JPH02133428A - Block copolymer, its production and resin composition - Google Patents

Abstract

PURPOSE:To produce a block copolymer of improved heat resistance by forming a polyphenylene sulfide-containing reaction solution in the first step and performing the formation and bonding of a phenylene sulfide ketone part in the second step by using the reaction solution. CONSTITUTION:An aprotic polar organic solvent (e.g., N-methyl-2-pyrrolidone) containing a dihalobenzene (e.g., p-dichlorobenzene) and an alkali metal sulfide (e.g., sodium sulfide) is heated to form a reaction solution containing a polyphenylene sulfide (step 1). A dihaloaromatic ketone (e.g., 4,4'- dichlorobenzophenone) is added to this reaction solution, and the obtained mixture is heated in the presence of an alkali metal sulfide and an aprotic polar organic solvent to form a block copolymer (step 2). Thus, a block copolymer comprising a polyphenylene sulfide part and a polyphenylene sulfide ketone part can be obtained, and this copolymer is excellent in heat resistance.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is based on a polyphenylene sulfide (hereinafter referred to as PPS) moiety and a polyphenylene sulfide ketone (hereinafter referred to as PP) moiety.
The present invention relates to a block copolymer consisting of a portion (referred to as 5K), a method for producing the same, and a resin composition with further improved heat resistance than PPS resin.

BACKGROUND ART PPSVII resin has excellent properties as an engineering plastic, such as excellent chemical resistance, heat resistance, and electrical insulation properties, and is used for various purposes, mainly injection molding.

-a, electronic components such as ICs, transistors, resistors, or capacitors are coated or sealed with synthetic resin such as epoxy resin for the purpose of maintaining electrical insulation, mechanical protection, and preventing changes in characteristics due to external atmosphere. This is widely practiced.

Since ppsti resin has the above-mentioned excellent properties, it has recently been expected to be applied to the field of sealants for electronic components. On the other hand, with the recent rapid progress toward higher integration of ICs and surface mounting of circuits, further improvements in heat resistance such as solder resistance are required for encapsulants.

To meet this demand, by blending a polymer with even more heat resistance than ppsvA resin, we have developed a highly heat-resistant plastic.
Attempts have been made to create glue compositions made of psm fat. Kaisho 63-356
No. 53 discloses a method of blending polyparabanic acid.

On the other hand, as a block copolymer of PPS, JP-A-61
-14228 discloses a pro-7 copolymer with polym-phenylene sulfide, JP-A-61225218 discloses a block copolymer with polysulfone, and JP-A-61225218 discloses a block copolymer with polysulfone.
JP-205157 discloses a block copolymer with polyphenylene sulfide sulfone.

<Problem to be solved by the invention> However, the above-mentioned Japanese Patent Application Laid-Open No. 53-73228, Japanese Patent Application Laid-Open No. 56-45506, and Japanese Patent Application Laid-Open No. 63-356
In the method described in Publication No. 53, the resins are not compatible with each other,
The compatibility was insufficient, there was almost no improvement in heat resistance, and it was far from being practical.

On the other hand, JP-A-61-14228, JP-A-61-2
The methods disclosed in JP-A No. 25218 and JP-A No. 62-205157 both attempt to improve the brittleness of ppsVA fat by introducing a block of non-grade polymer into PPS. There was no effect at all on increasing the heat resistance of PPS resin.

Therefore, the present invention has higher heat resistance and i
An object of the present invention is to obtain a block copolymer having the following properties, to efficiently produce the block copolymer, and to obtain a resin composition having higher heat resistance than PPS resin.

Means for Solving the Problems> That is, the present invention consists of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety,
A first step is to heat an aprotic polar organic solvent containing a block copolymer, dihalobenzene, and an alkali metal sulfide with a melt flow rate in the range of 1 to 1,000 °C to produce a reaction solution containing polyphenylene sulfide. The second step consists of adding a dihaloaromatic ketone to the reaction solution and heating it in the presence of an alkali metal sulfide and an aprotic polar organic solvent to produce a block copolymer. A method for producing a block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, characterized by heating a protic polar organic solvent containing a dihaloaromatic ketone and an alkali metal sulfide to produce a polyphenylene sulfide ketone. a first step of producing a reaction solution containing dihalobenzene, and heating the reaction solution in the presence of an alkali metal sulfide and an aprotic polar organic solvent;
A method for producing a block copolymer comprising a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, the method comprising a second step of producing a block copolymer, an aprotic polar organic compound containing dihalobenzene and an alkali metal sulfide; A first step of heating a solvent to produce a reaction solution containing polyphenylene sulfide, and heating an aprotic polar organic solvent containing a dihaloaromatic ketone and an alkali metal sulfide to produce a reaction solution containing polyphenylene sulfide. a second step of producing a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, and a third step of mixing and heating the reaction liquid obtained in each step to produce a block copolymer. and a resin composition comprising a block copolymer comprising a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, and polyphenylene sulfide and/or polyphenylene sulfide ketone.

The block copolymer of the present invention is a polymer containing 70 mol % or more, more preferably 90 mol % or more of PP 8-position constituting the block copolymer of the present invention, and when the repeating unit is less than 70 mol %, the block copolymer has excellent properties. Hard to get.

Furthermore, less than 30 mol% of the repeating units in the PPS portion can be composed of repeating units having the following WA structural formula.

On the other hand, the block copolymer of the present invention is a polymer containing 70 mol % or more, more preferably 90 mol % or more of the repeating unit represented by Copolymers are difficult to obtain.

In addition, the above PP5K portion is 30 mol% of its repeating unit.
It is possible to construct the following unit with a repeating unit having the following structural formula.

The molar ratio of the PPS moiety and the PP5K moiety in terms of repeating units in the block copolymer of the present invention is arbitrary. This block copolymer has a melt flow rate at 372°C of 1 to i, ooo. Usually, the block copolymer of the present invention has a glass transition temperature (Tg) of 70 to 15
It has a crystal melting point (Tm) of 260 to 370°C at 0°C.

Tg and Tm are determined by measuring 10 mg of a sample in a substantially amorphous state that has been rapidly cooled from a molten state using a PerkinElmer differential scanning calorimeter (DSCI) under a nitrogen atmosphere at a heating rate of 20°C/min. It is expressed as the temperature that shows the knick and melting peak, respectively, when measured.

The block copolymer of the present invention has a PPS moiety and a PP5
The K section can be manufactured by any method possible to form each block and to connect both blocks.

Specific manufacturing methods include a method in which one block is formed and then the other block is formed, and both blocks are combined at the same time, and a method in which both blocks are formed individually and then combined. It will be done.

As described above, except for considering the formation and bonding of blocks and the type of repeating units, the method for producing the block copolymer of the present invention is similar to the conventional method for producing PPS and PP5K (Japanese Patent Publication No. 45-3368, Special Public Service 1977-1
No. 2240 and JP-A No. 63-113020, etc.) and essentially! That is, the method for producing a block copolymer of the present invention comprises desalting condensation of an alkali metal sulfide and a dihaloaromatic compound by heating in an aprotic polar organic solvent.

As the alkali metal sulfide used in the production of the block copolymer of the present invention, sulfides such as lithium, sodium, potassium, and rubidium are preferable, and sulfides of sodium and lithium are particularly preferable from the viewpoint of reactivity. The sulfide may be obtained by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide.

Next, the aprotic polar organic solvent is preferably one that is substantially liquid at the reaction temperature and pressure.

Specifically, formamide, acetamide, N-methylamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε- Amides such as caprolactam, hexamethylphosphoramide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, urea and lactams, sulfones such as sulfolane and dimethylsulfolane, nitriles such as benzonitrile, methylphenyl Mention may be made of ketones such as getones and mixtures thereof.

Among these solvents, amides, lactams and sulfones are particularly preferred.

Among the dihaloaromatic compounds used in the production of the pro-buta copolymer of the present invention, as the dihalobenzene that should form the PPS moiety, valadichlorobenzene, valadibromobenzene, etc. are preferably used, and the PP5K moiety should be formed. As the dihaloaromatic compound, 4,4-1 dichlorobenzophenone and the like are preferably used. Further, as the dihaloaromatic compound which can be used to some extent together with the dihaloaromatic compound necessary to form the above-mentioned block, the following are preferable.

(In the above formula, X and Y are halogen atoms, R1 and R2
represents an alkyl group having 1 to 20 carbon atoms) and 1.2.
Polyfunctional compounds having three or more halogen groups such as 3- or 1,2,4-trihelobenzene can be used. Furthermore, a polymerization catalyst such as an alkali metal carboxylate salt may be used for the purpose of increasing the degree of polymerization.

The above manufacturing method will be described in more detail.

[Manufacturing method (■)] Manufacturing method (I) produces PP on the spot as a repeating unit of the PPS part.
The 5K part! It consists of performing one return unit.

The raw material, alkali metal sulfide (containing water of crystallization), is placed in an organic solvent and heated to approximately 200°C to distill off water, thereby removing water from the reaction system.

Thereafter, an amount of dihalobenzene corresponding to 0.95 to 1.05/sulfide (1 mol) is added to give 160 to 3
A reaction mixture containing PPS is produced by heating to 0.00"C and performing a polymerization reaction. The required time is usually 0.5~
It takes about 30 hours.

On the other hand, after dehydrating the raw material alkali metal sulfide in an organic solvent in the same manner as above, the dihaloaromatic getone is usually
An amount corresponding to 5 to 1.05/sulfide (1 mole) is added to prepare an unreacted mixture.

The block copolymer of the present invention can be obtained by mixing this unreacted mixture and the reaction mixture containing PPS at a predetermined ratio and heating the mixture to 160 to 300°C to carry out a polymerization reaction. .

The polymer can usually be recovered in the form of granules or powder by washing, separating, and drying as necessary, in the same manner as in the method for producing PPS.

[Manufacturing method (■)] Manufacturing method (II) is the opposite of manufacturing method (I).
After forming the block of 5K part, PPS on the spot
It consists of forming and joining parts.

In this method, in the same manner as in production method (I), an alkali metal sulfide is added to a 81 solvent and dehydrated by heating to obtain a dihaloaromatic getone, usually 0.95 to 1°05/sulfide (mol 1 mol). A corresponding amount of PP5K is added thereto and heated to 160 to 300°C to carry out a polymerization reaction to produce a reaction mixture containing PP5K.

On the other hand, in the same manner as in the production method (I>), an alkali metal sulfide is added to an organic solvent, and after heating and dehydration, dihalobenzene is usually 0.95 to 1.05/[1 ull (mol 1
Add indigo equivalent to mol) to make an unreacted mixture.

The block copolymer of the present invention can be obtained by mixing this unreacted mixture and the reaction mixture containing PP5K at a predetermined ratio and heating the mixture to 160 to 300"C to carry out a polymerization reaction. The block copolymer can be recovered and purified in the same manner as in production method (I).

[Manufacturing method (■)] Manufacturing method (I) involves forming each block separately,
It consists of combining the two.

The block copolymer of the present invention can be produced by mixing the reaction mixture of production method (I) and the reaction mixture of production method (n) at a predetermined ratio, and heating the mixture to 160 to 300°C to carry out a polymerization reaction. can be obtained.

Recovery and purification of the block copolymer may be performed in the same manner as in the production method (I>).

The resin composition of the present invention comprises the block copolymers 1 to 10
When using PPS for the 0-layer plate part, pps
0 to 99 times, PP5 when used together with PP5K
Preferably, K is contained in an amount of 0 to 99 parts by weight.

It is a polymer containing 70 mol% or more of repeating units represented by polyphenylene sulfide used in the present invention, more preferably 90 mol% or more of -F, and heat resistance will be impaired if the repeating units do not contain 70 mol%. Undesirable.

Generally, pps is a polymer with relatively small molecular decoy obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. In the case of the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, after polymerization, it can be heated in an oxygen atmosphere or treated with peroxide, etc. It is also possible to increase the degree of polymerization and use it by adding a crosslinking agent and heating it, and in the present invention, it is possible to use PPS obtained by any method.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula, etc.

The melt viscosity of PPS used in the present invention is not particularly limited as long as it can be kneaded with the block copolymer, but it is usually 1.
00~10,000 voids (320°C1 shear rate 10
3/sec) is used.

PP5K used in the present invention has a PA structure of 70 mol%.
As mentioned above, a polymer containing 90 mol% or more is more preferable, and if the repeating unit is less than 70 mol%, heat resistance will be impaired, so it is not preferable.

The method for manufacturing PP5K used in the present invention is disclosed in Japanese Patent Application Laid-open No. 63-11.
Although PP5 can be obtained by a manufacturing method typified by Publication No. 3020, in the present invention, PP5 obtained by any method can be used.
This is possible by using K.

The melt viscosity of PP5K used in the present invention is not particularly limited as long as it can be kneaded with the Pro-Tsuku copolymer, but it is usually 100 to 10,000 voids (372°C1 shear rate 103/sec). is used.

In addition, the block copolymer and resin composition of the present invention may contain antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet inhibitors, colorants, flame retardants, etc., as long as they do not impair the effects of the present invention. In addition, for the purpose of controlling the degree of crosslinking of the PPS portion of the block copolymer, conventional peroxidants and small amounts of various polymers can be added. Crosslinking accelerators such as thiophosphinic acid metal salts described or JP-A-58204
It is also possible to incorporate crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP-A No. 045, JP-A-58-2040116, and the like.

The block copolymer and resin composition of the present invention may contain fibrous and/or granular reinforcing agents, if necessary. 30 per 100 parts by weight of total resin components
It is possible to blend within a range not exceeding 0 parts by weight,
It is possible to improve strength, rigidity, heat resistance, dimensional stability, etc. by blending normally in a range of 10 to 300 parts by weight.

Examples of such fibrous reinforcing agents include non-photographic fibers such as glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers, and carbon fibers.

Granular reinforcing agents include wollastenite, sericite, kaolin, mica, clay, talc, silicates such as alumina silicate, alumina, silicon chloride, metal oxides such as magnesium oxide, zirconium oxide, and titanium oxide, and calcium carbonate. , carbonates such as magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide, Saroyan,
Examples include silica, which may be hollow,
These reinforcing agents can be used in combination of two or more,
If necessary, it can be pretreated with a silane-based or titanium-based coupling agent before use.

The method for preparing the composition of the present invention is not particularly limited, but a typical method is to melt-knead the resin component and the reinforcing agent in an extruder at a temperature higher than the melting point of the resin, and then pelletize the mixture.

Note that the mixing temperature of Shinobu Ml is preferably 280 to 400°C.

The present invention will be explained in more detail with reference to Examples below.

<Example> Reference Example 1 (Polymerization of PPSK) Sodium sulfide 3.26ksr (25
(containing 40% water of crystallization) and 7.9 kg of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were charged, and the temperature was gradually raised to 205 ''C while stirring, and 1.9 kg of water was added.
Approximately 1.51 kg of distillate containing 36 kg was removed. 4,4-dichlorobenzophenone 6.28 kr (25
mol) and N M P 6 k+r and 250°
The reaction product heated for 3 hours at
I got about 5.2 kr for 5K.

The same operation was repeated and used in the examples described below.

Example 1 An autoclave was charged with 3.26 kg of sodium sulfide (25 moles, containing 40% water of crystallization), 4 f of sodium hydroxide, sodium acetate, 1.36 kg of trihydrate (approximately 10 moles), and 7.9 kg of NMP, and stirred. While Xu Ma 2
The distillate water was heated to 0.05°C and contained 136 kg of water.
5" was removed. The residual mixture contains 3.75b2 (25.5 mol) of 1,4-dichlorobenzene and NMP2
The mixture was heated at 265° C. for 4 hours to prepare PPS reaction mixture M<A>, which was removed from the autoclave and stored. The same operation was repeated for the following operations.

An autoclave was charged with 3.26 kg of sodium sulfide (25 mol, containing 40% water of crystallization) and 7.9 mg of NMP, and the temperature was gradually raised to 205'C while stirring, and distilled water containing 1.36 kg of water was dissolved. 5" was removed. To the residue 4,4"-dichlorobenzophenone 6.28 +r
(25 mol) and NMP were added and cooled with stirring to prepare an unreacted mixture (H), which was taken out from the autoclave and stored. The same operation was repeated and subjected to the operations described below.

Reaction mixture 1 (A)/unreacted mixture; ri in autoclave
i, (H) respectively 11.8ksr/6.63kf,
8, 45kf/ 11, lkr, 5.07+qr
/15.5kg and reacted at 250°C for 3 hours.

After the reaction, the reaction mixture was washed 5 times with hot water at 70°C and dried under reduced pressure at 80°C for 24 hours to obtain block copolymers (1-1m (1,-2) and (1-3), respectively). I got it.

The melt flow rate at 372°C of the obtained block copolymer was measured and was as shown in Table 1.

In addition, the obtained block copolymer was melted and pressed at a temperature approximately 30°C higher than the melting point using a high-temperature press, and quenched with water to prepare a film, which was used as a sample.
When Tg and Tm were measured, they were as shown in Table 1.

Comparative Example 1 A PPS reaction solution (A) was prepared in exactly the same manner as in Example 1, washed 5 times with warm water at 70°C, and incubated at 80°C for 24 hours.
Dry under reduced pressure for an hour. Melt viscosity 2.5.00 poise (3
Powdered pps at 20°C, shear rate 1,000 sec-1)
<Comparative Example 1) Approximately 2 kg was obtained.

The second PPS'rg? When J' Trn was measured, it was as shown in Table 1.

Table 1 clearly shows that both Tg and Tm of the block copolymer of Example 1 of the present invention are higher than that of PPS.

Example 2 An autoclave was charged with 3.26 kg of sodium sulfide (25 moles, containing 40% water of crystallization) and 7.9 m of NMP, and the temperature was gradually raised to 205°C with stirring, and a distillate containing 1.36 kg of water was charged. Approximately 1.51 liters of water were removed. The residue contained 6.28 kf of 4,4-dichlorobenzophenone (
25 mol) and 6 kg of NMP were added and heated at 250°C for 30 minutes.
The mixture was heated for an hour to prepare a PP5K reaction mixture (B), which was removed from the autoclave and stored. The same operation was repeated and subjected to the operations described below.

3.26 kg of sodium sulfide (25 mol, containing 40% water of crystallization) and 7.9 kl of N M P in an autoclave
The temperature was gradually raised to 205°C while stirring, and about 1.5 layers of distilled water containing 1.36 kr of water were removed.

3.75 kg (25 kg) of 1,4-dichlorobenzene was added to the residue.
.

The same turret work was repeated, and the following was completed by Uzuru's turret work.
Reaction mixture 1 (B)/unreacted mixture (I) in an autoclave
) respectively 15.5ksr/4.68kg and 11.1
kg/7.80kg and 6.631qr/10.9kg, and reacted at 250°C for 8 hours.

After the reaction, the block copolymers (2-1), (2-2) and (2-
3> was obtained. The melt flow rate, Tg and Tm of the obtained block copolymer were as shown in Table 1.

Example 3 Reaction mixture (A) and (
B) respectively 11, 8h2/6, 63kr, 8
, 45kr/11, 1+r and 5.07kg
/15.

After completion of the 6 reactions in which 5 kg were prepared and reacted at 250°C for 200 hours, they were washed and dried in the same manner as in Example 1 to obtain block copolymers (3-1>, (32) and (
3-3) was obtained.

Melt flow rate, Tg of the obtained block copolymer
and Tm were as listed in Table 1.

Comparative Example 2 The unreacted mixture (I'') and (I) prepared in Examples 1 and 2 were 11.1i+g/7.80hg and 1
Prepared at a ratio of 5.5kg/4.68m, heated at 250℃
After the reaction was completed for 0 hours, the reaction solution was washed and dried in the same manner as in Example 1 to obtain random copolymers (Comparative Example 2).
-1) and (Comparative Example 2-2) were obtained. The obtained random copolymer was measured in the same manner as in Example 1, and the results shown in Table 1 were obtained.

Example 4 Block copolymerization 141 obtained in Example 1: (1-1), (
1-2) and (1-3) were each blended with glass fibers (three-way chopped fibers) in the proportions listed in Table 2, melted and kneaded by screw extrusion set at 300 to 380″C, Pelletized 0th order pellets
The sample was supplied to a screw in-line injection molding machine set at 00 to 380''C, and a test piece was molded at a mold temperature of 150°C.

The heat distortion temperature (ASTM
D-648) is as shown in Table 2, and had an extremely high heat distortion temperature.

Example 5 Block copolymer (3-1> and (3-1) obtained in Example 3
-2) was pelletized and injection molded in the same manner as in Example 4, and the heat distortion temperature evaluated was as shown in Table 2.

Comparative Example 3 Evaluation was made on test pieces obtained by pelletizing and injection molding the PPS powder obtained in Comparative Example 1 as it was and by blending glass fiber in the proportions listed in Table 2 in the same manner as in Example 4. The heat distortion temperatures obtained were as listed in Table 2.

Example 6 Using the block copolymer (2-2) obtained in Example 2, the PPS powder obtained in Comparative Example 1 was triblended in the proportions listed in Table 2, and then The heat distortion temperatures evaluated for test pieces pelletized and injection molded in the same manner are as shown in Table 2.

Example 7 Using the block copolymer (1-1) obtained in Example 1, the PPS powder and glass fiber obtained in Comparative Example 1 were triblended in the proportions listed in Table 2, and then Example 4 was prepared. The heat distortion temperatures evaluated for test pieces pelletized and injection molded in the same manner as described in Table 2 are as shown in Table 2.

The heat distortion temperature was clearly higher than that of Comparative Example 3 in which the block copolymer of the present invention was not blended.

Example 8 Using the block copolymer (1-2) obtained in Example 1, the PP5K powder obtained in Reference Example 1 was triblended in the proportions listed in Table 2, and then the same procedure as in Example 4 was carried out. The heat distortion temperatures evaluated for the test pieces pelletized and injection molded using the method described in Table 2 are as shown in Table 2.

Comparative Example 4 Random copolymer obtained in Comparative Example 2 (Comparative Example 2-1)
and (Comparative Example 2-2), P obtained in Comparative Example 1
After tri-blending PS powder and glass fiber in the proportions shown in Table 2, the test pieces were pelletized and injection molded in the same manner as in Example 1. The heat distortion temperatures evaluated were as shown in Table 2. Ta.

Example 9 Using the block copolymer (2-3) obtained in Example 2, the PP5K powder and glass fiber prepared in Reference Example 1 were triblended in the proportions listed in Table 2, and then The heat distortion temperatures evaluated for test pieces pelletized and injection molded in the same manner as in Example 1 were as shown in Table 2.

Example 10 Using the block copolymer (3-2) obtained in Example 3, PPS powder obtained in Comparative Example 1, PP5 obtained in Reference Example 1 '11)
After tri-blending K powder and glass fiber in the proportions listed in Table 2, pelletization was carried out in the same manner as in Example 4.
The heat distortion temperatures evaluated for the injection molded test pieces were as shown in Table 2.

Comparative Example 5 The PPS powder obtained in Comparative Example 1, the PP5K powder obtained in Reference Example 1, and glass fiber were triblended in the proportions listed in Table 2, and then pelletized and injection molded in the same manner as in Example 1. The heat distortion temperatures evaluated for the test pieces were as listed in Table 2.

<Effects of the Invention> The block copolymer and its resin composition of the present invention have better heat resistance than conventional ppsvII resins.

Furthermore, the production method of the present invention allows efficient production of block copolymers.

Claims (5)

[Claims] (1) A block copolymer consisting of a polyphenylene sulfide part and a polyphenylene sulfide ketone part, and having a melt flow rate at 372°C of 1 to 1,000. (2) A first step of heating an aprotic polar organic solvent containing dihalobenzene and an alkali metal sulfide to produce a reaction solution containing polyphenylene sulfide, and adding a dihaloaromatic ketone to this reaction solution, A block copolymer consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, comprising a second step of heating in the presence of an alkali metal sulfide and an aprotic polar organic solvent to produce a block copolymer. Method for producing polymers. (3) A first step of heating an aprotic polar organic solvent containing a dihaloaromatic ketone and an alkali metal sulfide to produce a reaction solution containing a polyphenylene sulfide ketone, and adding dihalobenzene to this reaction solution. , a block consisting of a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety, comprising a second step of heating in the presence of an alkali metal sulfide and an aprotic polar organic solvent to produce a block copolymer. Method for producing copolymer. (4) A first step of heating an aprotic polar organic solvent containing dihalobenzene and an alkali metal sulfide to produce a reaction solution containing polyphenylene sulfide, and an aprotic polar organic solvent containing a dihaloaromatic ketone and an alkali metal sulfide. A second step in which a polar organic solvent is heated to produce a reaction solution containing polyphenylene sulfide, and a third step in which the reaction solutions obtained in each step are mixed and heated to produce a block copolymer. 1. A method for producing a block copolymer comprising a polyphenylene sulfide moiety and a polyphenylene sulfide ketone moiety. (5) A resin composition comprising a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, and polyphenylene sulfide and/or polyphenylene sulfide ketone.