block (A) and a polyarylene thioether block (B), characterized in that the reactions in each step are carried out under the conditions (a) to (g) below. Method for producing copolymers.

(a) In the first step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0. .8 to 1.05 (mol 1 mol), and polymerization is carried out until the average degree of polymerization of the polyarylene thioether prepolymer becomes 10 or more.

(b) In the second step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 2.5 to 15 (mol/kg),
The reaction is carried out at a temperature in the range 60-300°C. However, the reaction time at 210°C or higher must be within 10 hours.

(C) In the third step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg).

(d) In the third step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (the total amount of alkali metal sulfides charged in the first and second steps) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0.95 to 1.2.
(1 mole).

(e) The ratio of the total polyarylene thioether prepolymer to the total polyarylenchioether ketone prepolymer is 0.05 to 5 by weight.

(f) The reaction in the third step is carried out at a temperature range of 150 to 300°C, provided that the reaction time at 210°C or higher is io
Within hours.

(g) Melt viscosity of the block copolymer produced in the third step (measured at 350°C and shear rate of 1200/sec)
Carry out the reaction until it becomes 2 to ioo, ooo boys.

(4) A molded article made of the polyarylene thioether block copolymer.

(5) For 100 parts by weight of the polyarylene thiolether block copolymer, a metal of Group ⅠA of the periodic table (
(excluding magnesium); Aromatic carboxylates, carbonates, hydroxides, and phosphates (including condensates) of Group IA metals of the periodic table. , borates (including condensates); 0.1 to 30 parts by weight of at least one basic compound selected from the group consisting of; and a hindered phenol compound, a phosphorus compound, and a hindered amine compound. Stabilized polyarylene thioether block copolymer containing 0 to 10 parts by weight of at least one selected antioxidant (6) A molded article made of the stabilized polyarylene thioether block copolymer. .

The following two aspects of the present invention will be described in detail.

(Leaving space below) (Polyarylene thioether block copolymer) Proccobo polymer 6 The polyarylene thioether block copolymer of the present invention has the following formula: -〇〇- group and -S- group are separated via a benzene ring. This is a block copolymer that alternately contains one or more PTK blocks (A) having the following as the main constituents and PATH blocks (B) having the following as the main constituents.

The configuration of the block of the present invention is (A) + (B) - (A) ), (B) - (A
) type (m is O or an integer greater than or equal to 1), (A>((B
)-(A)), (B) type (n is O or an integer of 1 or more)
Any configuration having both blocks alternately may be used.

It is necessary that the ratio of the total amount of blocks (B) to the total amount of blocks (A) is in the range of 0.05 to 5 by weight, preferably 0.1 to 4, more preferably 0.
．． It ranges from 15 to 3.

Block (A) has the role of imparting high heat resistance and crystallinity to the block copolymer, and block (B) contributes to lowering processing temperature and granulation while maintaining high crystallinity. Therefore, block () for the total amount of blocks (^)
A block copolymer in which the ratio of the total amount of B) is in the range from 0.05 to less than 1, preferably from 0.11 to less than 1, has particularly excellent heat resistance and high crystallinity; -5, preferably in the range of 1-4, the block copolymer retains excellent crystallinity and has particularly excellent processability. However, if the weight ratio of the total amount of block CB> to the total amount of block (A) is less than 0.05, the processing temperature and granulation of the resulting block copolymer will be insufficiently lowered, and conversely, if the weight ratio exceeds 5. If this is the case, the heat resistance will be greatly reduced, and the balance between heat resistance and workability will be disrupted, so none of the options 5 are preferable.

The average degree of polymerization of block (B) needs to be 10 or more, preferably 20 or more.

If the average degree of polymerization of the block (B) is less than 10, the resulting block copolymer becomes a copolymer similar to a random copolymer, which is undesirable because the property costs such as crystallinity, heat resistance, and thermal stability are significantly reduced. Moreover, if the average degree of polymerization of block (B) is too small, there is a problem that it is difficult to obtain a high molecular weight block copolymer.

In addition, block (A> and block (B)) may contain other repeating units as their main constituents, such as: Can be done.

an alkyl group, m is an integer of O to 4), and the like.

These other repeating units are usually introduced into the block copolymer by using various corresponding diheroaromatic compounds as comonomers.

Regarding the physical properties and characteristics of the polyarylene thioether block copolymer of the present invention having a block acupoint of 1 mer, processability, melt stability,
This will be explained in detail from the viewpoint of crystallinity, etc.

(1) Processability The melting point of the PTK homopolymer is about 360°C. Amount of decrease in melting point ΔTm due to copolymerization with different monomers = [3
60° C.-Tm (copolymer melting point)] is generally proportional to the amount of decrease in melt processing temperature. Therefore, 67 m becomes an index representing the effect of lowering the processing temperature, that is, the effect of improving workability.

67m is 10~80℃, more preferably 20~70℃
, more preferably in the range of 30 to 60°C. If 67m is less than 10°C, the effect of improving workability may be insufficient; on the other hand, if 67m exceeds 80°C,
Both are unfavorable because there is a risk that the block copolymer will lose its characteristics as a heat-resistant resin.

(2) Crystallinity One of the major features of the block copolymer of the present invention is that it has excellent processability and at the same time has crystallinity. Crystallinity provides a copolymer with high heat resistance, and in order for a block copolymer to have high heat resistance, it is essential that the block copolymer has sufficient crystallinity.

Generally, the melt crystallization enthalpy ΔHmc is proportional to the amount of crystallization when the molten polymer crystallizes. On the other hand, the melt crystallization temperature Tmc is a measure of the ease of crystallization.

Therefore, the enthalpy of melt crystallization measured when a polymer is heated to 400°C in an inert gas atmosphere and immediately lowered at a rate of 10°C/min using a differential scanning calorimeter (hereinafter abbreviated as DSC) ΔHm,c (400°C) and melt crystallization temperature Tmc (400°C) can be measures of the crystallinity of the block copolymer of the invention.

In addition, the residual melt crystallization enthalpy ΔHmc described later
(400℃/10 minutes) and the melt crystallization temperature T at that time
mc (400° C., 710 minutes) can be used not only as a measure of thermal stability (melt stability) but also as a measure of crystallinity.

The block copolymer of the present invention has a ΔHm c (400°C
) is 15 J/g or more, more preferably 20 J/g
Above, it is more preferable that it is 25 J/g or more. Furthermore, T m c (400°C) is 18
It is desirable that the temperature is 0°C or higher, more preferably 200°C or higher. If the ΔHmc (400°C) is less than t5J/g or the Tmc (400°C) is less than 180°C, the heat resistance as a highly heat-resistant polymer may be insufficient, and this is not preferred.

(3) Thermal stability An important feature of the block copolymer of the present invention is that it has a high degree of thermal stability (melt stability) to the extent that it can be applied to the Funatsuri melt processing method.

Polymers with poor thermal stability tend to undergo curing reactions or decomposition reactions accompanied by loss of crystallinity or increase in melt viscosity during melt processing.

Therefore, by examining the residual crystallinity of a polymer after it is maintained at a high temperature higher than the melt processing temperature for a certain period of time, it can be used as an index of the melt processing suitability of the polymer. Residual crystallinity can be quantitatively evaluated by measuring the enthalpy of melt crystallization with DEC.

Specifically, the block copolymer was held at 50°C for 5 minutes in an inert gas atmosphere, and then heated to 400°C at a rate of 75°C/min.
4. Residual melt crystallization enthalpy ΔHm when held at a temperature of 0°C (a high temperature higher than the melt processing temperature) for 10 minutes and then lowered at a rate of 10°C/min
c (400° C./10 minutes) and the melt crystallization temperature Tmc (400° C./10 minutes) at that time can be used as a measure of thermal stability.

If the copolymer has poor thermal stability, it will undergo a crosslinking reaction and lose most of its crystallinity under the condition of being held at the above-mentioned high temperature of 400° C. for 10 minutes.

The block copolymer of the present invention has ΔHmc (400°C/
10 minutes) is IOJ/g or more, more preferably t5J/g
above, more preferably 20 J/g or more, and a Tmc (400°C/10 minutes) of 170°C or more, more preferably 180°C or more, even more preferably 19
It is a polymer that has physical properties of 0°C or higher.

Block copolymers with ΔHmc (400°C/10 min) of less than tOJ/g or Tmc (400°C/10 min) of less than 170°C tend to lose crystallinity and increase viscosity during melt processing. It is difficult to apply processing methods.

In addition, as a measure of thermal stability, the ratio of melt crystallization enthalpy to residual melt crystallization enthalpy, that is, ΔHmc (400 °C) / ΔHmc (400 °C 710
minute) is also a guideline; the smaller this ratio, the less thermal denaturation. Therefore, ΔHme (400°C/10 minutes) is x, O
J/g or more and the ratio is preferably 5 or less, more preferably 3 or less.

(Left below) (4) Melt viscosity In the present invention, the melt viscosity η2 is used as an index of the molecular weight of the block copolymer.

Specifically, a polymer sample was loaded into a cavilograph (manufactured by Toyo Seiki Co., Ltd.) equipped with a nozzle with an inner diameter of 1 mmφ and L/D = 10/1, preheated at 350°C for 5 minutes, and melted at a shear rate of 1200/sec. Measure the viscosity η°.

The block copolymer of the present invention has a melt viscosity n0 of 2 to 1.
．． 00,000 bois, preferably 5 to 5
0,000 boise, more preferably 10-30.00
It is from 0 Boys.

If the melt viscosity η is less than 2 voices, the molecular weight is small and the fluidity is too high, making general melt processing difficult, and even if a melt-molded product is obtained, its mechanical properties are significantly inferior, so it is not preferable. Also, the melt viscosity of 4 lines is 100,000
Polymers with a higher molecular weight than Voic are undesirable because their molecular weight is too large and their fluidity is too low, making general melt processing difficult.

(Method for producing block copolymer) Various methods can be considered for producing the block copolymer. For example, (2) A method in which a dihaloaromatic compound containing 4,4'-dihalobenzophenone as a main component and an alkali metal sulfide are added to a pre-prepared PATH block (B) and reacted to produce a PTK block (A). , ■ A dihaloaromatic compound containing dihalobenzene as a main component and an alkali metal sulfide are added to the pre-prepared PTK block (A) and reacted,
Examples include a method of generating a PATH block, and (2) a method of chemically bonding a separately prepared PTK block (A> and a PATH block (B)).

As a result of intensive study of these methods, the present inventors found that methods (1) and (2) are suitable for obtaining the block copolymer of the present invention.

A. Block cobomer - In the method for producing a block copolymer of the present invention, an alkaline earth sulfide and a dihaloaromatic compound are used as polymer raw materials, and an organic amide solvent and water (including water of hydration) are mainly used as a reaction medium. used.

(1) Alkali metal sulfide The alkali metal sulfide used in the present invention includes lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.

These alkali metal sulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

In particular, sulfides that are hydrates or aqueous mixtures whose coexisting moisture content falls within the range of the present invention have the advantage that dehydration operations before polymerization can be omitted.

Among these alkali metal sulfides, sodium sulfide is industrially preferred because it is inexpensive. in the reactor
Alkali metal sulfides formed at 5 itu can also be used.

In terms of an industrial raw material with few impurities, commercially available crystalline sodium sulfide pentahydrate can be preferably used.

(2) Dihaloaromatic compound The dihaloaromatic compound used to form the PTK block (A) (including the PTK prepolymer) in the present invention is 4,4'-dichlorobenzophenone and/or
Alternatively, the main component is dihalobenzophenone consisting of 4,4'-dibromobenzophenone.

The dihaloaromatic compound used to form the PATH block (B) (PATE prepolymer) has dihalobenzene such as p-dichlorobenzene and m-dichlorobenzene as a main component.

Other copolymerizable dihaloaromatic compounds include, for example, dihalobenzophenone (excluding 4,4′ monomer),
Dihaloalkylbenzene, dihalobiphenyl, dihalodiphenylsulfone, dihalonaphthalene, bis(Yakuchi phenyl)methane, dihalopyridine, dihalothiophene,
Examples include dihalobenzonitrile and mixtures thereof. As the halogen substituent, chlorine or bromine is preferably used from the viewpoint of economy. However, it is possible to use a small amount of a fluorine compound, such as difluorobenzophenone, within a range that does not have an excessive effect on cost.

In addition, it is permissible to produce a block copolymer with a branched or crosslinked structure by allowing a polyhalo compound of 8 days or more to exist in the reaction system, as long as the processability and physical properties of the block copolymer are not significantly degraded. Ru. Examples of polyhalo compounds of 8 days or more used for this purpose include bis(dichlorobenzoyl)benzene, bis(dibromobenzoyl)benzene, trichlorobenzophenone, tribromobenzophenone, tetrachlorobenzophenone, tetrabromobenzophenone, trichlorobenzene, Bromobenzene, tetrachlorobenzene,
and mixtures thereof.

(3) Specific amide solvent As the reaction medium used in the method for producing the block copolymer of the present invention, aprotic polar organic solvents with excellent thermal stability and alkali resistance are used, especially organic amide solvents (
(including carbamic acid amides) are preferably used.

Examples of such organic amide solvents include N-methylpyrrolidone, N-ethylpyrrolidone, hexamethylphosphoric triamide, tetramethylurea, dimethylimidazolidinone, and dimethylacetamide. These can also be used as mixed solvents.

Among organic amide solvents, N-methylpyrrolidone or a mixed solvent thereof is particularly preferred from the viewpoint of ease of obtaining a thermally stable block copolymer, thermal/chemical stability, economic efficiency, and the like.

B, A and - A conventionally known PATH polymerization method can be employed to prepare the PATH prepolymer in the present invention. However, the reactions that form PTK blocks in the presence of PATE prepolymers, the preparation of PTK prepolymers, and the reactions that combine PTK and PATE prepolymers to form block copolymers require special conditions, i.e., the reaction system. Increasing the amount of coexisting moisture inside,
It is necessary to appropriately control the monomer composition, appropriately control the polymerization temperature, and conduct the reaction at high temperature within a short and controlled time. Furthermore, selecting an appropriate material for the reaction device, stabilizing treatment at the final stage of the reaction, etc. is effective in producing a block copolymer having more preferable physical properties.

Unless these reaction conditions are appropriately controlled, it is not possible to obtain a crystalline block copolymer that has thermal stability (melt stability) suitable for boat melt processing.

<Prepolymer manufacturing method> (1) PATH prepolymer PAT used as a raw material for the block copolymer of the present invention
The E prepolymer is prepared by mixing a dihaloaromatic compound containing an alkali metal sulfide and dihalobenzene as main components in an organic amide solvent in the presence of water under the following conditions (a, ) to (c).
It can be produced by carrying out a dehalogenation/sulfurization reaction.

(a) The ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), preferably 0.5 to 4.5
(mole/kg).

(b) The ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0.8 to 1.05 (1 mol), preferably 0.8 to 1.0, more preferably 0.
Must be in the range of 85 to 0.95 (1 mole).

(c) The reaction is carried out at 200-280°C, preferably at 210-280°C.
The temperature should be kept at 50°C, and the process should be continued until the average degree of polymerization of the produced prepolymer reaches 10 or more, preferably 20 or more.

In addition, the above condition (b) is set such that the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0.95 (
When the amount is 1 mol) or more, particularly 1.0 (1 mol) or more, it can be further treated with an alkali metal sulfide to produce a PATE prepolymer having a large number of thiolate groups as reactive end groups. PATE prepolymer has a slight crosslinked structure and/or
Alternatively, a branched structure may be introduced.

The PATH prepolymer is a polymer having an average degree of polymerization of 10 or more, preferably 20 or more, in view of the physical properties of the resulting block copolymer.

The number average molecular weight of the PATH block in the present invention is determined by the number of terminal thiol groups, thiolate groups and terminal halogen groups at the prepolymer stage.

On the other hand, from the viewpoint of reactivity, the ratio of the terminal thiolate group (including thiol group) to the terminal halogen group of the PATE prepolymer chain is 0.3 (mol 1 mol) or more;
More preferably, it is a polymer of 0.5 (mol 1 mol) or more. If this ratio is less than 0.3, PAT
The reactivity of the terminals of the H prepolymer is insufficient, making it difficult to obtain a block copolymer.

Among these, paraphenylene sulfide units are preferred because they provide particularly excellent block copolymers in terms of crystallinity, thermal stability, heat resistance, mechanical properties, and the like.

(2) PTK prepolymer PTK used as a raw material for the block copolymer of the present invention
The prepolymer can be manufactured by the following method.

That is, an alkali metal sulfide and a dihaloaromatic compound containing 4,4'-dichlorobenzophenone and/or 4,4'-dibromobenzophenone as main components are mixed in an organic amide solvent in the presence of water in the following manner ( a) ~ (b)
It can be produced by a method of dehalogenation/sulfurization reaction under the following conditions.

(a) The ratio of the amount of coexisting water to the amount of organic amide solvent charged is in the range of 2.5 to 15 (mol/kg).

(b) carrying out the reaction at a temperature in the range of 60-300<0>C;

However, the reaction time at 210°C or higher must be within 10 hours.

The PTK prepolymer may be one in which a slight crosslinked structure and/or branched structure is introduced by introducing a small amount of a polypenzophenone having an age of 8 days or more into the polymerization reaction system.

<Production method of block copolymer (Part 1)> As a production method of the block copolymer of the present invention, PATE
There is a method of preparing a prepolymer and forming a PTK block in the presence of the PATE prepolymer. This method essentially includes the following two steps.

■ In the coexistence of moisture, a dihaloaromatic compound containing dihalobenzene as the main component and a bridged amide solvent containing alkali metal sulfide are heated, and the main constituent is PATE prepolymer containing reactive end groups. a first step of forming a reaction solution; An aromatic compound, an alkali metal sulfide, an organic amide solvent, and water are mixed, and the mixture is heated to produce The second step is to generate a PTK block whose main components are:

PTK block (A) and PAT, characterized in that the reaction in each step is carried out under the following conditions (a) to (f).
A method for producing a polyarylene thioether block copolymer containing an H block (B).

(a) In the first step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0. .8 to 1.05 (1 mol), P
Polymerization is carried out until the average degree of polymerization of the ATE prepolymer becomes 10 or more.

(b) In the second step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg).

(C) In the second step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (total amount of alkali metal sulfides charged in the first step and second step) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0.95 to 1.2.
(1 mole).

(d) The ratio of the charged amount of the dihalo aromatic compound whose main component is dihalobenzophenone to the charged amount of the dihalo aromatic compound whose main component is dihalobenzene is in the range of 0.1 to 10 (1 mol). to do.

(e) Conducting the reaction in the second step at a temperature range of 150 to 300°C. However, the reaction time at 210°C or higher is 10
Within hours.

(f) Melt viscosity of the block copolymer produced in the second step (measured at 350°C and a shear rate of 1200/sec)
The reaction should be carried out until the number is 2 to 100,000 voids.

Method for producing a block copolymer (part 2)> As a method for producing a block copolymer of the present invention, PATE
There is a method in which a prepolymer and a PTK prepolymer are prepared in advance, and the PATE prepolymer and PTK prepolymer are reacted and bonded. This method essentially includes the following three steps.

■In the coexistence of water, a dihaloaromatic compound containing dihalobenzene as the main component and an organic amide solvent containing an alkali metal sulfide are heated to react with PATE prepolymer containing PATE prepolymer having reactive end groups as the main constituent. A first step of forming a liquid; ■ In the coexistence of water, a dihaloaromatic compound mainly composed of dihalobenzophenone consisting of 4,4'-dichlorobenzophenone and/or 4,4'-dibromobenzophenone and an alkali metal. By heating an organic amide solvent containing sulfide, [wherein the -C〇- group and -8- group are mainly composed of a bond 1 at the rose position via a benzene ring and have a reactive terminal group] a second step of forming a reaction solution containing a PTK prepolymer, and a third step of mixing and reacting the reaction solution containing the PATE prepolymer obtained in each of the above steps with the reaction solution containing the PTK prepolymer. It consists of at least three steps, and is characterized in that the reaction in each step is carried out under the following conditions (a) to (g). PTK block (A) and PATH
A method for producing a polyarylene thioether block copolymer containing block (B).

(a) In the first step, the ratio of the amount of coexisting moisture to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is O18. ~1.05 (1 mole), P
Polymerization is carried out until the average degree of polymerization of the ATE prepolymer becomes 10 or more.

(b) In the second step, the ratio of the amount of coexisting water to the amount of child amide solvent charged is 2.5 to 15 (mol/g), and the reaction is carried out at a temperature in the range of 60 to 300°C. However, the reaction time at 210°C or higher must be within 10 hours.

(C) In the third step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg).

(d) In the third step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (the total amount of alkali metal sulfides charged in the first and second steps) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0195 to 1.2.
(1 mole).

(e) The ratio of total PATE prepolymer to total PTK prepolymer is 0.05 to 5 by weight.

(f) Conducting the reaction in the third step at a temperature range of 150 to 300°C. However, the reaction time at 210°C or higher is 10
Within hours.

(g) Melt viscosity of the block copolymer produced in the third step (measured at 350°C and shear rate of 12007 seconds)
Carry out the reaction until it becomes 2 to ioo, ooo boys.

Reaction Conditions> The reaction conditions in the P 1' K prepolymer and block copolymer synthesis step, which are the characteristics of the block copolymer production method of the present invention, will be described in further detail.

(1) Coexisting water content In the method for producing PTK prepolymers and block copolymers of the present invention, the coexisting water content in the reaction system is determined by the amount of water present in the organic amide solvent @1. 2.5-15 per kg
A desirable range is moles, more preferably 3.5 to 14 moles.

PTK with high thermal stability when the coexisting moisture content is less than 2.5 mol
Prepolymers and block copolymers are difficult to obtain, and decomposition reactions are also likely to occur during the reaction. On the other hand, if the amount of coexisting water exceeds 15 moles, the reaction rate decreases and only a low degree of polymerization can be obtained.

In order to adjust the amount of coexisting water in the reaction system, prior to the start of the reaction, reduce the amount of water by heat, etc., or reduce the amount of water by adding water. J11I can be performed.

(2) Monomer Charge Composition An important charge composition in the method for producing a block copolymer of the present invention is the ratio of the total amount of dihaloaromatic compounds charged to the total amount of alkali metal sulfides charged.

However, the amount of total alkali metal sulfide charged means the sum of the amount of alkali metal sulfide charged during PTK prepolymer and/or PATE prepolymer synthesis and the amount of alkali metal sulfide charged during block copolymer synthesis. do.

During block copolymer synthesis, the ratio of the total amount of dihaloaromatic compounds charged to the total amount of alkali metal sulfides charged is 0.
．． 95 to 1.2 (mol 1 mol), more preferably 0.9
7 to 1.10 (1 mole), more preferably 0.9
The range is preferably 8 to 1.05 (1 mol).

If this ratio is less than 0.95, it is difficult to obtain a block copolymer with excellent thermal stability, and decomposition reactions are likely to occur during the reaction. For other mosquitoes, if this ratio exceeds 1.2, it is not preferable because only a low molecular weight block copolymer can be obtained.

In addition, when synthesizing a block copolymer using only a part of each prepolymer produced by PTK prepolymer and/or PATE prepolymer synthesis, the amount of alkali metal sulfide charged and dihalogen The amount of aromatic compound to be charged is the value calculated by its usage ratio.

In addition, regarding the charging composition, regarding the ratio of the charging amount of alkali metal sulfide to the charging amount of organic amide solvent, the ratio of charging amount of alkali metal sulfide to j! 0.3 per mole of organic amide solvent
A range of 5 kg, more preferably 0.5 to 3 kg is desirable. If the amount of organic amide solvent charged is less than 0.3 kg, the viscosity of the reaction system becomes high, stirring becomes difficult, and decomposition reactions are likely to occur due to local heating, which is not preferable.

On the other hand, if the amount of organic amide solvent charged exceeds 5 kg, the amount of polymer produced per volume of the reactor will be low (which is economically disadvantageous). It is necessary that the ratio of the charged amount to the charged amount of all organic amide solvents be within the above range.

In the present invention, the term "amount J of alkali metal sulfide charged" refers to "amount J of alkali metal sulfide" when loss of alkali metal sulfide occurs before the start of the reaction due to dehydration operation or the like.

It means the amount remaining after subtracting the loss from the actual amount of preparation. Also, "amount of dihaloaromatic compound charged"
does not include the amount of the halogen-substituted aromatic compound added in the stabilization treatment (described later) at the final stage of the reaction.

(3) Reaction temperature and reaction time In the method for producing a PTK prepolymer of the present invention, the reaction is carried out at a temperature within the range of 60 to 300°C. Preferably 150-290°C, more preferably 220-280°C
is within the range of

If the reaction temperature is less than 60° C., it takes too much time to obtain a PTK prepolymer, which is economically disadvantageous. On the other hand, at temperatures exceeding 300℃.

It is difficult to obtain a PTK prepolymer with excellent thermal stability, and there is also a risk of decomposition occurring during the reaction.

In the method for producing a block copolymer of the present invention, the reaction is carried out at a temperature within the range of 150 to 300°C. Preferably 200-290°C, more preferably 210-280°C
within the range of ℃.

If the reaction temperature is less than 150° C., it takes too much time to obtain a block copolymer, which is economically disadvantageous. On the other hand, if the temperature exceeds 300°C, it will be difficult to obtain a block copolymer with excellent thermal stability (and there is a risk of decomposition occurring during the reaction).

The polymerization time required to obtain a PTK prepolymer and block copolymer with a desired molecular weight is shorter as the polymerization temperature is higher (on the contrary, it is longer as the polymerization temperature is lower. Therefore, the polymerization time is usually carried out at a high temperature of 210°C or higher. However, if the reaction is continued at a high temperature of 210°C or more for more than 10 hours, it will be difficult to obtain PTK prepolymers and block copolymers with excellent thermal stability. .

Therefore, in the present invention, the reaction is carried out at a temperature in the range of 150 to 300°C, and the reaction time at 210°C or higher is adjusted to within 10 hours.

(4) Reactor In the method for producing PTK prepolymers and block copolymers of the present invention, the reactor (preliminary operation for reaction,
(including equipment used for dehydration, etc.)
It is preferable that at least the portion that comes into direct contact with the reaction liquid is made of an inert, corrosion-resistant material that does not react with the reaction liquid.

Such corrosion-resistant materials include titanium materials such as titanium and alloys containing titanium, and corrosion-resistant materials containing nickel, such as Hastelloy C (t(aynesStellit)).
A heat-resistant nickel alloy manufactured by e, containing approximately 55 to 60 nickel.
%, molybdenum about 15-19%, chromium about 13-1
6% nickel-molybdenum-chromium alloy) or austenitic steel (e.g., about 28-38% nickel, about 19-21% chromium, about 3-3% copper)
4%.

In addition, it is preferable to use a reaction device made of Carpenter 20), which is a special austenitic steel containing molybdenum, etc. Among these, it is particularly preferable to use a reaction device made of titanium material.

Using a reactor constructed of corrosion-resistant materials such as those described above results in highly heat resistant and high molecular weight PTK prepolymers and block copolymers.

(5) Treatment at the final stage of the reaction Although a thermostable block copolymer can be obtained by the above production method, it is possible to further improve the thermal stability by adding a certain type of halogen-substituted aromatic compound to the reaction system at the final stage of the reaction. Improved block copolymers can be obtained.

However, in the present invention, the "end stage of the reaction" refers to the period after approximately 1/3 of the period from the start of the reaction to the end of the reaction. Note that the amount of the halogen-substituted aromatic compound added at the final stage of the reaction is not included in the amount of the dihaloaromatic compound mentioned above.

The halogen-substituted aromatic compound used in the stabilization treatment at the final stage of the reaction is at least one halogen-substituted aromatic compound containing one or more substituents having an electron-withdrawing property equal to or greater than that of the (-Co-) group. preferable.

Examples of such halogen-substituted aromatic compounds include bis(chlorobenzoyl)benzene, bis(polychlorobenzoyl)benzene, bis(bromobenzoyl)benzene, bis(polybromobenzoyl)benzene, 4.
4'-dichlorobenzophenone, 4.4'-dibromobenzophenone, dichlorobenzophenone excluding 4.4'-isomer, dibromobenzophenone excluding 4.4'-isomer, difluorobenzophenone, dichlorodiphenylsulfone, dibromodiphenylsulfone, monochloro Benzophenone, monobromobenzophenone, monofluorobenzophenone, chloroacetophenone, dichloroacetophenone, chloro, nitrobenynozene, etc.
and lv compounds thereof.

Among them, 4,4' dichlorobenzophenone and/or 4,4'-dibromobenzophenone used as monomers have an excellent effect of improving thermal stability, and the recovery and purification of the organic amide solvent used after the reaction is easy. This is particularly preferred because it is easy and economical.

The amount of the halogen-substituted aromatic compound used for the final reaction treatment is 0.1 to 100 mol, more preferably 0.5 to 20 mol, and even more preferably 1 to 10 mol per 100 mol of alkali metal sulfide. Mole is desirable. If the amount added is less than 0.1 mol, the effect of improving thermal stability is poor, and even if the amount is more than 100 mol, the improving effect tends to be saturated and is not economical.

In this reaction final stage treatment method, the above-mentioned halogen-substituted aromatic compound is added to the polymerization reaction system at the final stage of the reaction.
0°C, more preferably 550 to 290°C, more preferably 220 to 280°C, for 0.1 to 20 hours, more preferably 0.1 to 8 hours,
If it is less than 60°C or less than 0.1 hour, the reaction may be insufficient, and if it is more than 300°C or more than 20 hours, the thermal stability of the block copolymer may deteriorate, which is not preferable.

(6) Granulation conditions One of the major features of the method for producing a block copolymer of the present invention is that the block copolymer can be obtained in the form of granules by appropriately selecting the reaction conditions for the block copolymer described above. . At least 50% by weight of the block copolymer to be produced has a mesh size of 75 μm (200 μm).
The reaction conditions for obtaining granules that can be recovered through a mesh screen will be described in further detail.

(i) Content weight ratio of the total amount of block (A) and the total amount of block (B) in the block copolymer block (B)
) greatly contributes to the granulation of the block copolymer, so the weight ratio of block (B) contained in the block copolymer is an important condition. When the block copolymer of the present invention is to be obtained in the form of granules, the block (A)
It is necessary that the ratio of the total amount of block (B) to the total amount of block (B) be 0.2 or more in terms of weight ratio, preferably 0.
．． It is 3 or more, more preferably 0.4 or more.

If this ratio is less than 0.2, it will be difficult to obtain the block copolymer in the form of granules. On the other hand, if it exceeds 5, the heat resistance of the block copolymer will be greatly reduced, which is not preferable.

(ii) Reaction temperature and reaction time for granulation When the block copolymer is to be obtained as granules, the temperature should be raised to a high temperature of at least 240 to 290°C, more preferably 250 to 280°C, during or at the end of the reaction. is desirable.

If the reaction temperature is less than 240°C, it will be difficult to obtain a block copolymer in the form of granules, and if the reaction temperature exceeds 290°C, it will be difficult to obtain a block copolymer with excellent thermal stability.

The reaction time required to obtain the desired granulated block copolymer is shorter as the reaction temperature is higher; conversely, as the reaction temperature is lower, the reaction time is longer.
It is advantageous from the viewpoint of productivity to carry out the reaction at a high temperature of .degree. C. or higher. However, if the reaction takes place at a high temperature of 250°C or higher,
If this continues for more than a certain period of time, it becomes difficult to obtain a PTK prepolymer and block copolymer with excellent thermal stability.

C. To recover the block copolymer from the reaction solution, after the reaction (including the final stage treatment) is completed, the reaction solution is concentrated by removing part or all of the solvent by flashing and/or distillation. In some cases, the concentrated solution is further heated to remove residual solvent, the resulting solid or concentrated solution is washed with water and/or an organic solvent to remove soluble components such as formed salts, and then heated and dried again. A method for recovering the polymer can be applied.

By appropriately selecting the reaction conditions in the method for producing a block copolymer of the present invention, 50% by weight or more of the block copolymer to be produced has a mesh size of 75 μm (200 meshes), more preferably 106 μm (140 meshes), and still more preferably 150 μm (too many meshes). It can be obtained as a granulate that is sieved onto a mesh screen.

In this way, the block copolymer can be easily collected as particulate matter using a screen or the like from the reaction solution after the reaction is completed. A dry polymer can be obtained by washing the collected particulate polymer with water and/or an organic solvent and drying it by heating. Block copolymers are granular and have excellent handling properties, so they can be separated, washed, and
Transportation, weighing, etc. can be carried out easily.

(Left below) (Stabilized block copolymer) By adding a specific basic compound to the polyarylene thioether block copolymer of the present invention, the increase in melt viscosity due to thermal denaturation and thermal deterioration during melt processing can be prevented. It is possible to reduce and prevent deterioration of crystallinity, adhesion of thermal decomposition products in resin retention parts of melt processing equipment, etc. Moreover, when the basic compound and a specific antioxidant are used together, their stabilizing effects are further promoted.

The basic compound is a non-oxidizing, heat-resistant, and non-volatile compound, specifically, a metal of Group IIA of the periodic table (
However, hydroxides, oxides, and aromatic carboxylates of metals in Group IA of the periodic table (excluding magnesium), and aromatic carboxylates, carbonates, hydroxides, and phosphates (including condensates) of Group IA metals in the periodic table. ), borates (including condensates), and the like.

Among these basic compounds, hydroxides or oxides of calcium and barium; lithium aromatic carboxylic acids such as naphthalene mono- or polycarboxylic acids, arylbenzoic acids, benzene mono- or polycarboxylic acids, and hydroxybenzoic acids; , sodium or potassium salts are preferred. Among these, calcium and barium hydroxides are particularly preferred.

The blending ratio of the basic compound is 0.1 parts by weight per 100 parts by weight of the polyarylene thioether block copolymer.
-30 parts by weight, preferably 0.2-25 parts by weight, more preferably 0.3-20 parts by weight. If the proportion of the basic compound is less than 0.1 parts by weight, the stabilizing effect will be insufficient, and if it exceeds 30 parts by weight, there is a risk of decomposing the block copolymer or deteriorating the electrical properties. be.

Antioxidants used in combination with basic compounds include radical chain inhibitors and peroxide decomposers. Specifically,
Examples include hindered phenol compounds, phosphorus compounds, and hindered amine compounds.

Examples of hindered phenol compounds include l,
3.5-) riftyl-2,4,6-1-lis-(3,5
-di-t-butyl-4-hydroxybenzyl)benzene and its similar compounds; octadecyl-3-(3,5-
di-t-butyl-4-hydroxyphenyl)propionate, bentaenolithyltetrakis [3-(3,5
-di-t-butyl-4-hydroxyphenyl)propionate 1.2.2-thio-diethylenebis[3-(3,
5-di-t-butyl-4-hydroxyphenyl)propionate] and the like can be mentioned as a representative example.

As the phosphorus compound, one containing a trivalent phosphorus atom is preferably used.

Typical trivalent phosphorus compounds include tris(2,4-di-t-butylphenyl)phosphite and bis(2,6-di-t-butyl-4-methylphenyl). ) Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 4,4
'-biphenylene diphosphinic acid tetrakis (2,4
-di-t-butylphenyl] and the like.

A typical hindered amine compound is poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-1-riazine-2,4-diyl) ((2 , 2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)1 and similar compounds thereof.

Preferably, the antioxidant has low volatility and is difficult to decompose.
In particular, the above-mentioned phosphorus compounds are preferably used. The antioxidants can be used alone or in combination of two or more. When used together, a combination of a radical chain inhibitor and a peroxide decomposer is preferred.

The blending ratio of the antioxidant is 0 to 10 parts by weight based on 100 parts by weight of the polyarylene thioether block copolymer.
Parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. If the blending ratio of the antioxidant is less than 0.05 parts by weight, the stabilizing effect is insufficient,
On the other hand, if it exceeds the IO overlapping part, there is a risk that gas components will be generated in large quantities and electrical characteristics will deteriorate.

(Molded product) The polyarylenthioether-based block copolymer and the stabilized polyarylentioether-based block copolymer of the present invention can be molded into various molded products by the Funatsuri melt processing method.

The block copolymer of the present invention is fed, for example, into an extruder equipped with a shaping die or nozzle in the air or preferably in an inert gas atmosphere, and the cylinder temperature is 300 to 420°C. Average residence time of resin in cylinder 0
．． Extrusion and shaping for 5 to 60 minutes, preferably 2 to 30 minutes, and if necessary, at 150 to 350°C,
Various extruded products can be obtained by annealing for 1 to 100 hours.

For example, the block copolymer of the present invention is supplied to an injection molding machine equipped with a molding die in the atmosphere or preferably in an inert gas atmosphere, and the cylinder temperature is 300 to 400℃.
20°C, mold temperature 50-230°C, average resin residence time in the cylinder 1-3000 seconds, preferably 3-100 seconds.
Injection molding is carried out under the following molding conditions: 0 seconds, injection holding pressure 10-10'kg/cm, injection cycle 1-3000 seconds, and if necessary, annealing at 150-350°C for 1-100 hours. injection molded products can be obtained.

ii) A method of supplying the block copolymer of the present invention, for example, to an extruder equipped with a T-die in the atmosphere or preferably in an inert gas atmosphere, and melt-extruding it to form a film ( T-die method) or a method of pressing and shaping into a film while melting and heating using a high-temperature press (hot press method), if necessary at a temperature of 160 to 350 ° C. While applying stress (pressure), limit the deformation to within ±20% and heat set for 1 to 3000 seconds, and if necessary, further heat set for 1 to 3000 seconds at a temperature of 150 to 340°C under substantially no stress. An unstretched film can be obtained by thermal relaxation.

Further, an unstretched film can also be obtained by using a polyarylene thioether block copolymer by an inflation molding method or a compression molding method. moreover,
It can also be combined with other resins to form a multilayer film.

The unstretched film of the present invention is usually 0.5 to 5000 μm1
Preferably, it has an average thickness of 1 to 3000 μm.

The extruder, injection molding machine, and T-die extruder preferably have a portion that comes into contact with the resin melt made of a non-ferrous corrosion-resistant metal. Moreover, one with a vent is preferable.

From the block copolymer of the present invention, hollow molded products such as bottles, tanks, vibrators, tubes, etc. can be made by blow molding, and plates, etc. can be made by pultrusion molding, etc.
Long objects such as vibrators, tubes, rods, profiles, etc. can be obtained.

(Applications) The block copolymer of the present invention is crystalline and can be applied to general melt processing methods, and is molded into various heat-resistant molded articles and used for various purposes.

For example, extrusion molded products are used for sheets, plates, vibrators, tubes, coated wires, etc., injection molded products are used for electronic/electrical parts, automobile parts, etc., and unstretched films are used for magnetic recording base films, capacitors, etc. Used for films, printed wiring boards, insulating films, prepreg sheets, etc.

(Margins below) [Examples] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

[Example 1] (Manufacturing method 1) (Synthesis of PATE prepolymer) Hydrous soda sulfide (water content 54.0% by weight) 3.2 kg and N-methylpyrrolidone (hereinafter abbreviated as NMP) 6.5 kg
2.45 kg of NMP solution containing 1.358 kg of water and 13.4 g of hydrogen sulfide were poured out, and then 0.142 kg of water was charged into a titanium-lined polymerization can. and then p-
Dichlorobenzene (hereinafter abbreviated as PDCB) 2.443
A mixed solution of 3.82 kg of NMP and 3.82 kg of NMP was supplied.
Polymerization was carried out at 20° C. for 10 hours (PDCB/soda sulfide 01 mol, amount of coexisting water/NMP=3.1 mol/kg).

A reaction liquid slurry (S
) was taken, and the remaining monomer amount, terminal thiolate group, terminal thiol group, and terminal chlorine group were measured by the method described below.

PDCB in reaction slurry determined by gas chromato method
The amount of (residual monomer) was 0.3% by weight of the charged amount. The concentration of terminal thiolate groups and terminal thiol groups was 439 XlO-' equivalents per 1 g of prepolymer P+;
The concentration of terminal chlorine groups was 29XlO-' equivalents. The number average molecular weight of prepolymer P, determined from the number of these terminal groups, was 4274 (average degree of polymerization 40).

Shokyuhoba (Analysis of terminal thiol groups or thiolate groups) Immediately after the polymerization reaction of the prepolymer is completed, a portion of the reaction solution is sampled, poured into water to precipitate the prepolymer, separated by filtration, and placed in distilled water. The prepolymer samples were washed, then treated with dilute hydrochloric acid to convert the terminal thiolate groups to thiol groups, washed in distilled water for 30 minutes, acetone for 30 minutes, and dried under reduced pressure in a vacuum dryer at room temperature. Obtained.

Then, immediately weigh about 101 g to 1 g of the prepolymer sample, put it in a sealed test tube, and add 2.5 mβ of acetone.
and 2.5 ml of an acetone solution consisting of 50 mmol of iodoacetamide was added, sealed, heated at 100°C for 60 minutes, cooled with water, opened, and the liquid phase was separated.
Absorbance at 450 nm (absorbance of iodine) was measured using a spectrophotometer. Using a calibration curve prepared in advance for the model, the terminal thiol group concentration was calculated from the absorbance. (The sample amount is based on the concentration of thiol groups in the acetone slurry.
The same dry sample (appropriately selected so as to be in the millimolar range) was analyzed three times, and the average value of the terminal thiol group concentration was determined.

Analysis of terminal halogen atoms> Quantitative analysis of terminal halogen atoms was performed using a fluorescence Xl1 analyzer (Rigaku Denki ■, model 3080E2).

<How to determine the number average molecular weight> The number average molecular weight was determined from the measured values of the terminal thiol group (including the thiolate group) and the terminal halogen group using the following formula.

Number average Sample weight (g) Furthermore, the average degree of polymerization was calculated from the number average molecular weight.

(Block copolymer synthesis) Hydrous soda sulfide (water content 54.0% by weight) 2477g, 4
．． 688 g of 4'-dichlorobenzophenone (hereinafter abbreviated as DCBP), 8.212 g of the reaction solution slurry (S,)
20 kg, NMP 2.93 kg and water 1.09 kg
The mixture was charged into a titanium-lined polymerization can, and after purging with nitrogen, the temperature was raised and polymerization was carried out at 260°C for 2 hours.

The reaction conditions for synthesizing the block copolymer were as follows.

■The total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides (the sum of the effective amount of sodium sulfide charged during prepolymer P1 synthesis and the amount of sodium sulfide charged during block copolymer synthesis) [Prepolymer (Pl) synthesis] PDC of time
The molar ratio of the amount of B charged and the total amount of DCBP charged during block copolymer synthesis] was 1. It is Ol.

■The ratio of the amount of DCBP charged to the amount of PDCB during prepolymer (Pl) synthesis is approximately 0.47 by weight (
=32/68), and the molar ratio is approximately 0.28.

(2) The ratio of coexisting moisture to organic amide (NMP) is about 10 mol/kg.

(Recovery of Block Copolymer) The obtained reaction solution slurry was diluted with about the same amount of NMP, and the particulate polymer was separated using a screen with an opening of 150 μm (100 mesh).

NMP washing and water washing were repeated three times each, followed by drying under reduced pressure at 100° C. all day and night to obtain a block copolymer (B1). The recovery rate of block copolymer B was 80%.

(Attributes of Block Copolymer B) Block copolymer B1 was burr-shaped particles with an average particle size of 711 μm, and a bulk specific gravity of 0.58 g/d.

Infrared spectral analysis (IR) shows 1640 cm-
A sharp absorption peak based on the ketone group is observed at '. Wide-angle X-ray diffraction (using RAD-B system manufactured by Rigaku Denki ■) showed a diffraction pattern due to the block copolymer that was clearly different from PATH homopolymer, PTK homopolymer, and blends thereof.

The sulfur content in block copolymer B1 was determined by the combustion flask method and the ion chromatography method (IC method). That is, block copolymer 81 is burned in a flask, absorbed in hydrogen peroxide solution, and the sulfur content in the polymer is converted into a sulfuric acid radical using an ion chromatography device (Yokogawa Electric Corporation) equipped with a conductivity detector.
Company 1! The sulfur content was determined using JIC-500).

The weight fraction W, (wt%) in the block copolymer can be calculated by the following formula.

Wb=100X [Examples 2 to 8] (Manufacturing method 1) (P A, T
Synthesis of E prepolymer) Polyp was prepared in the same manner as in Example 1.
- A reaction liquid slurry (B2) containing a prepolymer P2 of phenylenethioether (PPTE) was obtained. The number average molecular weight of prepolymer P is 3760 (average degree of polymerization 35)
Met.

(Synthesis of block copolymers B2 to B8) Using hydrated sodium sulfide (water content 5460% by weight), DCBP, and reaction liquid slurry (B2) as shown in Table 1, the measured value W = 25.3
%, calculated value W1 = 1.5.01%, W, = 29.63%
The Wb obtained by substituting was 70%.

(Physical properties of block copolymer) The melt viscosity of block copolymer B was 250 voids. Tmc and ΔHmc are shown in Table 1.

Water and NM were added under the same polymerization conditions as in Example 1, except that the 1β autoclave was charged with
P was added, and polymerization, post-treatment, and drying were performed.

(Physical properties of block copolymer) The measurement results are summarized in Table 1. The melt viscosities of block copolymers B, B, B, and B were 410 voids, 390 voids, and 180 voids, respectively.

[Example 9] (Manufacturing method 1) Polymerization was carried out under the same polymerization conditions as in Example 6, except that instead of polymerizing at 260°C for 2 hours, it was polymerized at 230°C for 5 hours. The polymerization reactor was cooled, and the reaction liquid slurry was taken out and sieved through a screen with an opening of 75 μm (200 meshes), but no particulate polymer could be recovered. This slurry was poured into about 3 liters of acetone to precipitate the polymer, which was filtered using filter paper (Type 5 A), washed twice with acetone and water, and deliquified to obtain a wet polymer. The obtained wet polymer was dried at 100° C. to obtain a fine powder of polymer B9. The melt viscosity of the obtained block copolymer B9 was 35 voids.

The measurement results of physical properties etc. are summarized in Table 1.

[Comparative Example 1] (Synthesis of PTK homopolymer) 9.0 mol of DCBP, 9.0 mol of hydrous sodium sulfide (water content 53.6% by weight), and 9.0 mol of NMP. Pour Okg into a titanium polymerization can, replace it with nitrogen, and heat it at 240℃ for 2 hours and 26 hours.
The reaction was maintained at 0°C for 30 minutes (coexisting water content/NMP
= 5.0 mol/kg), the polymerization reactor was cooled, the slurry which was the reaction liquid was taken out, and part of it was heated to 75 μm (200 mol/kg).
However, no particulate polymer could be recovered.

Pour the remaining slurry into about 20 liters of acetone,
The polymer was precipitated and filtered, washed twice with acetone and water, and drained to obtain a wet polymer. The obtained wet polymer was dried under reduced pressure at 80° C. for 24 hours to obtain a fine powder of Polymer R (eye poly-colored powder).

The particle size of the obtained polymer R+ was measured using an image analyzer (Omnicon, Takasu Seisakusho ■). Average particle size is 10.6μ
m, particles with a diameter of 6 μm or less accounted for 60.5% by weight. Further, the amount of particles larger than 30 μm was only 0.4% by weight. The bulk specific gravity of Polymer R was 0.24 g/dj2.

The obtained polymer R3 is soluble in 98% concentrated sulfuric acid, but insoluble in α-chloronaphthalene even at 225°C.

[Comparative Example 2] (Pelletization experiment by redissolving homopolymer) 135 g of finely powdered PTK polymer R obtained in Comparative Example 1 and 65 g of polyp-phenylenethioether (Fortron #W214 manufactured by Kureha Chemical Co., Ltd.) , NMP500g, water 45g
The mixture was charged into a titanium polymerization can at 1° C. and maintained at 260° C. for 2 hours.

After cooling, the obtained slurry was separated into boxes using a screen with an opening of 75 μm (200 meshes), and the granular polymer was collected. Finely powdered polymer was recovered from the filtrate using filter paper (Type 5 A).

Each recovered polymer was washed and dried in the same manner as in Example 1 to obtain 151 g of granular polymer R and 37 [fine powder polymer].

Granular polymer R2, like poly p-phenylenethioether, was insoluble in 98% concentrated sulfuric acid and soluble in α-chloronaphthalene at 225°C. Moreover, its transition point was almost the same as that of poly p-phenylenethioether.

[Comparative Example 3] (Synthesis of random copolymer) DCBPo, 4 mol, hydrated sodium sulfide (water content 54.0% by weight) 0.5 mol, PDCBo, 1 mol, NMP500
g was charged into a lβ titanium polymerization can and reacted at 260°C for 2 hours [Coexisting water content/NMP = 5 mol/kg, DCB
P/PDCB=87/13 (weight ratio) 1° The slurry, which is a reaction liquid containing the random copolymer Rs, was dark brown and smelled of polymer decomposition.

As a result of gas chromatograph analysis, the remaining monomer was P.
DCB, which accounted for 33% of the amount charged. Although the reaction solution slurry was separated into boxes using a screen with openings of 75 μm (200 meshes), no particulate polymer could be recovered.

[Comparative Example 4] (Synthesis of random copolymer) Instead of DCBPo, 4 mol, PDCBo, 1 mol, D
Polymerization was carried out in the same manner as in Comparative Example 3, except that 1 mol of CBPo and 4 mol of PDCBo were charged [coexisting water content/NMP=5 mol/kg, DCBP/PDCB=30/
70 (weight ratio)].

The reaction liquid slurry was black-red and had a bad odor.

The particles were separated into boxes using a screen with an opening of 75 μm (200 meshes), but no particulate polymer could be recovered.

Finely powdered polymer was recovered from the filtrate using filter paper (Type 5 A), washed and dried in the same manner as in Example 1. The Tm of the resulting random copolymer R4 is 240° C., which is considerably lower than the melting points of poly p-phenylenethioether and PTK homopolymer.

[Comparative Example 5] (Pelletization experiment by redissolving PTK) 106 g of the fine powder PTK polymer obtained in Comparative Example 1 was
The mixture was charged into a 1β titanium polymerization can with 500 g of MP and 45 g of water and held at 260° C. for 2 hours. After cooling, the slurry was separated into boxes using a screen with openings of 75 μm (200 meshes), but no particulate polymer could be recovered.

[Comparative Example 6] (Synthesis of PTK homopolymer) 5 mol of DCBPo, 0.5 mol of hydrated sodium sulfide (water content 54.0% by weight), and 500 g of NMP were placed in a titanium polymerization can of 1I2, and the mixture was purged with nitrogen. The mixture was kept at 260°C for 2 hours to react. The polymerization reactor was cooled, and the reaction liquid slurry was sieved through a screen with openings of 75 μm (200 meshes), but no particulate polymer could be recovered.

[Example 1O] (Production method 2) (Synthesis of PTK prepolymer) DCBPo, 531 mol, hydrated sodium sulfide (moisture 54.
0% by weight) 0.282 mol, 77 g of water and NMP51
1 g was placed in a 72 titanium polymerization can, the atmosphere was replaced with nitrogen, and 2
React by holding at 00°C for 1 hour (coexisting water content/NMP
= about 11 mol/kg), and a reaction liquid slurry (KS, ) containing a PTK prepolymer (K, ) was obtained.

(Synthesis of block copolymer) Reaction liquid slurry 3 containing the PPTE prepolymer P8
．． 489.5g, 'PTK prepolymer containing 1 reaction liquid slurry KS, 315.4g, water 31.7g lI2
It was charged into a titanium polymerization can, purged with nitrogen, and heated at 260℃ for 2 hours.
The mixture was allowed to react for a certain period of time.

The reaction conditions for synthesizing the block copolymer were as follows.

■Total amount of dihaloaromatic compound charged (synthesis of prepolymer P2) relative to total amount of alkali metal sulfide charged (total amount of sodium sulfide charged during synthesis of prepolymer P2 and amount of sodium sulfide charged during synthesis of PTK prepolymer 1) The molar ratio of the amount of PDCB charged at time to the amount of DCBP charged to the PTK prepolymer at the time of synthesis] was 1.04.

■The ratio of PATH block and PTK block is approximately 58+
42 (weight ratio).

(2) The ratio of coexisting water content to the amount of organic amide (NMP) charged is approximately 9.5 mol/kg.

(Recovery of block copolymer) The obtained reaction liquid slurry was diluted with about the same amount of NMP, sieved to remove particulate polymer using a screen with an opening of 150 μm (100 meshes), and washed with NMP and water three times. Repeatedly drying under reduced pressure at 100°C overnight until the average particle size was 68.
A bur-shaped polymer B1° of 3 μm was obtained.

The recovery rate was 78%.

(Physical properties of block copolymer) Block copolymer B. The melt viscosity was 199 voids. Tmc, ΔHmc, etc. are collectively shown in Table 1.

(Left below) [Example 11] (Manufacturing method 2) (Synthesis of PATH prepolymer) 3.2 kg of hydrated sodium sulfide (water content 53.7% by weight) and 6.0 kg of NMP were charged into a titanium-lined polymerization tube, and nitrogen gas was added. While gradually raising the temperature to 200℃ in an atmosphere, water 1
．． 2.541 kg of rllP solution containing 326 kg and 0838 mol of hydrogen sulfide were distilled, and then 0.123 kg of water
and then PDCB2.35kg and NMP4.51
kg, and polymerized at 220° C. for 10 hours (PDCB/sodium sulfide = 0.86 mol 1 mol, coexisting water content/NMP = approximately 3 mol/kg) to produce PPTE prepolymer P. A reaction liquid slurry S was obtained. The number average molecular weight of prepolymer P is 1530 (average degree of polymerization 1
4).

(Synthesis of PTK prepolymer) 3.640 mol of DCBP, hydrated sodium sulfide (water content 53.0 mol)
7% by weight) 2.039 mol, 176 g of water and NMP4
．． 004 kg was charged into a 2012 titanium polymerization can, purged with nitrogen, and kept at 220°C for 1 hour to react (coexisting water content/NMP = approximately 5 mol/kg) to form a reaction liquid slurry containing PTK prepolymer (K2). (KSz) was obtained.

(Synthesis of block copolymer) Reaction liquid slurry KS containing 2 in the PTK prepolymer
A charge bot equipped with a heating device was attached to a 20ρ titanium polymerization can containing 2 (slurry temperature 220°C), and 9.12 kg of the reaction slurry Ss containing the PPTE prepolymer P was charged into this pot. After the temperature was raised to 220° C., the PTK prepolymer was added to a reaction liquid slurry K S 2 containing 2, and further 1.146 g of water was added and mixed.

The reaction mixture was further maintained at 260°C for 2 hours, and after the temperature was lowered to 240°C, the final stage of the reaction was carried out. In the final stage of the reaction, 4356 mol of DCBPo and 5 kg of NMPo were added and then heated at 240°C for 0. This was carried out by reacting for 2 hours.

The reaction conditions for synthesizing the block copolymer were as follows.

■Total amount of dihaloaromatic compound charged relative to the total amount of alkali metal sulfide (total amount of sodium sulfide charged during synthesis of prepolymer P3 and amount of sodium sulfide charged during synthesis of prepolymer 2) [during synthesis of prepolymer P8] The molar ratio of the amount of PDCB charged, the prepolymer, and the total amount of DCBP charged at the time of synthesis] was 0.99.

■The ratio of PATH block and PTK block is approximately 60:
40 (weight ratio).

(2) The ratio of the amount of coexisting water to the amount of organic amide (NMP) charged is about 10 mol/kg.

(Recovery of block copolymer) In the same manner as in Example 10, block copolymer B++
I got it. The recovery rate was 78%.

(Physical properties of block copolymer) The physical properties of block copolymer B I+ are as follows.

Melt viscosity; 650 Boies transition temperature; 7g 104℃ Tm 301℃ and 324℃ Melt crystallization temperature; T m c (400℃) 252℃ T m c (400℃/10 minutes) 221℃ Melt crystallization enthalpy; ΔHm c ( 400°C) 43 J/g Residual melt crystallization enthalpy; ΔHm c (400°C 710 minutes) 36 J/g
The ratio (weight ratio) of the total amount of PATH repeating units to the total amount of TK repeating units was 1.6 (62/38).

(Solubility of block copolymers in solvents) Block copolymer B1, block copolymer Blt synthesized in Examples, PTK homopolymer R1 synthesized in Comparative Example 1, and poly p-phenylenethioether (Fortron ■ #W214 manufactured by Kureha Chemical Industry ■) After each heat press,
Cool to create amorphous sheets, and each amorphous sheet is
The dissolution behavior was investigated by placing it in the solvent shown in the table.

As shown in Table 2, the block copolymer has properties different from those of the homopolymer of its constituent units, such as PTK homopolymer and poly p-phenylenethioether homopolymer.

(Left below) [Example 12] (Production method 2) During PATE prepolymer synthesis, the ratio of the amount of PDCB charged to the amount of sodium sulfide was set at 0.94 (1 mol).
The molar ratio of the total amount of dihaloaromatic compound to the total amount of alkali metal sulfide charged during block copolymer synthesis was adjusted by adjusting the ratio of the amount of DCBP charged to the amount of sodium sulfide charged during PTK prepolymer synthesis. The reaction and post-treatment were carried out in the same manner as in Example 11, except that Bl! was set to 1.01, and the block copolymer Bl! I got it. Recovery rate is 77%
Met.

(Physical properties of block copolymer) The physical properties of block copolymer 81□ are as follows.

Melt viscosity; 350 Boyes Melt crystallization temperature; T m c (400°C, 710 minutes) 228°C Residual melt crystallization enthalpy ΔHm c (400°C, 710 minutes) 4. OJ/g.
The ratio (weight ratio) of the total amount of PATH repeating units to the total amount of PTK repeating units was 1.3 (63/47).

[Example 13] Regarding block copolymer B1 synthesized in Example 1,
Various basic compounds were added to this and the melt stability was investigated.

That is, dry powders of various basic compounds were added to block copolymer B1, and after blending using a tumbler blender, the cylinder diameter was 19 mmφ, L/D = 25
The block copolymers containing basic compounds are fed into a single-screw extruder, melt-kneaded at a cylinder temperature of 350°C, extruded into strands, cooled, and cut to form pellets of each basic compound-containing block copolymer.
Samples were prepared. This was used as a sample for melt stability evaluation.

The melt stability of each stabilizer-containing pellet was evaluated as follows. That is, approximately 20 g of pellets were placed in the barrel of a cavilograph heated to 350 °C, and the melt viscosities η6, η, 0, and ηgo (measured at a shear rate of 1200/sec) after 5, 30, and 60 minutes were measured. measure,
η:. /η;, η:0/η: were determined. The ratio of these is 1
The closer the value is to the value, the better the melt stability is. Also,
Block copolymer B to which no basic compound is added,
The melt viscosities and their ratios were also measured in the same manner.

The results are summarized in Table 3.

[Comparative Example 7] A pellet was prepared in the same manner as in Example 13, except that NaCβ and calcium stearate were added as additive compounds, and each melt viscosity and their ratio were measured (Experiment Nos. 7-1 and 7). -2).

In addition, 0 parts of calcium hydroxide was added to 100 parts by weight of polyarylene thioether ketone homopolymer (PTK-1).
．． A pellet was prepared in the same manner as in Example 13, except that a composition containing 5 parts by weight was used and the cylinder temperature was 370"C, and each melt viscosity and their ratio were measured (
Experiment number 7-3).

Furthermore, polybara phenylene thioether (manufactured by Kenbetsu Kagaku Kogyo Co., Ltd.; 1
- in chloronaphthalene, concentration 0.4 g/dJ2.208
The solution viscosity at 77 inh (°C) is 0.48).A pellet was prepared by blending 100 parts by weight with 0.5 parts by weight of calcium hydroxide, and the melt viscosity η: η,. and η,. /η: was measured (Experiment No. 7-4).

The results are summarized in Table 3.

Note that PTK-1 used in Experiment No. 7-3 was synthesized as follows.

90 moles of DCBP, 90 moles of hydrous sodium sulfide (water content 53.6% by weight), and 90 kg of NMP were charged into a titanium polymerization can (coexisting water content/NMP = 5 moles/kg), and after nitrogen substitution, the temperature was raised from room temperature to 240°C by 1.5%. The temperature rises in 24 hours.
The mixture was kept at 0°C for 2 hours to react. Next, for stabilization treatment at the final stage of the reaction, 4.5 mol of DCBP and 18 mol of NMP were added.
kg and 90 moles of water were added, and the reaction was further carried out at 240°C for 1 hour.

The polymer chain is cooled, and the reaction solution slurry is taken out and poured into about 200β acetone to precipitate the polymer, filtered, washed twice with acetone and water, and deliquified to remove the wet polymer. Obtained.

The obtained wet polymer was dried under reduced pressure at 100° C. for 12 hours to obtain PTK-1. The melting point of this PTK-1 (powder) was 360°C.

In addition, PTK-1 was added to 98% sulfuric acid at a concentration of 0.5 g/
The reduced viscosity ηred measured at 25°C using an Ubbelohde viscosity tube is 0.63d.
β/g.

(Left below) As is clear from Experiment No. 13-1 in Table 3, the block copolymer of the present invention does not melt even when held at 350°C for 30 minutes, which is around the melt processing temperature, even without adding a stabilizer. The viscosity remains almost unchanged, indicating good melt stability.

From Experiment Nos. 13-2 to 13-6, the melt stability was further improved by adding a basic compound to this block copolymer, and the melt viscosity hardly changed even after being held at 350°C for 60 minutes. I can see that there isn't.

Also, the adhesion of decomposition products to the barrel of the cavilograph was reduced.

On the other hand, from Experiment Nos. 7-1 and 7-2, it can be seen that even if NaCl2 or calcium stearate is added, there is no melt stabilizing effect, or the melt stability is actually inhibited, such as by foaming.

In addition, for PTK homopolymer, the addition of calcium hydroxide has a melt stabilizing effect (Experiment No. 7-
3) For PATH homopolymer, η of pellets extruded without adding a basic compound. /η; was 0.7, whereas ηso/η5 of the pellet to which calcium hydroxide was added was 0.4 (Experiment No. 7-4), indicating that the melt stability was rather deteriorated.

[Example 14] As a block copolymer, B1 synthesized in Example 1 or B synthesized in Example 11 was used, and these polymers were treated with a basic compound shown in Table 4, or a basic compound and an antioxidant. was added, pellet samples were prepared in the same manner as in Example 13, and the melt stability was examined. However, in order to expand the evaluation of the differences in melt stability of each sample, in addition to the evaluation conditions of 350°C and a shear rate of 1200/sec, we used the value of melt viscosity measured at 370°C and a shear rate of 1200/sec. there was.

The measurement results are shown in Table 4.

As is clear from Table 4, melt stability is improved by adding a basic compound and an antioxidant to the block copolymer of the present invention.

Additionally, the adhesion of decomposition products to the barrel of the cavilograph has been significantly reduced.

In addition, in Table 4, each antioxidant used is as follows.

±Z ball rising 1 (a) PEP 36; (7' Deca-Y-Nsu Co.,
Product name MARK PEP36) Bis-(2,6-di
-tert-butyli-methyl pheny
l)-pentaerythritoldiphosp
Hite (b) IRGAFO3168; (Ciba Geigy, product name) Trts (2,4-di-t
ert-butylphenyllphosphorite
(cl P-EPQ; (Sandoz Co., product name 5A)
NDSTAB P-EPQ) Phosphorous
acid[1,1-biphenyl-4,4'diy
l-bis tetrakis [2,4-bis(
1,1-dimethyl-ethyl)phenyl
] ester] (d) WESTON 618
．． (Polgreener, product name) Distear
yl pentaerythritol diphos
phite hindered phenol human (e) AO-220, (7'Deca・7-Gas Co., Ltd.,
Product name) 1,3.5-trimethyl-2,4,
6-tris-(3,5-di-tert-butyl
-4-hydroxybenzyl)benzene similar compound hindered amine 4 (f) CHIMASSORB 944 LD; (Ciba Gai X- Co., Ltd., trade name) PoLy [(6-(L, L,
3.3- tetramethylbut/Llimi
n.

-1,35-triazine-2,4-diil)
((2,2,6,6-tetramethyl-4
-piperidyl) iminolhexamet
hylene ((2,2,6,6-tetramet
hyl-4-piperidyl)iminol](
(Left below) [Example 15] Using block copolymer B synthesized in Example 1, pellet samples were prepared according to the formulation shown in Table 5.

These pellets are fed into an injection molding machine under a nitrogen stream,
An injection molded product was obtained by molding under the following molding conditions: cylinder temperature of 350°C, mold temperature of 160°C, injection and holding pressure of 1000 kg/cm, and injection cycle of about 40 seconds.

By adding the stabilizer, long-run properties during molding were improved and the adhesion of decomposition products to processing machines was reduced.

Table 5 shows the formulation and the physical properties and solvent resistance of the injection molded product.

(Margins below) Table (*1) Manufactured by Adeka Argus, product name MARK (12
Immersed at 1225°C for 5 minutes (N 3) Immersed at 200°C for 5 minutes (Umbrella 4) Immersed at room temperature for 30 minutes EP36 [Example 16] Using block copolymer B1 synthesized in Example 1, Beret samples were prepared according to the formulation shown in Table 6.

These pellets were fed into a 35mmφ single-screw extruder equipped with a small T-die, melted and extruded at a cylinder temperature of 350°C, and rapidly cooled with a cooling roll, each having an average thickness of 150μ.
An unstretched film of m was prepared.

The resulting unstretched film was cut into pieces with a width of 10 mm and a length of 20 mm, and the strength and elongation were measured using a Tensilon (RTM-100 model, manufactured by Toyo Baldwin Co., Ltd.). The measured temperature is 23
℃, and the deformation rate was 10 mm/min (50%/min).

Addition of the stabilizer improved long-run performance during molding and reduced adhesion of decomposition products to processing machines.

In addition, the soldering heat resistance (10 seconds) is determined by applying 2
The time-annealed sample was immersed for 10 seconds.
It is expressed as the highest solder bath temperature that does not cause changes in appearance such as wrinkles or deformation. The solder bath temperature was controlled in 5°C increments.

The results are shown in Table 6.

Table 6 (*l) Manufactured by Adeka Argus, product name AO-220 (
$2) By [lithium bromide/water] system density gradient tube method.

($3) Annealed at 280℃ for 30 minutes.

(Book 4) Immersed at 225°C for 5 minutes ($5) Immersed at 200°C for 5 minutes (Book 6) Immersed at room temperature for 30 minutes (blank below) [Effects of the Invention] According to the present invention, heat resistance, workability, It is possible to economically provide a crystalline polyarylene thioether block copolymer that has excellent handling properties. Further, according to the present invention, it is possible to provide a stabilized polyarylene thioether block copolymer.

Furthermore, according to the present invention, various molded products made of polyarylene thioether block copolymers can be obtained.

Claims (27)

[Claims] (1) Polyarylene thioether ketone whose main constituent is a repeating unit ▲ Numerical formulas, chemical formulas, tables, etc.・Block (A) and repeating unit ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ A polyarylene thioether block copolymer containing alternating at least one or more polyarylene thioether blocks (B) each having the following as its main constituents, (A) block ( Block (B) for the total amount of A)
(b) the average degree of polymerization of the block (B) is 10 or more, and (c) the melt viscosity (350°C, shear rate 1200/sec). 2 to 100,000 poise), defined as: (2) The melt crystallization temperature Tmc (400°C/10 minutes) of the polyarylene thioether block copolymer is 17
At 0°C or higher, the residual melt crystallization enthalpy ΔHmc (4
2. The polyarylene thioether block copolymer according to claim 1, wherein the polyarylene thioether-based block copolymer has a heat dissipation rate (00°C/10 minutes) of 10 J/g or more. [However, Tmc (400°C/10 minutes) and ΔHmc
(400°C/10 min) is a differential scanning calorimeter. After holding the block copolymer at 50°C for 5 minutes in an inert gas atmosphere, the temperature was raised to 400°C at a rate of 75°C/min.
These are the melt crystallization peak temperature and melt crystallization enthalpy when the temperature was lowered at a rate of 10° C./min after holding the temperature for 10 minutes. ] (3) The polyarylene thioether block copolymer according to claim 1, wherein the polyarylene thioether block (B) has a repeating unit ▲a mathematical formula, a chemical formula, a table, etc.▼ as a main constituent. (4) The polyarylene thioether based block copolymer according to claim 1, wherein the ratio of the total amount of blocks (B) to the total amount of blocks (A) is in the range of 0.05 to less than 1 in terms of weight ratio. block copolymer. (5) The polyarylene thioether block copolymer according to claim 1, wherein the ratio of the total amount of blocks (B) to the total amount of blocks (A) in the polyarylenchioether block copolymer is in the range of 1 to 5 by weight. (6) [1] In the presence of moisture, a dihaloaromatic compound containing dihalobenzene as the main component and an organic amide solvent containing an alkali metal sulfide are heated to form a repeating unit ▲Mathematical formula, chemical formula, table, etc.▼ A first step of forming a reaction solution containing a polyarylene thioether prepolymer having a reactive end group as a main component; [2] The reaction solution obtained in the first step and 4,4'-dichlorobenzophenone and/or a dihaloaromatic compound mainly composed of dihalobenzophenone consisting of 4,4'-dibromobenzophenone, an alkali metal sulfide, an organic amide solvent, and water, and heating the mixture to produce a repeating unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, -CO- group and -S- group are bonded to the para position via a benzene ring] Generates a polyarylene thioetherketone block whose main constituent is A polyarylene thioetherketone block (A) and a polyarylene comprising at least two steps of a second step, and the reaction in each step is carried out under the following conditions (a) to (f). Thioether
A method for producing a polyarylene thioether block copolymer containing block (B). (a) In the first step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0. .8 to 1.05 (mol/mol), and polymerization is carried out until the average degree of polymerization of the polyarylene thioether prepolymer becomes 10 or more. (b) In the second step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg). (c) In the second step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (total amount of alkali metal sulfides charged in the first step and second step) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0.95 to 1.2.
(mole/mole). (d) The ratio of the charged amount of the dihalo aromatic compound containing dihalobenzophenone as the main component to the charged amount of the dihalo aromatic compound containing dihalobenzene as the main component is in the range of 0.1 to 10 (mol/mol). to do. (e) Conducting the reaction in the second step at a temperature range of 150 to 300°C. However, the reaction time at 210°C or higher is 10
Within hours. (f) Melt viscosity of the block copolymer produced in the second step (measured at 350°C and a shear rate of 1200/sec)
The reaction should be carried out until the value is 2 to 100,000 poise. (7) The method for producing a polyarylene thioether block copolymer according to claim 6, wherein the polyarylenchioether prepolymer has a repeating unit ▲a mathematical formula, a chemical formula, a table, etc.▼ as a main constituent. (8) The method for producing a polyarylene thioether block copolymer according to claim 6, wherein a reaction apparatus is used in which at least the part in contact with the reaction liquid is made of a corrosion-resistant material. (9) The method for producing a polyarylene thioether block copolymer according to claim 8, wherein the corrosion-resistant material is a titanium material. (10) The method for producing a polyarylene thioether block copolymer according to claim 6, wherein the organic amide solvent is at least one selected from N-methylpyrrolidone and N-ethylpyrrolidone. (11) The polyarylene thioether according to claim 6, wherein in obtaining the polyarylene thioether block copolymer, 50% by weight or more of the resulting block copolymer is a granular material that can be collected through a mesh with an opening of 75 μm. A method for producing block copolymers. (12) [1] In the coexistence of moisture, a dihaloaromatic compound containing dihalobenzene as the main component and an organic amide solvent containing an alkali metal sulfide are heated to form a repeating unit ▲Mathematical formula, chemical formula, table, etc.▼ A first step of forming a reaction solution containing a polyarylene thioether prepolymer having a reactive end group as a main component; [2] 4,4'-dichlorobenzophenone and/or 4,4, in the presence of water; By heating a dihaloaromatic compound mainly composed of dihalobenzophenone consisting of 4'-dibromobenzophenone and an organic amide solvent containing an alkali metal sulfide, repeating units ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, -CO- group and -S- group are bonded to the para position via a benzene ring] is the main constituent, and the second step is to form a reaction solution containing a polyarylene thioetherketone prepolymer having a reactive end group. and [3] a third step of mixing and reacting the reaction solution containing the polyarylene thioether prepolymer obtained in each of the above steps with the reaction solution containing the polyarylenchioether ketone prepolymer. A polyarylene comprising a polyarylene thioether ketone block (A) and a polyarylene thioether block (B), characterized in that the reactions in each step are carried out under the following conditions (a) to (g). A method for producing a thioether block copolymer. (a) In the first step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 0.2 to 5 (mol/kg), and the ratio of the amount of dihaloaromatic compound charged to the amount of alkali metal sulfide charged is 0. .8 to 1.05 (mol/mol), and polymerization is carried out until the average degree of polymerization of the polyarylene thioether prepolymer becomes 10 or more. (b) In the second step, the ratio of the amount of coexisting water to the amount of organic amide solvent charged is 2.5 to 15 (mol/kg),
The reaction is carried out at a temperature in the range 60-300°C. However, the reaction time at 210°C or higher must be within 10 hours. (c) In the third step, the ratio of the amount of coexisting water to the organic amide solvent is in the range of 2.5 to 15 (mol/kg). (d) In the third step, the total amount of dihaloaromatic compounds charged relative to the total amount of alkali metal sulfides charged (the total amount of alkali metal sulfides charged in the first and second steps) (
The ratio of the total charge amount of dihaloaromatic compounds containing dihalobenzene and dihalobenzophenone is 0.95 to 1.2.
(mole/mole). (e) The ratio of the total polyarylene thioether prepolymer to the total polyarylenchioether ketone prepolymer is 0.05 to 5 by weight. (f) Conducting the reaction in the third step at a temperature range of 150 to 300°C. However, the reaction time at 210°C or higher is 10
Within hours. (g) Melt viscosity of the block copolymer produced in the third step (measured at 350°C and shear rate of 1200/sec)
The reaction should be carried out until the value is 2 to 100,000 poise. (13) The method for producing a polyarylene thioether-based block copolymer according to claim 12, wherein the polyarylene thioether prepolymer has a repeating unit ▲a mathematical formula, a chemical formula, a table, etc.▼ as a main constituent. (14) The method for producing a polyarylene thioether block copolymer according to claim 12, wherein a reaction apparatus is used in which at least the part in contact with the reaction liquid is made of a corrosion-resistant material. (15) The method for producing a polyarylene thioether block copolymer according to claim 12, wherein the corrosion-resistant material is a titanium material. (16) The method for producing a polyarylene thioether block copolymer according to claim 12, wherein the organic amide solvent is at least one selected from N-methylpyrrolidone and N-ethylpyrrolidone. (17) The polyarylene thioether according to claim 12, wherein in obtaining the polyarylene thioether block copolymer, 50% by weight or more of the produced block copolymer is a granular material that can be collected through a mesh with an opening of 75 μm. A method for producing block copolymers. (18) A molded article comprising the polyarylene thioether block copolymer according to claim 1. (19) A molded article comprising the polyarylene thioether block copolymer according to claim 2. (20) A molded article comprising a polyarylene thiolether block copolymer according to claim 18, wherein the molded article is an extrusion molded article, an injection molded article, or an unstretched film. (21) A molded article comprising a polyarylene thiolether block copolymer according to claim 19, wherein the molded article is an extrusion molded article, an injection molded article, or an unstretched film. (22) For 100 parts by weight of the polyarylene thioether block copolymer according to claim 1,
Hydroxides, oxides, aromatic carboxylates of Group IA metals (excluding magnesium); Aromatic carboxylates, carbonates, hydroxides, phosphates of Group IA metals of the Periodic Table ( at least one basic compound selected from the group consisting of: (including condensates), borates (including condensates);
1 to 30 parts by weight, and 0 to 10 parts by weight of at least one antioxidant selected from hindered phenol compounds, phosphorus compounds, and hindered amine compounds. block copolymer. (23) The melt crystallization temperature Tmc (400°C/10 minutes) of the polyarylene thioether block copolymer is 1
At 70°C or higher, the residual melt crystallization enthalpy ΔHmc (
400°C/10 minutes) is 10 J/g or more.
The stabilized polyarylene thioether block copolymer described. (24) A molded article comprising the stabilized polyarylene thioether block copolymer according to claim 22. (25) A molded article made of the stabilized polyarylene thioether block copolymer according to claim 24, wherein the molded article is an extrusion molded article, an injection molded article, or an unstretched film. (26) A molded article comprising the stabilized polyarylene thiolether block copolymer according to claim 23. (27) A molded article made of the stabilized polyarylene thioether block copolymer according to claim 26, wherein the molded article is an extrusion molded article, an injection molded article, or an unstretched film.