JP6844369B2 - Polyarylene sulfide block copolymer and its production method - Google Patents

Description

The present invention is a polyarylene sulfide block copolymer and a method for producing the same. The polyarylene sulfide block has excellent heat resistance, heat aging resistance, electrical insulation, high flexibility and high toughness, and excellent long-term heat resistance. It relates to block copolymers.

Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) is a resin having properties suitable as an engineering plastic, such as excellent heat resistance, barrier property, chemical resistance, electrical insulation, moisture heat resistance, and flame retardancy. In particular, polyphenylene sulfide resin can be molded into various molded parts, films, sheets, fibers, etc. by injection molding and extrusion molding, and is a field that requires heat resistance and chemical resistance such as electrical / electronic parts, mechanical parts, and automobile parts. Widely used in.

On the other hand, polyarylene sulfide is inferior to other engineering plastics in terms of impact resistance, toughness, flexibility, and moldability, and is modified by compounding with a dissimilar polymer to improve them. The method is being tried. For example, a blend of olefin-based elastomers can be mentioned as a method for imparting toughness and flexibility to polyarylene sulfide. In this case, since the heat resistance of the olefin-based elastomer is low, heat aging under high temperature conditions is remarkable and toughness is obtained. , There was a problem that flexibility was reduced.

Therefore, a method of compounding polydimethylsiloxane as a highly tough and highly flexible component that can withstand use under high temperature conditions has been studied, but the solubility parameter of polydimethylsiloxane is significantly different from the solubility parameter of PPS. , Polymer alloying is extremely difficult, and it is not possible to achieve a satisfactory improvement in terms of imparting toughness and flexibility.

Against this background, in order to impart high toughness and high flexibility, polydimethylsiloxane is chemically bonded and copolymerized to drastically modify the main chain skeleton of polyarylene sulfide. Complex methods are being studied. However, the problem at this time is that polyarylene sulfide has a small amount of reactive functional groups in the molecular chain and is inferior in interaction and reactivity with other engineering plastics such as polyamide and polyester. Therefore, various studies have been conducted to positively introduce a reactive functional group into polyarylene sulfide to efficiently copolymerize it with polyorganosiloxane.

For example, Patent Document 1 reports a method of introducing an amino group as a reactive functional group into the main chain terminal of polyarylene sulfide and reacting it with polydimethylsiloxane having an epoxy group. As another method, Patent Document 2 reports a method in which an amino group is introduced as a reactive functional group at the end of the main chain to react bisphenol A dianhydride with polydimethylsiloxane having an amino group. In addition, Patent Document 3 reports a method of introducing a large amount of carboxyl groups as reactive functional groups into the main chain terminal of polyarylene sulfide and reacting with polydimethylsiloxane having an epoxy group.

Japanese Unexamined Patent Publication No. 6-239972 Japanese Unexamined Patent Publication No. 64-45433 International Publication No. 2015-151921

However, in the method of Patent Document 1, since the content of the reactive functional group of polyarylene sulfide is small, the copolymerization amount of polydimethylsiloxane is insufficient, and not only excellent flexibility cannot be obtained, but also polyarylene. It is hard to say that the bond consisting of the amino group of sulfide and the epoxy group of polydimethylsiloxane is strong, and brittleness due to decomposition of the chemical bond between blocks was observed during long-term heat treatment.

In the method of Patent Document 2, polyarylene sulfide contains a sufficient reactive functional group, but since both polyarylene sulfide and the reactive functional group of polydimethylsiloxane are amino groups, bisphenol A is used to mediate them. The reaction is taking place with the bisanoxide. As a result, not only excellent flexibility could not be obtained, but also components other than polyarylene sulfide and polydimethylsiloxane having high heat resistance were introduced, so that embrittlement was observed during long-term heat treatment. Further, since the polyarylene sulfide obtained by the method of Patent Document 2 has a molecular weight of about that of an oligomer, the molecular weight of the obtained polyarylene sulfide block copolymer is relatively low, and there is a problem that sufficient toughness cannot be obtained. It was.

In the method of Patent Document 3, polyarylene sulfide contains a sufficient reactive functional group and a large amount of polydimethylsiloxane can be introduced, so that toughness and flexibility are improved. On the other hand, it cannot be said that the ester bond consisting of the carboxyl group of polyarylene sulfide and the epoxy group of polydimethylsiloxane is strong, and embrittlement due to decomposition of the chemical bond between blocks was observed during long-term heat treatment.

As described above, it has been difficult to achieve both heat resistance, chemical resistance and high toughness, high flexibility, heat aging resistance, and long-term heat resistance of polyarylene sulfide by the prior art.

The present invention provides a novel polyarylene sulfide block copolymer having excellent flexibility, toughness, electrical insulation and long-term heat resistance without impairing the inherent heat resistance and chemical resistance of polyarylene sulfide. Is the subject.

Therefore, as a result of diligent studies to solve the above problems, the present inventors have obtained by heating (X) polyarylene sulfide having a specific structure and (Y) polyorganosiloxane having a specific functional group. We have found that a polyarylene sulfide block copolymer having excellent flexibility, toughness, and electrical insulation and excellent long-term heat resistance can be obtained without impairing heat resistance and chemical resistance, and have reached the present invention.

That is, the present invention is as follows.
1. 1. A method for producing a polyarylene sulfide block copolymer, which comprises reacting (X) polyarylene sulfide having an acid anhydride group at the terminal with (Y) polyorganosiloxane containing an amino group.
2. The method for producing a polyarylene sulfide block copolymer according to 1, wherein the content of the acid anhydride group contained in the (X) polyarylene sulfide is 180 μmol / g or more.
3. 3. For at least (i) sulfur source, (ii) dihalogenated aromatic compound, (iii) organic polar solvent, and 1 mol of sulfur atom in the reaction system, the following general formula (Ia) and / or the following general formula (I) The mixture containing 0.01 to 40 mol% of the monohalogenated compound having the (iv) reactive functional group represented by (b) is heated to obtain the (X) polyarylene sulfide, which is then contained with an amino group. (Y) The method for producing a polyarylene sulfide block copolymer according to any one of claims 1 and 2, wherein the polyorganosiloxane is reacted.

(In formulas (Ia) and (Ib), V represents a halogen and W represents a carboxyl group or a metal salt thereof.)
4. Assuming that the sum of (x) and (y) is 100% by weight,
(X) Polyarylene sulfide unit 1 to 99% by weight,
(Y) Containing 99 to 1% by weight of polyorganosiloxane unit ,
It has a structure in which (x) polyarylene sulfide unit and (y) polyorganosiloxane unit are bonded via an imide group, has a glass transition temperature of 80 ° C. or lower, and has a molecular weight retention rate of 70 as defined below. Polyarylene sulfide block copolymer characterized by being% or more,
Molecular weight retention rate (%) = ( 180 ° C x 300h weight average molecular weight after heat treatment) / (weight average molecular weight before heat treatment ) x 100 (%)
5. The polyarylene sulfide block copolymer according to 4, which comprises 40 to 85% by weight of the (x) polyarylene sulfide unit and 15 to 60% by weight of the (y) polyorganosiloxane unit.
A molded product comprising the polyarylene sulfide block copolymer according to any one of 6.4 to 5 or a composition containing the polyarylene sulfide block copolymer.
Is.

According to the present invention, a polyarylene sulfide block copolymer having both high flexibility and high toughness, and excellent electrical insulation and long-term heat resistance without impairing the original heat resistance and chemical resistance of polyarylene sulfide. Can be obtained.

Hereinafter, the present invention will be described in detail.

(1) Polyarylene sulfide block copolymer The polyarylene sulfide block copolymer in the present invention is a block copolymer containing a polyarylene sulfide unit and a polyorganosiloxane unit.

The polyarylene sulfide unit in the present invention is a structural unit having a repeating unit of the formula, − (Ar—S) − as a main constituent unit, preferably containing 80 mol% or more of the repeating unit. As Ar, there are units represented by the following formulas (C) to (M), and the formula (C) is particularly preferable.

(R1 and R2 are substituents selected from hydrogen, alkyl group, alkoxy group and halogen group, and R1 and R2 may be the same or different).

As long as this repeating unit is used as the main constituent unit, a small amount of branching units or cross-linking units represented by the following formulas (N) to (P) and the like can be included. The copolymerization amount of these branching units or cross-linking units is preferably in the range of 0 to 1 mol% with respect to 1 mol of the- (Ar-S)-unit.

In addition, the polyarylene sulfide unit in the present invention may be any of a random copolymer containing the above repeating unit, a block copolymer, and a mixture thereof.

Typical examples of these include polyphenylene sulfide units, polyphenylene sulfide sulfone units, polyphenylene sulfide ketone units, random copolymers thereof, block copolymers, and mixtures thereof. A particularly preferable polyarylene sulfide unit is a p-phenylene sulfide unit as a main constituent unit of a polymer.

80 mol% or more, particularly 90 mol% or more of polyphenylene sulfide can be mentioned.

The number of repetitions of the polyarylene sulfide unit in the present invention is an integer of 5 or more. On the other hand, the upper limit thereof is 200 or less, preferably 120 or less, and 80 or less from the viewpoint of increasing the weight fraction of polyorganosiloxane in the polyarylene sulfide block copolymer to obtain sufficient modification. Especially preferable.

The polyorganosiloxane unit in the present invention has a repeating unit represented by the general formula (Q) as a main constituent unit.

Here, R3 and R4 represent alkyl groups of C1 to C10 or aromatic groups of C6 to C10. Specifically, examples of R3 include alkyl groups such as methyl group, ethyl group and propyl group, and aromatic groups such as phenyl group and naphthyl group. n is 1 or more, preferably 5 or more, and particularly preferably 10 or more. On the other hand, the upper limit thereof is 100 or less, preferably 60 or less, and particularly preferably 40 or less from the viewpoint of compatibility with polyarylene sulfide and an organic polar solvent.

Further, in the polyarylene sulfide block copolymer of the present invention, the polyarylene sulfide unit and the polyorganosiloxane unit represented by the general formula (Q) are linked via a structure other than the repeating unit of each block. However, the terminal structures derived from the repeating unit may be directly connected to each other. Further, a plurality of the same repeating units may be connected.

According to the present invention, the content of polyorganosiloxane units in the polyarylene sulfide block copolymer is 1% by weight or more and 99% by weight or less, assuming that the total of polyarylene sulfide units and polyorganosiloxane units is 100% by weight. A polyarylene sulfide block copolymer such as that in the range can be obtained. If the content of the polyorganosiloxane unit in the polyarylene sulfide block copolymer is less than 1% by weight, there is a problem that sufficient flexibility, toughness, and electrical insulation cannot be obtained, while it exceeds 99% by weight. In some cases, there is a problem that properties derived from polyphenylene sulfide units such as heat resistance and chemical resistance are difficult to be exhibited. According to the present invention, the upper limit of the content of the polyorganosiloxane unit is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 60% by weight or less for molding processability. An excellent polyarylene sulfide block copolymer can be obtained. Further, according to the present invention, the lower limit of the content of the polyorganosiloxane unit is 1% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, and particularly preferably 20% by weight. As described above, a polyarylene sulfide block copolymer showing practical tensile elongation is obtained, particularly preferably at 30% by weight or more. The content of the polyorganosiloxane unit in the polyarylene sulfide block copolymer is calculated by multiplying the mole fraction of the Si atom obtained from the element analysis by the molecular weight of the organosiloxane repeating unit.

The lower limit of the melting point of the polyarylene sulfide block copolymer of the present invention is preferably 245 ° C. or higher, more preferably 250 ° C. or higher. On the other hand, the upper limit of the melting point of the polyphenylene sulfide block copolymer is preferably 290 ° C. or lower. When the melting point of the polyphenylene sulfide block copolymer is in the above-mentioned preferable range, properties derived from the polyarylene sulfide unit such as heat resistance and chemical resistance are likely to be exhibited, and in terms of imparting high flexibility and high toughness. It is enough. The melting point here is raised from 0 ° C. to 340 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter, held at 340 ° C. for 1 minute, and reaches 100 ° C. at a rate of 20 ° C./min. It can be defined as the value of the melting peak temperature detected when the temperature is lowered, held at 100 ° C. for 1 minute, and the temperature is raised to 340 ° C. at a rate of 20 ° C./min.

The glass transition temperature of the polyarylene sulfide block copolymer of the present invention is preferably 80 ° C. or lower from the viewpoint of imparting flexibility and toughness, and is preferably 75 ° C. or lower in order to obtain more excellent flexibility and toughness. In order to obtain more excellent flexibility and toughness, 65 ° C. or lower is preferable, and 60 ° C. or lower is particularly preferable. The lower limit of the glass transition temperature is not particularly limited, but it is preferably 40 ° C. or higher in order to maintain the inherent properties of polyarylene sulfide. The glass transition temperature here can be defined as an inflection point of the baseline shift detected when the temperature is raised from 0 ° C. to 340 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter.

In the polyarylene sulfide block copolymer of the present invention, it is preferable that block copolymerization of (X) polyarylene sulfide and (Y) polyorganosiloxane does not cause side reactions, and the reaction can be efficiently performed in a multi-block manner. When it progresses, the motility of the main chain is improved, so that the rate of cold crystallization is improved, and a polyarylene sulfide block copolymer having a cold crystallization temperature of 120 ° C. or less can be obtained. Further, more preferably, a polyarylene sulfide block copolymer having excellent flexibility / toughness and molding processability can be obtained at a cold crystallization temperature of 115 ° C. or lower. As described above, when the cold crystallization temperature is lowered, there are various advantages in terms of molding. For example, if the crystallization rate is improved, the molding cycle is shortened, which leads to cost reduction. Alternatively, the mold temperature can be lowered, which is advantageous in terms of energy and safety. The lower limit of the cold crystallization temperature is not particularly limited, but it is preferably 70 ° C. or higher in order to maintain the inherent properties of polyarylene sulfide. The cold crystallization temperature here can be defined as the value of the exothermic peak temperature detected when the temperature is raised from 0 ° C. to 340 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter.

According to the present invention, a polyarylene sulfide block copolymer having a weight average molecular weight of 25,000 or more is preferable, more preferably 30,000 or more, particularly preferably 35,000 or more, and particularly preferably 35,000 or more. A polyarylene sulfide block copolymer having more practical flexibility and toughness at 40,000 or more can be obtained. Further, according to the present invention, a polyarylene sulfide block copolymer having an upper limit of its weight average molecular weight of 100,000 or less can be obtained, preferably 90,000 or less, and particularly preferably 80,000 or less. A polyarylene sulfide block copolymer having excellent molding processability can be obtained. When the weight average molecular weight of the polyarylene sulfide block copolymer is less than 25,000, the toughness of the obtained polyarylene sulfide block copolymer tends to be insufficient, while the weight of the polyarylene sulfide block copolymer is insufficient. When the average molecular weight exceeds 100,000, the melt viscosity of the polyarylene sulfide block copolymer becomes high, and the molding processability deteriorates.

The polyarylene sulfide block copolymer of the present invention has excellent heat resistance, and a polyarylene sulfide block copolymer having a molecular weight retention rate of 70% or more as defined below can be obtained. The molecular weight retention of the polyarylene sulfide block copolymer is preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and 95% or more from the viewpoint of dramatically modifying long-term heat resistance. Especially preferable. The molecular weight retention rate here can be determined by the following formula by measuring the weight average molecular weight of a film having a thickness of 0.2 mm before and after heat treatment at 180 ° C. for 300 hours, and can be defined as a percentage.
Molecular weight retention rate (%) = ( 180 ° C x 300h weight average molecular weight after heat treatment) / (weight average molecular weight before heat treatment ) x 100 (%)

Further, the molecular weight distribution of the polyarylene sulfide block copolymer of the present invention is preferably monomodal. When the molecular weight distribution of the polyarylene sulfide block copolymer is monomodal, it means that the block copolymerization of (X) polyphenylene sulfide and (Y) polyorganosiloxane is sufficient, and a sufficient modification effect can be obtained. Be done. Further, the molecular weight distribution of the polyphenylene sulfide block copolymer preferably has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 6.0 or less as an index that the block copolymerization is sufficiently progressing, and toughness due to a low molecular weight component. In order to prevent the decrease, the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 5.0 or less is more preferable. The weight average molecular weight and the molecular weight distribution here are values calculated in terms of polystyrene by gel permeation chromatography (GPC).

Further, the polyarylene sulfide block copolymer of the present invention preferably has a peak at ^{1716 cm -1} , which is a characteristic absorption band of an imide group, as measured by FT-IR, and further, the absorbance of the peak at ^{1716 cm -1 ( The ratio of b1) divided by the absorbance (c1) of the peak of 3066 cm-1} , which is the absorption of the CH bond of the benzene ring, is more preferably 1.0 or more, and more preferably 1.5 or more. More preferably, it is particularly preferably 2.0 or more, and even more preferably 2.5 or more, from the viewpoint of obtaining heat resistance.

(2) (X) Polyarylene Sulfide The (X) polyarylene sulfide in the present invention has a repeating unit of the formula, − (Ar—S) − as a main constituent unit, preferably 80 mol% or more of the repeating unit. contains. As Ar, there are units represented by the following formulas (C) to (M), and the formula (C) is particularly preferable.

(R1 and R2 are substituents selected from hydrogen, alkyl group, alkoxy group and halogen group, and R1 and R2 may be the same or different).

As long as this repeating unit is used as the main constituent unit, a small amount of branching units or cross-linking units represented by the following formulas (N) to (P) and the like can be included. The copolymerization amount of these branching units or cross-linking units is preferably in the range of 0 to 1 mol% with respect to 1 mol of the- (Ar-S)-unit.

Further, the (X) polyarylene sulfide in the present invention may be any of a random copolymer containing the above repeating unit, a block copolymer, and a mixture thereof.

Typical examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers and mixtures thereof. A particularly preferred polyarylene sulfide is the p-phenylene sulfide unit as the main building block of the polymer.

80 mol% or more, particularly 90 mol% or more of polyphenylene sulfide can be mentioned.

The (X) polyarylene sulfide in the present invention needs to have an acid anhydride group at the end of its main chain. Further, even if a part of the contained acid anhydride group is ring-opened and modified to an adjacent dicarboxyl group, when the reaction with the (Y) polyorganosiloxane is performed, the adjacent dicarboxyl group is dehydrated by heating and the acid. Since the effect of the present invention is not impaired by modifying to an anhydride group, there is no problem even if a part of the contained acid anhydride group is modified to an adjacent dicarboxyl group.

On the other hand, the (X) polyarylene sulfide may have a part of functional groups obtained as a side reaction in the polymerization process.

Since the polyarylene sulfide (X) has an acid anhydride group at the end of its main chain, the thermal stability of the reactive functional group does not decrease. In addition, the vicinity of the reactive functional group is sterically crowded, and the contact frequency does not decrease during copolymerization with (Y) polyorganosiloxane, so that the reaction efficiency does not decrease.

The weight average molecular weight of the (X) polyarylene sulfide obtained in the present invention is preferably 2500 g / mol or more, more preferably 3,000 g / mol or more. When the weight average molecular weight is 2500 g / mol or more, heat resistance, chemical resistance and the like are not impaired. On the other hand, the upper limit thereof is preferably 20000 g / mol or less, and more preferably 15000 g / mol or less. When the weight average molecular weight is 25,000 g / mol or less, the reactive functional group at the end of the molecular chain does not decrease as the molecular weight increases. The weight average molecular weight here is a value calculated in terms of polystyrene by gel permeation chromatography (GPC).

The number average molecular weight of the (X) polyarylene sulfide obtained in the present invention is preferably 1500 g / mol or more, and more preferably 2000 g / mol or more. When the number average molecular weight is 1500 g / mol or more, heat resistance, chemical resistance and the like are not impaired. On the other hand, the upper limit thereof is preferably 10000 g / mol or less, more preferably 8000 g / mol or less, and particularly preferably 7000 g / mol or less. When the number average molecular weight is 10,000 g / mol or less, the reactive functional group at the end of the molecular chain does not decrease as the molecular weight increases. The number average molecular weight here is a value calculated in terms of polystyrene by gel permeation chromatography (GPC).

The dispersity (Mw / Mn) represented by the weight average molecular weight / number average molecular weight of the (X) polyarylene sulfide used in the present invention is preferably 3.0 or less, and particularly preferably 2.5 or less. When the dispersity of (X) polyarylene sulfide is low, the reactivity of each molecular chain becomes uniform, and copolymerization with (Y) polyorganosiloxane proceeds more efficiently.

The content of the acid anhydride group of the (X) polyarylene sulfide of the present invention is preferably 180 μmol / g or more, more preferably 300 μmol / g or more, and particularly preferably 400 μmol / g or more, and (X) polyarylene sulfide. When the functional group content of is 180 μmol / g or more, copolymerization with (Y) polyorganosiloxane proceeds, and a sufficient modification effect can be obtained. The acid anhydride group content of the (X) polyarylene sulfide of the present invention is preferably 2,000 μmol / g or less, and particularly preferably 1,500 μmol / g or less. When the upper limit of the functional group content is 2,000 μmol / g or less, the molecular weight of (X) polyarylene sulfide decreases as the functional group content increases, and the heat resistance is not impaired.

There is a concern that a part of the acid anhydride group may open and be modified to an adjacent dicarboxyl group, resulting in a measurement error. However, before the measurement, for example, at 120 ° C. for 4 hours, at 340 ° C. for 4 minutes, etc. It is possible to close all the adjacent dicarboxyl groups to the acid anhydride group by heating.

Further, the (X) polyarylene sulfide obtained in the present invention is preferably not only having an acid anhydride group at the terminal, but also having a high introduction rate of a reactive functional group occupying the entire terminal of the molecular chain. As this index, the terminal functional group ratio is used in the present invention. However, the terminal functional group ratio is determined by ((functional group content (mol / g) / (1 / number average molecular weight (g / mol) × 2)) × 100 (%), and the unit is a percentage. According to the present invention, (X) polyarylene sulfide having a terminal functional group ratio of 85% or more, more preferably 90% or more can be obtained. Particularly preferably 95% or more, (Y). (X) polyarylene sulfide that efficiently promotes copolymerization with polyorganosiloxane can be obtained. If the terminal functional group ratio is 85% or more, the copolymerization with (Y) polyorganosiloxane can be performed. Since the reaction does not stop unintentionally, there is a tendency to obtain a polyarylene sulfide copolymer having a higher molecular weight and excellent toughness and heat resistance.

The lower limit of the melting point of the (X) polyarylene sulfide of the present invention is preferably 270 ° C. or higher. On the other hand, the upper limit of the melting point is preferably 290 ° C. or lower. When the melting point is in the above range, the properties derived from PAS such as heat resistance and chemical resistance of the polyarylene sulfide copolymer are likely to be exhibited. The melting point here is raised from 0 ° C. to 340 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter, held at 340 ° C. for 1 minute, and reaches 100 ° C. at a rate of 20 ° C./min. It can be defined as the value of the melting peak temperature detected when the temperature is lowered, held at 100 ° C. for 1 minute, and the temperature is raised to 340 ° C. at a rate of 20 ° C./min.

The chlorine content of the (X) polyarylene sulfide obtained in the present invention is preferably 3500 ppm or less, more preferably 2500 ppm or less, particularly preferably 1500 ppm or less, reducing the environmental load and selectively introducing a reactive functional group at the terminal. 1000 ppm or less is particularly preferable from the viewpoint of causing the reaction. When the chlorine content is 3500 ppm or less, the introduction of the reactive functional group into the molecular chain terminal of (X) polyarylene sulfide is not insufficient.

The method for producing (X) polyarylene sulfide used for synthesizing the block copolymer of the present invention will be specifically described below. Alkali metal hydrosulfide, alkali metal hydroxide, organic polar solvent, dihalogenation. After describing the raw materials of aromatic compounds, monohalogenated aromatic compounds having reactive functional groups, polymerization aids, and branching / cross-linking agents, dehydration steps, polymerization reaction steps, polymer recovery, and other post-treatments will be described.

(3) (X) Method for producing polyarylene sulfide [Sulfur source]
In the present invention, alkali metal hydrosulfide or alkali metal sulfide is used as the sulfur source.

Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides. In addition, it is also possible to use an alkali metal sulfide that can be a precursor of the alkali metal hydrosulfide. Specific examples of the alkali metal hydrosulfide include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

When the sulfur source is a mixture of alkali metal hydrosulfide and alkali metal sulfide, the total molar amount of alkali metal hydrosulfide and alkali metal sulfide is the molar amount of sulfur source used for the polymerization reaction. It becomes.

In the present invention, the amount of the sulfur source or the amount of the sulfur atom in the system is actually when a partial loss of the sulfur source or the sulfur atom in the system occurs before the start of the polymerization reaction due to a dehydration operation or the like. It shall mean the residual amount obtained by subtracting the loss amount from the charged amount of.

[Alkali metal hydroxide]
In the present invention, a sulfur source prepared in situ in the reaction system from the above-mentioned alkali metal hydrosulfide and alkali metal hydroxide can also be used. Further, a sulfur source can be prepared from alkali metal hydrosulfide and alkali metal hydroxide, and this can be transferred to a polymerization tank for use.

In this case, as specific examples of the alkali metal hydroxide, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more thereof can be mentioned as preferable ones. In particular, sodium hydroxide is preferably used in terms of cost and availability.

Further, in the present invention, the alkali metal hydroxide can be used not only as a preparation of a sulfur source but also as a polymerization stabilizer for stabilizing a polymerization reaction system and suppressing side reactions such as a decomposition reaction. The substantial amount of alkali metal hydroxide used to efficiently obtain these effects is 1.0 mol of sulfur atoms in the system from the viewpoint of stabilizing the activity of the thiolate terminal growth chain in the polymerization system. On the other hand, it preferably exceeds 1.03 mol. The upper limit is preferably 2.0 mol or less, preferably 1.8 mol or less, and more preferably 1.6 mol or less. When the range exceeds 1.03 mol with respect to 1.0 mol of sulfur atoms in the system, (X) polyarylene sulfide does not tend to decompose, and when it is 2.0 mol or less, the amount of polymerization by-biomass is high. It doesn't generate much. However, the substantial amount of the alkali metal hydroxide described here is the amount that exists as an alkali metal hydroxide after being consumed for neutralization with other acidic compounds in the system.

In the present invention, when alkali metal sulfide, which is a precursor of alkali metal hydrosulfide, is used as the sulfur source, the alkali metal hydroxide mainly contributes as a polymerization stabilizer, but the amount used is, for example, alkali. When the metal sulfide is sodium sulfide, it is preferably 0.03 mol or more with respect to 1 mol of sodium sulfide. Further, as the upper limit, 1.0 mol or less is preferable, 0.8 mol or less is more preferable, and 0.6 mol or less can be exemplified as a more preferable range.

[Organic polar solvent]
In the present invention, an organic polar solvent is used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidi. Because aprotic organic solvents such as non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfoxide, and mixtures thereof have high reaction stability. Is preferably used for. Of these, N-methyl-2-pyrrolidone (NMP) is particularly preferably used.

In the present invention, the amount of the organic polar solvent used as the polymerization solvent for (X) polyarylene sulfide is not particularly limited, but from the viewpoint of stable reactivity, 2.5 mol or more per 1.0 mol of sulfur atoms in the system is used. Preferably, from the viewpoint of economic efficiency, a range of less than 5.5 mol, preferably less than 5.0 mol, and more preferably less than 4.5 mol per 1.0 mol of sulfur atoms in the system is selected.

[Dihalogenated aromatic compounds]
The dihalogenated aromatic compound used in the present invention includes dihalogenated benzene such as p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene and p-dibromobenzene, 2,3-dichlorobenzoic acid and 2,4-dichlorobenzoic acid. Acids, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid and their salts, 2,3-dichlorophenol, 2,4- Dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol and salts thereof, 2,3-dichloroaniline, 2,4-dichloroaniline, Reactive functional groups such as 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 4-amino-2,5-dichlorobenzoic acid and salts thereof. Examples thereof include benzene having dihalogenate, and it is also possible to use two or more different dihalogenated aromatic compounds in combination for producing a copolymer of (X) polyarylene sulfide. Of these, a dihalogenated aromatic compound containing p-dihalogenated benzene as a main component, typified by p-dichlorobenzene, is preferable.

In the present invention, it is preferable to obtain (X) polyarylene sulfide having many functional groups at the terminal of the molecular chain, and it is not preferable to use a dihalogenated aromatic compound in a large excess because it causes an increase in the amount of halogen at the terminal. .. Therefore, the upper limit of the amount of the dihalogenated aromatic compound used is preferably less than 1.05 mol, more preferably less than 1.04 mol, and particularly preferably less than 1.03 mol, per 1.00 mol of sulfur atoms in the system. The range can be exemplified. Further, if the amount of the dihalogenated aromatic compound is too small, the growth chain at the thiolate terminal becomes excessive in the reaction system, which causes a decomposition reaction. Therefore, the lower limit of the amount of the dihalogenated aromatic compound used is preferably 0.75 mol or more, more preferably 0.8 mol or more per 1.00 mol of sulfur atoms in the system.

[Monohalogenated compound having a reactive functional group]
The monohalogenated compound having a reactive functional group used in the synthesis of (X) polyarylene sulfide of the present invention is a monohalogen represented by the following general formula (Ia) and / or general formula (Ib). Any chemical compound may be used.

(In formulas (Ia) and (Ib), V represents a halogen and W represents a carboxyl group or a metal salt thereof.)

Specific examples of such monohalogenated compounds include 3-chlorophthalic acid, sodium hydrogen 3-chlorophthalate, 3-chlorophthalic anhydride, 4-chlorophthalic acid, sodium hydrogen 4-chlorophthalate, and 4-chlorophthalic anhydride. And so on. From the viewpoint of reactivity and versatility during polymerization, 3-chlorophthalic acid, 4-chlorophthalic acid, sodium hydrogen 4-chlorophthalate, and 4-chlorophthalic anhydride are preferable monohalogenated compounds. In addition, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-amino-4-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid, 4 -Chlorobenzophenone-2-carboxylic acid, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-chlorobenzamide, 4-chlorobenzeneacetamide, 4 -Chlorobenzenesulfonamide, 4-amino-5-chlorophthalic acid, 4-chloro-5-nitrophthalic acid, 4-chlorobenzenesulfonic acid, 4-chlorobenzenethiol, 4'-chlorobenzophenone-2-carboxylic acid, 2-amino-5 Examples thereof include monohalogenated compounds such as −chlorobenzophenone, 3,5-diaminochlorobenzene and 5-chloroisophthalic acid. Further, these monohalogenated compounds may be used alone or in combination of two or more.

The lower limit of the amount of the monohalogenated compound having a reactive functional group used is preferably 0.01 mol% or more, preferably 1.00 mol% or more, and 10 mol% per 1.00 mol of sulfur atoms in the system. The above is more preferable, and 20 mol% or more is particularly preferable from the viewpoint of introducing a large amount of reactive functional groups into the terminals to increase the efficiency of the copolymerization reaction.

The upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, per 1.00 mol of sulfur atoms in the system. When the amount of the monohalogenated compound used exceeds 0.01 mol%, the introduction of the reactive terminal in the obtained (X) polyarylene sulfide is sufficient, while when it is 40 mol% or less, a decomposition reaction occurs. , (X) The molecular weight of the polyarylene sulfide does not decrease, and there is no disadvantage such as an increase in raw material cost.

Further, it is preferable that the total amount of the halogenated compound such as the dihalogenated aromatic compound and the monohalogenated compound is within a specific range, and the total amount of the halogenated compound with respect to 1.00 mol of sulfur atoms in the system is 0.95. It is preferably mol or more, more preferably 1.00 mol or more, and even more preferably 1.03 mol or more. On the other hand, the upper limit of the total amount of the halogenated compound with respect to 1.00 mol of sulfur atoms in the system is preferably less than 1.30 mol, more preferably less than 1.20 mol. If the total amount of halogenated compounds is 0.95 mol or more with respect to 1.00 mol of sulfur atoms in the system, there is no tendency to decompose, and if it is less than 1.30 mol, the molecular weight decreases and polyarylene sulfide is originally present. It does not mean that the heat resistance of is not exhibited.

The timing of adding the monohalogenated compound having a reactive functional group is not particularly limited, and the monohalogenated compound may be added at any of the dehydration step, the start of polymerization, and the middle of polymerization, which will be described later, and may be added in a plurality of times. May be added. The monohalogenated compound is preferably added at a conversion rate of less than 80%, more preferably less than 70%, and at the start of polymerization, that is, from the start of polymerization to the start of polymerization. Most preferably, it is added at the same time. When the monohalogenated compound is added at a preferable time in this way, a reflux device or a press-fitting device that prevents the monohalogenated compound from volatilizing is unnecessary, and the consumption of the monohalogenated compound is not completed at the end of polymerization. Does not remain in the polymerization system.

[Polymerization aid]
In the present invention, it is also one of the preferable embodiments to use a polymerization aid. One purpose of using the polymerization aid is to adjust the (X) polyarylene sulfide to a desired melt viscosity, while the other purpose is to reduce the amount of volatile components. Specific examples of such a polymerization aid include organic carboxylic acid metal salts, water, alkali metal chlorides (excluding sodium chloride), organic sulfonic acid metal salts, alkali metal sulfates, and alkaline earth metal oxidation. Things, alkali metal phosphates and alkaline earth metal phosphates and the like. These can be used alone or two or more at the same time. Of these, organic carboxylic acid metal salts and / or water are preferably used.

The organic carboxylic acid metal salt is a general formula R (COOM) n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. Is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. N is an integer of 1 to 3).) Can be mentioned as a preferable example. The organic carboxylic acid metal salt can also be used as a hydrate, an anhydride or an aqueous solution. Specific examples of the organic carboxylate metal salt include lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and the like. And their mixtures and the like. The organic carboxylic acid metal salt is obtained by adding an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates in approximately equal chemical equivalents and reacting them. May be formed by. Among the above organic carboxylic acid metal salts, the lithium salt has high solubility in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts have insufficient solubility in the reaction system. Sodium acetate, which is estimated to be inexpensive and has an appropriate solubility in the reaction system, is preferably used.

When the organic carboxylic acid metal salt is used as the polymerization aid, the amount used is preferably 0.01 mol or more, more preferably 0.02 mol or more, and the upper limit thereof with respect to 1.00 mol of sulfur atoms in the system. The range is preferably less than 0.70 mol, more preferably less than 0.60 mol, and particularly preferably less than 0.55 mol.

When an organic carboxylic acid metal salt is used as a polymerization aid, the timing of its addition is not particularly limited, and it may be added at any time during the dehydration step, the start of polymerization, or the middle of polymerization, which will be described later, and a plurality of times. However, from the viewpoint of ease of addition, it is preferable to add them at the same time at the start of the dehydration step or the start of polymerization.

When water is used as the polymerization aid, it is possible to use water alone, but it is preferable to use an organic carboxylic acid metal salt at the same time, whereby the effect as a polymerization aid can be further enhanced and less polymerization is performed. Even with the amount of the auxiliary agent used, it tends to be possible to obtain (X) polyarylene sulfide having a desired melt viscosity in a short time. In this case, the range of the preferable water content in the polymerization system is preferably 0.80 mol or more, more preferably 0.85 mol or more, based on 1.00 mol of sulfur atoms in the system. The upper limit is preferably less than 3.00 mol, more preferably less than 1.80 mol. If the amount of water is too large, the internal pressure of the reactor rises significantly, and a reactor having high pressure resistance is required, which tends to be unfavorable in terms of economy and safety. The conversion rate of the dihalogenated aromatic compound at the stage where the water content in the polymerization system is within the above range is 60 mol% or more, preferably 70% or more, more preferably 80% or more, still more preferably 90%, as described later. The above is preferable. Water produced as a by-product during polymerization can also be a polymerization aid.

Further, it is also one of the preferable modes to add water after the polymerization. The preferable range of the water content in the polymerization system after adding water after the polymerization is preferably 1.0 mol or more, preferably 1.5 mol or more, with respect to 1.0 mol of sulfur atoms in the system. The upper limit is preferably 15.0 mol or less, more preferably 10.0 mol or less.

[Branching / cross-linking agent]
In the present invention, it is possible to obtain an (X) polyarylene sulfide having a substantially linear PAS having a high melt fluidity and a reduced chlorine content and a reduced amount of volatile components, but branching or cross-linking. Polyhalogen compounds above trihalogenation (not necessarily aromatic compounds), active hydrogen-containing halogenated aromatic compounds, halogenated aromatic nitro compounds, etc., in order to form a polymer and adjust to the desired melt viscosity. It is also possible to use the branching / cross-linking agent of. As the polyhalogen compound, a commonly used compound can be used, but a polyhalogenated aromatic compound is preferable, and specific examples thereof include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, and the like. 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 1,4,6-trichloronaphthalene and the like can be mentioned, and 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene are preferable. Examples of the active hydrogen-containing halogenated aromatic compound include halogenated aromatic compounds having functional groups such as an amino group, a mercapto group and a hydroxyl group. Specific examples include 2,5-dichloroaniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 2,4,6-trichloroaniline, 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2 , 4'-diamino-2', 4-dichlorodiphenyl ether and the like. Examples of the halogenated aromatic nitro compound include 2,4-dinitrochlorobenzene, 2,5-dichloronitrobenzene, 2-nitro-4,4'-dichlorodiphenyl ether, and 3,3'-dinitro-4,4'-. Examples thereof include dichlorodiphenylsulfone, 2,5-dichloro-2-nitropyridine, 2-chloro-3,5-dinitropyridine and the like.

[Dehydration process]
In the method for producing (X) polyarylene sulfide of the present invention, the sulfur source is usually used in the form of a hydrate, but a dihalogenated aromatic compound or a monohalogenated aromatic compound having a reactive functional group is added. Before, it is preferable to heat the mixture containing the organic polar solvent and the sulfur source to remove an excess amount of water from the system. If too much water is removed by this operation, it is preferable to add the insufficient water to replenish the water.

Further, as described above, as a sulfur source, an alkali metal sulfide prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank should also be used. Can be done. This method is not particularly limited, but preferably, an alkali metal hydrosulfide and an alkali metal hydroxide are used as an organic polar solvent in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C. in an inert gas atmosphere. In addition, a method of distilling off water by raising the temperature to at least 150 ° C. or higher, preferably 180 ° C. to 260 ° C. under normal pressure or reduced pressure can be mentioned. A polymerization aid may be added at this stage. Further, in order to promote the distillation of water, toluene or the like may be added to carry out the reaction.

The amount of water in the system at the stage when the dehydration step is completed is preferably 0.90 or more and 1.10 mol or less per 1.00 mol of the charged sulfur source. Here, the amount of water in the system is the amount obtained by subtracting the amount of water removed from the system from the amount of water charged in the dehydration step. Further, the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.

After the dehydration step is completed, the reaction product prepared in the dehydration step is brought into contact with the dihalogenated aromatic compound and the monohalogenated aromatic compound having a reactive functional group in an organic polar solvent to carry out a polymerization reaction. The polymerization reaction step described later may be carried out in the same reactor as the step, or the polymerization reaction step may be carried out after transferring the reactant prepared in the dehydration step to a reaction vessel different from the dehydration step.

[Polymerization reaction step]
In the method for producing (X) polyarylene sulfide in the present invention, a polymerization step is carried out in which the reaction product prepared in the dehydration step described above is brought into contact with a dihalogenated aromatic compound or a monohalogenated compound in an organic polar solvent to carry out a polymerization reaction. .. At the start of the polymerization step, preferably under an inert gas atmosphere, 100 ° C. or higher, preferably 130 ° C. or higher is preferable, and the upper limit is 220 ° C. or lower, preferably 200 ° C. or lower. And add the dihalogenated aromatic compound. The order of charging these raw materials may be random or may be simultaneous.

This polymerization reaction is carried out in a temperature range of 200 ° C. or higher and lower than 280 ° C., but the polymerization conditions are not limited as long as the effects of the present invention can be obtained. For example, a method in which the temperature is raised at a constant rate and then the reaction is continued at 245 ° C. or higher and lower than 280 ° C. for a certain period of time. A method of heating and continuing the reaction for a certain period of time. After carrying out the reaction at a constant temperature of 200 ° C. or higher and lower than 245 ° C., particularly 230 ° C. or higher and lower than 245 ° C., the temperature is raised to 245 ° C. or higher and lower than 280 ° C. for a short time. There is a method of completing the reaction with. Further, in this polymerization reaction, the longer the reaction time is at a constant temperature for a certain period of time at 200 ° C. or higher and lower than 245 ° C., particularly at 230 ° C. or higher and lower than 245 ° C., the more efficiently the monohalogenated compound having a reactive functional group is polyarylene sulfide. Reacts with, and there is a tendency to obtain a preferable (X) polyarylene sulfide.

Further, the atmosphere in which the above-mentioned polymerization reaction is carried out is preferably in a non-oxidizing atmosphere, preferably in an atmosphere of an inert gas such as nitrogen, helium or argon, especially from the viewpoint of economy and ease of handling. It is preferably performed in a nitrogen atmosphere. Further, the reaction pressure in the polymerization reaction is not particularly limited because it cannot be unconditionally defined depending on the type and amount of the raw material and solvent used, the polymerization reaction temperature, and the like.

The reaction amount of the monohalogenated aromatic compound having a reactive functional group at the stage when the polymerization reaction step is completed is, for example, the functional group direct analysis by solid-state NMR, the absorption and functional group derived from the benzene ring by FT-IR. It can be evaluated by relative evaluation by comparison of absorption of origin, reaction amount calculated by subtracting residual amount from the charged amount of reactive functional group-containing monohalogenated aromatic compound before or during polymerization.

The reaction amount of the monohalogenated aromatic compound having a reactive functional group is preferably 0.01 mol or more, more preferably 0.10 mol or more, and 0.15 mol or more with respect to 1.00 mol of sulfur atoms in the system. Is particularly preferable.

The upper limit is preferably 0.40 mol or less, and more preferably 0.30 mol or less. The reaction amount in the present invention is the amount of a monohalogenated compound having a reactive functional group remaining in the sample sampled after the completion of the polymerization step, and is quantified by a gas chromatograph (GC-14B manufactured by Shimadzu Corporation) before polymerization or before polymerization. It is a value calculated by subtracting the residual amount from the amount charged during polymerization. The larger the reaction amount, the larger the amount of the reactive functional group introduced into the (X) polyarylene sulfide terminal, which tends to have higher reactivity, and the reaction amount is 0. If it is 40 mol or less, the molecular weight of (X) polyarylene sulfide is reduced, and the heat resistance is not lowered. On the other hand, if the reaction amount is 0.01 mol or more, the introduction of the reactive functional group into (X) polyarylene sulfide is not insufficient.

[Polymer recovery]
In the production of the (X) polyarylene sulfide of the present invention, after the completion of the polymerization step, the (X) polyarylene sulfide is recovered from the polymerization reaction product containing the (X) polyarylene sulfide component and the solvent obtained in the polymerization step. .. As a recovery method, for example, a flash method, that is, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 0.8 MPa or higher) state into an atmosphere of normal pressure or reduced pressure to recover the solvent and at the same time powder the polymer is granulated. The method of recovering the polymer or the quenching method, that is, the polymerization reaction product is gradually cooled from a high temperature and high pressure state to precipitate the (X) polyarylene sulfide component in the reaction system, and the temperature is 70 ° C. or higher, preferably 100 ° C. or higher. Examples thereof include a method of recovering a solid containing the (X) polyarylene sulfide component by filtering in a state.

If the (X) polyarylene sulfide having a large number of reactive functional groups introduced at the end of the polymer chain can be obtained without impairing the original heat resistance of PAS, which is the present invention, the method is limited to either the quench method or the flash method. Although it is not a thing, the flash method is economically superior in that it is possible to recover the solid matter at the same time as the solvent recovery, the recovery time is relatively short, and the amount of recovered material obtained is larger than that of the quench method. It was obtained by the quench method because it is a recovery method and the PAS obtained by the flash method contains a large amount of oligomer components having a reactive functional group at the end of the polymer chain as represented by the chloroform extraction component. This is a preferable recovery method in the present invention because it is easy to easily obtain a PAS having a large amount of reactive functional groups introduced as compared with the PAS. The amount of chloroform extracted that is preferable for obtaining (X) polyarylene sulfide having a high functional group content can be exemplified by 1.0% by weight or more, and more preferably 2.0% by weight or more. The amount of chloroform extracted here is expressed as a percentage of the weight of the polymer obtained when 10 g of the polymer is soxhlet-extracted with 100 g of chloroform at 90 ° C. and chloroform is distilled off from this extract.

As a preferred embodiment of the flash method, a method of ejecting a high-temperature and high-pressure polymerization reaction product obtained in the polymerization step into an atmosphere such as nitrogen or water vapor under normal pressure can be exemplified. In the flash method, the solvent can be efficiently recovered by utilizing the heat of vaporization of the solvent when the polymerization reaction product is flushed from the high temperature and high pressure state to the normal pressure state. Efficiency is reduced and productivity is reduced. Therefore, the temperature in the polymerization system at the time of flushing, that is, the temperature of the polymerization reaction product is preferably 250 ° C. or higher, more preferably 255 ° C. or higher. The temperature of the atmosphere such as nitrogen or water vapor when flushing under normal pressure is usually selected to be 150 to 250 ° C. If the solvent recovery from the polymerization reaction product is insufficient, nitrogen or water vapor at 150 to 250 ° C. after flushing is used. Heating may be continued in the atmosphere of.

Since the (X) polyarylene sulfide obtained by such a flash method contains ionic impurities such as alkali metal halides and alkali metal organic substances which are polymerization by-products, it is customary to perform cleaning. The cleaning conditions are not particularly limited as long as they are sufficient to remove such ionic impurities. Examples of the cleaning liquid include a method of cleaning with water or an organic solvent. Water is easy and inexpensive to obtain (X) polyarylene sulfide and contains an oligomer component to have a high functional group content. Can be exemplified as a preferable method. In order to obtain the (X) polyarylene sulfide having a reactive functional group at the terminal according to the present invention, the temperature of water is preferably 80 ° C. or higher, and hot water, an acid or an aqueous solution of an acid, an alkali metal salt or an alkali. It is preferable to carry out the treatment of immersing in any liquid of the aqueous solution of the earth metal salt at least once.

Further, it is preferable to carry out the dipping treatment at a temperature of 80 ° C. or higher twice or more, and the first treatment is carried out by dipping in any liquid of hot water, an alkali metal salt or an aqueous solution of an alkaline earth metal salt. Is preferable. Of course, when the treatment of immersing twice or more is performed, the cleaning temperature in each treatment may be different, or the treatment of immersing in two or more different liquids can be used in combination, and each treatment can be used in combination. In between, it is a more preferable method to go through a filtration step of separating the polymer and the cleaning liquid.

In the treatment of immersing the (X) polyarylene sulfide in the acid or the aqueous solution of the acid, the pH of the liquid after the treatment is preferably 2 to 8. The acid or an aqueous solution of an acid is an organic acid, an inorganic acid, or the above-mentioned water added with an organic acid, an inorganic acid, or the like to make it acidic. Examples of the organic acid and the inorganic acid to be used include acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and the like, and acetic acid and hydrochloric acid are preferable without limitation.

The amount of alkali metal salt or alkaline earth metal salt in the aqueous solution used for the treatment of immersing (X) polyarylene sulfide in the aqueous solution of alkali metal salt or alkaline earth metal salt is 0. 01 to 20% by weight is preferable, and 0.1 to 15% by weight is more preferable. The aqueous solution of an alkali metal salt or an alkaline earth metal salt is obtained by adding an alkali metal salt, an alkaline earth metal salt, or the like to the above water and dissolving it. Examples of the alkali metal salt and alkaline earth metal salt to be used include, but are not limited to, the calcium salt, potassium salt, sodium salt, magnesium salt and the like of the above organic acids.

The cleaning temperature for cleaning (X) polyarylene sulfide with a liquid is preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 150 ° C. or higher and 200 ° C. or lower, and further 180 ° C. or higher in terms of obtaining PAS with less ionic impurities. More preferably 200 ° C. or lower. The operation of the treatment with a liquid of 100 ° C. or higher is usually carried out by adding a predetermined amount of (X) polyarylene sulfide to a predetermined amount of liquid and heating and stirring at normal pressure or in a pressure vessel.

The water used for hot water, an aqueous acid solution, an alkali metal salt or an alkaline earth metal salt aqueous solution is preferably distilled water or deionized water. As for the ratio of (X) polyarylene sulfide to liquid, it is preferable that the amount of liquid is large, and usually, a bath ratio of 10 to 500 g of (X) polyarylene sulfide is preferably selected with respect to 1 liter of liquid, and 50 to 200 g is more preferable.

The cleaning additive may be used at any stage of the cleaning process, but in order to efficiently perform cleaning with a small amount of additive, the solid material recovered by the flash method is hot water at 80 ° C. or higher and 200 ° C. or lower. A method of immersing (X) polyarylene sulfide in an acid or an aqueous solution of an acid at 150 ° C. or higher after performing the treatment of immersing and filtering in the water several times is preferable.

[Other post-processing]
The (X) polyarylene sulfide thus obtained is dried under normal pressure and / or reduced pressure. The drying temperature is preferably in the range of 120 to 280 ° C, more preferably in the range of 140 to 250 ° C. The dry atmosphere may be an inert atmosphere such as nitrogen, helium or under reduced pressure, an oxidizing atmosphere such as oxygen or air, or a mixed atmosphere of air and nitrogen, but the inert atmosphere is preferable because of the melt viscosity. The drying time is preferably 0.5 to 50 hours, preferably 1 to 30 hours, and even more preferably 1 to 20 hours.

The (X) polyarylene sulfide obtained in the present invention is subjected to a temperature of 130 to 260 ° C. under an oxygen-containing atmosphere in order to remove volatile components or to increase the crosslinked high molecular weight to a preferable melt viscosity. It is also possible to process.

When dry heat treatment is performed for the purpose of suppressing cross-linking high molecular weight and removing volatile components, the heat treatment may be performed in a high oxygen concentration atmosphere or a low oxygen concentration atmosphere as long as the heat treatment temperature and heat treatment time are within a specific range. ..

As a condition of a high oxygen concentration atmosphere, the oxygen concentration is preferably 2% by volume or more, the heat treatment temperature is 160 to 270 ° C., and the heat treatment time is preferably 0.1 to 20 hours. However, under conditions of high oxygen concentration, the rate of reduction of volatile components is high, but at the same time, oxidative cross-linking proceeds rapidly, so that reactive functional groups tend to decrease. Therefore, it is generally preferable to perform the heat treatment at a low temperature for a long time or at a high temperature for a short time. Specific conditions for low-temperature and long-term heat treatment are preferably 160 ° C. or higher and 210 ° C. or lower for 1 hour or longer and 20 hours or shorter, and more preferably 170 ° C. or higher and 200 ° C. or lower for 1 hour or longer and 10 hours or shorter. When the heat treatment is performed at a temperature below 160 ° C., the effect of reducing volatile components is small. Further, even at a low temperature, if the heat treatment time exceeds 20 hours under the condition that the oxygen concentration is 2% by volume or more, the reactive functional groups tend to decrease. Specific conditions for high-temperature and short-time heat treatment are preferably 0.1 hour or more and less than 1 hour at 210 ° C. or higher and 270 ° C. or lower, and more preferably 0.2 to 0.8 hours at 220 ° C. or higher and 260 ° C. or lower. When the heat treatment temperature exceeds 270 ° C., oxidative cross-linking proceeds rapidly and the reactive functional groups tend to decrease. Further, even at a high temperature, when the heat treatment time is less than 0.1 hour under the condition of oxygen concentration of 2% by volume or more, the effect of reducing volatile components is small.

As a condition of a low oxygen concentration atmosphere, the oxygen concentration is preferably less than 2% by volume, the heat treatment temperature is preferably 210 to 270 ° C., and the heat treatment time is preferably 0.2 to 50 hours. Since the effect of reducing volatile components tends to be small when the oxygen concentration is low, it is generally preferable to carry out the heat treatment at a high temperature for a long time, and more preferably to carry out the heat treatment under a heat treatment temperature condition of 220 ° C. to 260 ° C. for 2 to 20 hours. .. When the heat treatment time is less than 210 ° C., it is difficult to reduce the volatile components, and when the heat treatment time exceeds 50 hours, the productivity is lowered.

When the dry heat treatment is performed for the purpose of increasing the molecular weight of the crosslinked material and adjusting the melt viscosity to a preferable level, the temperature is preferably 160 to 260 ° C., more preferably 170 to 250 ° C. Further, it is desirable that the oxygen concentration is 2% by volume or more, more preferably 8% by volume or more. The treatment time is preferably 1 to 100 hours, more preferably 2 to 50 hours, still more preferably 3 to 25 hours.

The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary type or a stirring blade is used. It is more preferable to use it.

(4) (Y) Polyorganosiloxane Containing Amino Group and / or Isocyanate Group The (Y) polyorganosiloxane containing an amino group and / or isocyanate group used in the present invention is (X) polyarylene sulfide. Anything that reacts efficiently may be used, and examples thereof include those represented by the following general formula (R).

Here, P and Q represent an amino group and / or an isocyanate group. P and Q may be the same or different. It does not matter if these functional groups are bonded to one end or the side chain of the polyorganosiloxane, but it is preferable that these functional groups are bonded to both ends from the viewpoint of efficient modification by block copolymerization. Further, R ¹ , R ² and R ³ indicate an alkyl group of C1 to C10 or an aromatic group of C6 to C10. Specifically, examples of R ¹ and R ² include alkyl groups such as methyl group, ethyl group and propyl group, and aromatic groups such as phenyl group and naphthyl group, which are preferably available from the viewpoint of availability. It is preferable to have a structure consisting of a methyl group, a phenyl group, or a combination thereof. As R ^3, a methyl group, an ethyl group, an alkyl group such as a propyl group, a phenyl group, there may be mentioned aromatic groups such as naphthyl group, a methyl group in view of easy availability, an ethyl group or a propyl group, preferable. n is 1 or more, preferably 5 or more, and particularly preferably 10 or more. On the other hand, the upper limit thereof is 100 or less, preferably 60 or less, and particularly preferably 40 or less from the viewpoint of compatibility with polyarylene sulfide and an organic polar solvent.

The functional group of the (Y) polyorganosiloxane containing an amino group and / or an isocyanate group is more preferably an amino group from the viewpoint of reactivity.

Further, the functional group content of the (Y) polyorganosiloxane containing an amino group and / or an isocyanate group varies depending on the combination with the functional group of the (X) polyarylene sulfide, and therefore cannot be unconditionally specified, but 100 μmol / g. The above is preferable, and from the viewpoint of increasing the amount of copolymerization with (X) polyarylene sulfide, 250 μmol / g or more is more preferable, and 400 μmol / g or more is particularly preferable. When the functional group content of the (Y) polyorganosiloxane having a functional group is 100 μmol / g or more, the copolymerization amount of the (Y) polyorganosiloxane is sufficient, so that a sufficient modification effect can be obtained. The upper limit thereof is not particularly limited, but is preferably 4,000 μmol / g or less, and particularly preferably 3,000 μmol / g or less. Specific examples of such (Y) polyorganosiloxane are KF-8010, KF-8012, KF-8008, X-22-161A, X-22-161B, and X-22, which are commercially available from Shinetsu Silicone. -1660B-3, KF-857, KF-8001, KF-862, KF-858, X-22-9192 and the like can be mentioned.

(5) Method for producing polyarylene sulfide block copolymer The following describes the method for producing the polyarylene sulfide block copolymer of the present invention, including a polymerization reaction step, polymer recovery, an inorganic filler, other additives, and uses.

[Polymerization reaction step]
In the method for producing a polyarylene sulfide block copolymer of the present invention, (X) polyarylene sulfide having an acid anhydride group at the terminal and (Y) polyorganosiloxane containing an amino group and / or an isocyanate group are heated. To react.

Further, the terminal functional group ratio of (X) polyarylene sulfide is preferably 85% or more, more preferably 90% or more, and 95 from the viewpoint of efficiently performing block copolymerization to obtain a high molecular weight polyarylene sulfide block copolymer. % Or more is particularly preferable.

However, the terminal functional group ratio is determined by ((functional group content (mol / g) / (1 / number average molecular weight (g / mol) × 2)) × 100 (%), and the unit is a percentage. Can be defined as.

The mixing ratio of (X) polyarylene sulfide and (Y) polyorganosiloxane includes the molecular weight and functional group content of (X) polyarylene sulfide to be used, the type and molecular weight of (Y) polyorganosiloxane, and the reaction conditions. Although it cannot be unconditionally specified because it depends on the above, the ratio of the amount of functional groups of (Y) polyorganosiloxane to the amount of functional groups of (X) polyarylene sulfide (hereinafter referred to as the functional group ratio) is 0.8. The above can be exemplified as a preferable range, and more preferably 1.0 or more, from the viewpoint of promoting block copolymerization more efficiently and increasing the molecular weight of the polyarylene sulfide block copolymer, 1 .2 or more is particularly preferable. On the other hand, as the upper limit thereof, 5.0 or less can be exemplified as a preferable range, and 3.0 or less is more preferable, and block copolymerization can proceed more efficiently, and the polyarylene sulfide block copolymer can be produced. From the viewpoint of promoting the increase in the molecular weight of the above, the amount is most preferably 2.0 or less. When the functional group ratio is 1.0 or more, the copolymerization reaction easily proceeds, so that a sufficient modification effect can be obtained. When the functional group ratio is 5.0 or less, the unreacted (Y) polyorganosiloxane does not increase, resulting in purification. The process is not complicated and the raw material cost does not increase.

Further, the reaction of (X) polyarylene sulfide and (Y) polyorganosiloxane by heating may be carried out by either melt polymerization using no solvent or solution polymerization in an organic polar solvent, if necessary. In the latter case, the use of an organic amide solvent is preferable, and specific examples thereof include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone, and N-. Caprolactams such as methyl-ε-caprolactam, aprotic organic solvents such as 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, etc. And a mixture thereof and the like are preferably used because of the high stability of the reaction. Of these, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone is preferable, and N-methyl-2-pyrrolidone is more preferably used. In addition to this, chloronaphthalene or the like that dissolves (X) polyarylene sulfide is also preferably used. The amount of the organic polar solvent used is not particularly limited, but is preferably 0.1 mol or more per 1 mol of the structural unit of (X) polyarylene sulfide, and (X) polyarylene sulfide and (Y) poly. From the viewpoint of sufficiently dissolving the organosiloxane and obtaining high reactivity, 1.0 mol or more is more preferable. The upper limit is preferably 5.0 mol or less, and more preferably 3.5 mol or less from an economical point of view.

Further, the above two reactions may be combined, and for example, an organic polar solvent may be added and heated after melt polymerization, or the organic polar solvent may be further added after heating in the organic polar solvent within the above preferable range. It can also be added and heated.

The temperature at which a mixture containing (X) polyarylene sulfide and (Y) polyorganosiloxane is heated and reacted depends on the molecular weight of (X) polyarylene sulfide, the type and molecular weight of (Y) polyorganosiloxane, and the like. Although it cannot be specified in the above, it is preferable that the temperature is higher than the temperature at which (X) polyarylene sulfide and (Y) polyorganosiloxane are melted or dissolved in an organic polar solvent, and as a specific example, it is preferably 200 ° C. or higher. It can be exemplified, more preferably 230 ° C. or higher, and even more preferably 250 ° C. or higher. Further, the upper limit of the reaction temperature can be exemplified by 400 ° C. or lower, preferably 380 ° C. or lower, and more preferably 350 ° C. or lower. When the reaction temperature is 200 ° C. or higher, the reaction efficiency is high and block copolymerization is sufficient, and when the reaction temperature is 400 ° C. or lower, (X) polyarylene sulfide and (Y) polyorganosiloxane are not thermally decomposed. Further, the reaction may be a one-step reaction carried out at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

Further, when the polyarylene sulfide block copolymer is produced by this production method, the timing of adding the (Y) polyorganosiloxane is not particularly limited, and the polyarylene sulfide block copolymer may be added at any time of the start of polymerization and the middle of polymerization. ..

The time for the copolymerization reaction of (X) polyarylene sulfide and (Y) polyorganosiloxane depends on the conditions such as the structure, molecular weight, and reaction temperature of (X) polyarylene sulfide and (Y) polyorganosiloxane used in the reaction. Therefore, although it cannot be unconditionally specified, 0.1 hours or more can be exemplified from the viewpoint of productivity and sufficient progress of the copolymerization reaction, and 0.5 hours or more is preferable. On the other hand, the upper limit of the reaction time is not particularly limited, but from the viewpoint of productivity, 10 hours or less, preferably 8 hours or less, more preferably 6 hours or less can be adopted. Further, the polymerization atmosphere in the method for producing a polyarylene sulfide block copolymer of the present invention is a reaction condition generally adopted for producing polyarylene sulfide, for example, a reaction under an inert atmosphere such as nitrogen, helium or argon. A reaction under reduced pressure or the like can be appropriately adopted.

[Polymer recovery]
The method for recovering the polyarylene sulfide block copolymer is not particularly limited. For example, it has low solubility in the polyarylene sulfide block copolymer component and is heated with a solvent that dissolves (Y) polyorganosiloxane, if necessary. An example is a method of recovering the polyarylene sulfide block copolymer as a solid by contacting with. Solvents having such characteristics are generally relatively low-polarity solvents, and the preferred solvent differs depending on the type of polyorganosiloxane used, and thus cannot be limited. However, for example, hydrocarbons typified by hexane, heptane, and octane. Aromatic hydrocarbons such as benzene, toluene and xylene, and long-chain alcohols such as hexanol, heptanol and octanol can be exemplified, and hexane is preferable from the viewpoint of availability and economy. Further, in order to remove the organic polar solvent as needed, the polyarylene sulfide block is brought into contact with a solvent having low solubility in the block copolymer component and miscible with the organic polar solvent under heating as necessary. A method of recovering the block copolymer as a solid may be combined. Solvents having such characteristics are generally relatively highly polar solvents, and the preferred solvent differs depending on the type of organic polar solvent used, and thus cannot be limited. For example, water, methanol, ethanol, propanol, isopropanol, butanol, hexanol, etc. Examples thereof include alcohols represented by, acetone, ketones represented by methyl ethyl ketone, acetate esters represented by ethyl acetate, butyl acetate and the like, and water, methanol and acetone are preferable from the viewpoint of availability and economy. Water is particularly preferred.

By performing the treatment with such a solvent, it is possible to reduce the amount of the unreacted (Y) polyorganosiloxane and the organic polar solvent contained in the polyarylene sulfide block copolymer. Since the polyarylene sulfide block copolymer is precipitated as a solid component by this treatment, it can be recovered by using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. It should be noted that these series of treatments can be repeated several times as needed, whereby the amount of unreacted (Y) polyorganosiloxane or organic polar solvent contained in the polyarylene sulfide block copolymer is further increased. It tends to be reduced.

[Inorganic filler]
The polyarylene sulfide block copolymer of the present invention can also be used as a composition containing an inorganic filler for the purpose of improving mechanical strength and the like as long as the effects of the present invention are not impaired. Specific examples of such inorganic fillers include glass fibers, carbon fibers, carbon nanotubes, carbon nanohorns, potassium titanate whiskers, zinc oxide whiskers, calcium carbonate whiskers, wallastenite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, and silicon carbide fibers. , Ceramic fiber, asbestos fiber, stone shaving fiber, metal fiber and other fibrous fillers, or fullerene, talc, wallastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silates such as silicates, silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, metal compounds such as iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and water. Hydroxide such as calcium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, non-fibrous fillers such as graphite are used. Of these, glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of food-proofing materials and fillers. Further, these inorganic fillers may be hollow, and two or more kinds thereof can be used in combination. Further, these inorganic fillers may be pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound before use. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the effects of preventing foodstuffs, lubricants, and imparting conductivity.

The blending amount of the inorganic filler is selected in the range of 30 parts by weight or less, preferably less than 10 parts by weight, and more preferably less than 1 part by weight with respect to 100 parts by weight of the polyarylene sulfide block copolymer. A range of 0.8 parts by weight or less is more preferable. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity. When the content of the inorganic filler is in the above-mentioned preferable range, it is effective in improving the elastic modulus of the material, but does not bring about a decrease in toughness.

[Other additives]
Further, a resin other than polyphenylene sulfide may be added to the polyarylene sulfide block copolymer of the present invention as long as the effects of the present invention are not impaired. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, and polythioether ketone. Examples thereof include resins, polyether ether ketone resins, polyimide resins, polyetherimide resins, polyether sulfone resins, polyamideimide resins, and tetrafluoride polyethylene resins.

Further, the following compounds can be added for the purpose of modification. Polyalkylene oxide oligoma compounds, thioether compounds, ester compounds, organophosphorus compounds and other plastics, organophosphorus compounds, polyether ether ketones and other crystal nucleating agents, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, anticoloring agents such as hypophosphates, (3,9-bis [2- (3- (3)) -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) and other phenolic compounds Antioxidants, phosphorus-based antioxidants such as (bis (2,4-dicumylphenyl) pentaerythritol-di-phosphite), and others such as water, lubricants, UV inhibitors, colorants, foaming agents, etc. Ordinary additives can be blended. The amount of the compound added is preferably 10% by weight or less, more preferably 1% by weight or less of the total composition. Within the above preferable range, the original characteristics are not impaired.

[Use]
The polyarylene sulfide block copolymer of the present invention can be used as it is, or as a composition containing the above-mentioned inorganic fillers and additives, by various molding methods such as injection molding, extrusion molding, compression molding, injection molding, and injection compression molding. It can be molded, but it is especially useful for injection molding and extrusion molding. Further, the polyphenylene sulfide block copolymer of the present invention is flexible and has extremely excellent tensile elongation at break and excellent heat aging resistance, so that it can be used for extrusion molding having a relatively high molding temperature and a long melt residence time. Especially useful. Examples of molded products obtained by extrusion molding include round bars, square bars, sheets, films, tubes, pipes, etc., and more specific applications include electrical insulation for water heater motors, air conditioner motors, drive motors, etc. Materials, film condensers, speaker diaphragms, magnetic tapes for recording, printed board materials, printed board peripheral parts, semiconductor packages, semiconductor transport trays, process / release films, protective films, automotive film sensors, wire cable insulation tapes , Insulated washer in lithium ion battery, hot water and cooling water, chemical tube, fuel tube for automobile, hot water pipe, chemical pipe for chemical plant, pipe for ultra-pure water and ultra-high purity solvent, Examples include automobile piping, piping pipes for Freon and supercritical carbon dioxide refrigerants, and workpiece holding rings for polishing equipment. In addition, wire harnesses and control wires for hybrid automobiles, electric automobiles, railways, motor coil windings for power generation equipment, heat-resistant electric wire cables for home appliances, flat cables used for wiring in automobiles, communication, etc. Examples thereof include a signal transformer for transmission, high frequency, audio, measurement, etc., or a coating molded body of a winding of an in-vehicle transformer.

Applications of molded products obtained by injection molding include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, machine breakers, knife switches, and other poles. Electrical equipment parts such as rods and electric parts cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, coil bobbins, condensers, variable condenser cases, optical pickups, oscillators, various terminal boards, metaphors, plugs. , Printed boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electronic components; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademarks) / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriters. Household and office electrical parts such as parts and word processor parts; office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machine-related parts: Optical equipment and precision machine-related parts such as microscopes, binoculars, cameras, watches, etc .; Alternator terminals, alternator connectors, IC regulators, potentiometer bases for light diers, exhaust gas valves, and other valves. , Fuel-related / exhaust system / intake system pipes and ducts, turbo duct, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature Sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, Wiper motor related parts, Dustributor, Starter switch, Starter relay, Transmission wire harness, Win Dwasher nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter , Automobile / vehicle-related parts such as an ignition device case, a gasket for a primary battery or a secondary battery of a mobile phone, a notebook computer, a video camera, a hybrid vehicle, an electric vehicle, and the like can be exemplified.

Among them, it is useful as a coating molded body for windings for motor coils of hybrid vehicles, electric vehicles, railways, and power generation equipment, and various fuel-related, exhaust system, and intake system pipes and ducts of automobiles exposed to high temperature environments, especially turbo ducts. Is.

Hereinafter, the present invention will be specifically described with reference to examples. These are exemplary and not limited thereto.

<Measurement of molecular weight>
The molecular weights of the (X) polyarylene sulfide and polyarylene sulfide block copolymers are the number average molecular weight (Mn) and the weight in terms of polystyrene by gel permeation chromatography (GPC), which is a type of size exclusion chromatography (SEC). The average molecular weight (Mw) and the degree of dispersion (= Mw / Mn) were calculated. The GPC measurement conditions are described below.
Equipment: SSC-7100 manufactured by Senshu Scientific Co., Ltd.
Column name: GPC3506 manufactured by Senshu Scientific Co., Ltd.
Eluent: 1-Chloronaphthalene detector: Differential refractive index detector Column temperature: 210 ° C
Pre-constant temperature bath temperature: 250 ° C
Pump constant temperature bath temperature: 50 ° C
Detector temperature: 210 ° C
Flow rate: 1.0 mL / min
Sample injection amount: 300 μL (slurry: about 0.2% by weight).

<Measurement of glass transition temperature, cold crystallization temperature and melting point>
(X) An amorphous film (thickness: 0.2 mm) of a polyarylene sulfide and polyarylene sulfide block copolymer was prepared, and the glass transition temperature, cold crystallization temperature and melting point were measured by a differential scanning calorimeter (DSC). did.

The preparation conditions for the pressed amorphous film are as follows.
-Wipe the surface of the Kapton film with acetone and place the sample on it.
・ Put Kapton film on top of each other and sandwich it with an aluminum sheet.
-Put it in a press die heated to 340 ° C.
・ After allowing to stay for 1 minute, pressurize 10 kgf.
・ After allowing to stay for 3 minutes, pressurize 40 kgf.
・ After allowing to stay for a total of 4 minutes, take out the Kapton film or aluminum sheet, soak it in the prepared water, and quench it.

The glass transition temperature was measured by DSC under the following conditions.
The pressed amorphous film obtained by the above method was heated from 0 ° C. to 340 ° C. at a rate of 20 ° C./min. The inflection point of the baseline shift detected at that time was defined as the glass transition temperature.

The cold crystallization temperature was measured by DSC under the following conditions.
The pressed amorphous film obtained by the above method was heated from 0 ° C. to 340 ° C. at a rate of 20 ° C./min. The value of the exothermic peak temperature detected at that time was defined as the cold crystallization temperature.

The melting point was measured by DSC under the following conditions.
The pressed amorphous film obtained by the above method was heated from 0 ° C. to 340 ° C. at a rate of 20 ° C./min.
-Then, the temperature was maintained at 340 ° C. for 1 minute, and the temperature was lowered to 100 ° C. at a rate of 20 ° C./min.
After that, the temperature was maintained at 100 ° C. for 1 minute, and the temperature was raised from 100 ° C. to 340 ° C. at a rate of 20 ° C./min. The value of the melting peak temperature detected at that time was taken as the melting point.

<Measurement of tensile elastic modulus and tensile elongation>
The tensile elastic modulus and tensile elongation of the polyarylene sulfide block copolymer are determined by punching a dumbbell having a thickness of 0.2 mm from the press crystallized film described below, and then using a Tensylon UTA2.5T tensile tester to obtain a distance between chucks of 25 mm. , It was measured by conducting a tensile test under the condition of a tensile speed of 1 mm / min.

The preparation conditions for the press crystallized film are as follows.
-Wipe the surface of the Kapton film with acetone and place the sample on it.
・ Put Kapton film on top of each other and sandwich it with an aluminum sheet.
-Put it in a press die heated to 340 ° C.
・ After allowing to stay for 1 minute, pressurize 10 kgf.
・ After allowing to stay for 3 minutes, pressurize 40 kgf.
・ After allowing to stay for a total of 4 minutes, take out the Kapton film or aluminum sheet and place it in a press die heated to 150 ° C.
・ After allowing to stay for 1 minute, remove the Kapton film or aluminum sheet together.

<Evaluation of film aspect>
The aspect evaluation of the press film of the polyarylene sulfide block copolymer was judged by the following evaluation criteria with respect to the above-mentioned press film.
×: Very brittle and cannot be subjected to a tensile test Δ: Has a certain degree of independence ○: Flexible and has good independence

<Measurement of molecular weight retention rate>
The press-crystallized film having a thickness of 0.2 mm was treated for 300 hours in a PHH202 hot air dryer manufactured by Espec, which was heated to 180 ° C., and then allowed to cool for 24 hours at room temperature to obtain a sample after heat treatment. Next, the molecular weights of the pressed crystallized film before the heat treatment and the sample after the heat treatment were measured, respectively, and calculated by the following formulas.
Molecular weight retention rate (%) = ( 180 ° C x 300h weight average molecular weight after heat treatment) / (weight average molecular weight before heat treatment ) x 100 (%)

<Analysis of polyorganosiloxane unit content>
The content of the polyorganosiloxane unit in the polyarylene sulfide block copolymer was calculated by multiplying the mole fraction of the Si atom obtained from the element analysis by the molecular weight of the organosiloxane used as the comonomer.

<Analysis of carboxyl group content>
First, benzoic acid was measured by FT-IR as a standard substance, and the absorption intensity (b1) of the peak of ^{3066 cm -1 , which is the absorption of the CH bond of the benzene ring, and the peak of 1704 cm -1} , which is the absorption of the carboxyl group. The absorption intensity (c1) of the above was read, and the amount of carboxyl groups (U1) and (U1) = (c1) / [(b1) / 5] with respect to one unit of the benzene ring were determined. Next, FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of (X) polyarylene sulfide obtained by the above method was measured. 3066cm reads absorption intensity of ^-1 (b2) and absorption intensity of 1704cm ^-1 (c2), a carboxyl group amount with respect to the benzene ring by one unit (U2), a (U2) = (c2) / [(b2) / 4] I asked. The carboxyl group content with respect to 1 g of PPS was calculated from the following formula. Carboxyl group content of PPS (μmol / g) = (U2) / (U1) /108.161 × 1000000.

<Acid anhydride group content>
First, a phthalic anhydride was measured by FT-IR as a standard, the absorption of the absorption intensity (b1) and the acid anhydride groups of the peak of 3066cm ^-1, which is an absorption of C-H bonds of the benzene ring 1850 cm ^{- The absorption intensity (c1) of the peak of 1} was read, and the amount of acid anhydride group (U1) and (U1) = (c1) / [(b1) / 5] with respect to 1 unit of the benzene ring was determined. Next, FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of (X) polyarylene sulfide obtained by the above method was measured. 3066cm reads absorption intensity of ^-1 (b2) and absorption intensity of 1850cm ^-1 (c2), a carboxyl group amount with respect to the benzene ring by one unit (U2), a (U2) = (c2) / [(b2) / 4] I asked. The acid anhydride group content with respect to 1 g of PPS was calculated from the following formula. Acid anhydride group content of PPS (μmol / g) = (U2) / (U1) /108.161 × 1000000. In addition, there is a concern that a measurement error may occur due to the partial opening of the ring of the acid anhydride group and modification to the adjacent dicarboxyl group. Since the carboxyl group closes to the acid anhydride group, the acid anhydride group content can be quantified by using the amorphous film as described above.

<Amino group content>
First, aniline was measured by FT-IR as a standard substance, and ^{the absorption intensity (b1) of the peak of 3066 cm -1} , which is the absorption of the CH bond of the benzene ring, and the peak of ^{3400 cm -1} , which is the absorption of the amino group, were measured. The absorption intensity (c1) was read to determine the amount of acid anhydride group (U1) and (U1) = (c1) / [(b1) / 5] with respect to 1 unit of the benzene ring. Next, FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the amorphous film of (X) polyarylene sulfide obtained by the above method was measured. It reads the absorption intensity of absorption intensity (b2) and 3400 cm ^-1 of the 3066cm ^-1 (c2), an amino group amount with respect to the benzene ring by one unit (U2), a (U2) = (c2) / [(b2) / 4] I asked. The amino group content with respect to 1 g of PPS was calculated from the following formula. Amino group content of PPS (μmol / g) = (U2) / (U1) /108.161 × 1000000

<Calculation of absorbance ratio>
The press amorphous film FT-IR (IR-810 type infrared spectrophotometer manufactured by JASCO Corporation) of the polyarylene sulfide block copolymer obtained by the above method was measured. ^{It was determined by dividing the absorbance of the peak of 1716 cm -1} , which is the characteristic absorption band of the imide group, by the absorbance (c1) of the peak of ^{3066 cm -1} , which is the absorption of the CH bond of the benzene ring.

<Calculation of terminal functional group ratio>
Using the functional group content and the number average molecular weight obtained by the above method, it was calculated by the following formula.
Terminal functional group ratio (%) = (functional group content (mol / g) / (1 / number average molecular weight (g / mol) x 2)) x 100 (%)

<Analysis of chlorine content>
Using an automatic sample combustion device AQF-100 manufactured by Dia Instruments, 1 to 2 mg of polymer is burned at a final temperature of 1000 ° C., the generated gas component is absorbed in 10 mL of water containing a dilute oxidizing agent, and the absorbent solution is carbonated. The total chlorine content in the polymer was measured by subjecting it to an ion chromatography system ICS1500 manufactured by DIONEX Co., Ltd. using a mixed aqueous solution of sodium / sodium hydrogen carbonate as a mobile phase.

<Analysis of chloroform extraction amount>
10 g of the polymer was soxhlet-extracted with 100 g of chloroform at 90 ° C. for 3 hours, and the weight of the component obtained when chloroform was distilled off from this extract was determined as a percentage with respect to the weight of the polymer.

<Reaction amount of monohalogenated compound having functional group>
The amount of the reactive functional group-containing monohalogenated compound remaining in the polymerization reaction product obtained after the completion of the polymerization step was quantified using a gas chromatograph GC-14B manufactured by Shimadzu Corporation, and calculated by subtracting the residual amount from the charged amount. did.

[Reference Example 1] Here, a method for producing (X) polyphenylene sulfide having an acid anhydride group at the terminal, which is obtained by the method of the present invention, will be described.

8.27 kg (70.0 mol) of 47.5% sodium hydrosulfide, 3.14 kg (75.5 mol) of 96% sodium hydroxide, N-methyl-2 in a 70 liter autoclave with a stirrer and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol) and ion-exchanged water 5.50 kg were charged and gradually heated to 225 ° C. over about 3 hours while passing nitrogen under normal pressure to 9.82 kg of water and NMP 0. When 28 kg was distilled off, heating was finished and cooling was started. The amount of residual water in the system per 1 mol of the charged alkali metal hydrosulfide at this time was 1.01 mol including the water consumed for the hydrolysis of NMP. Moreover, since the amount of hydrogen sulfide scattered was 1.4 mol, the amount of the sulfidizing agent in the system after this step was 68.6 mol.

Then, the mixture was cooled to 200 ° C., p-dichlorobenzene (p-DCB) 9.580 kg (65.2 mol), 4-chlorophthalic anhydride 0.377 kg (2.06 mol), NMP 9.37 kg (94.50 mol). After the addition of mol), the reaction vessel was sealed under nitrogen gas, heated to 275 ° C. at a rate of 0.6 ° C./min with stirring at 240 rpm, and reacted at 275 ° C. for 60 minutes.

Immediately after the reaction was completed, the autoclave bottom plug valve was opened, the contents were flushed to a device equipped with a stirrer, and in a device equipped with a stirrer at 230 ° C. until 95% or more of the NMP used during polymerization was volatilized and removed. The mixture was dried for 5 hours, and a solid containing PPS and salts was recovered.

The obtained recovered product and 74 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75 ° C. for 15 minutes, and then filtered through a filter to obtain a cake. After washing the obtained cake with ion-exchanged water at 75 ° C. for 15 minutes and filtering it three times, 74 liters of cake and ion-exchanged water and 0.5 kg of acetic acid were placed in an autoclave equipped with a stirrer, and the inside of the autoclave was filled with nitrogen. After replacement with, the temperature was raised to 195 ° C. After that, the autoclave was cooled and the contents were taken out. The contents were filtered to obtain a cake. The obtained cake was dried at 120 ° C. for 4 hours under a nitrogen stream to obtain a dried PPS. The (X) polyphenylene sulfide produced by such a method is designated as X-1.

[Reference example 2]
The amount of p-dichlorobenzene (p-DCB) used during the polymerization was 9.28 kg (63.11 mol), the amount of 96% sodium hydroxide was 4.29 kg (102.9 mol), and 4-chlorophthalic acid was used. Polymerization and washing were carried out in the same manner as in Reference Example 1 except that the amount of anhydride was 2.877 kg (15.78 mol). The (X) polyphenylene sulfide produced by such a method is designated as X-2.

[Reference example 3]
The reaction vessel was sealed under nitrogen gas, heated to 240 ° C. at a rate of 0.6 ° C./min with stirring at 240 rpm, and polymerized and washed in the same manner as in Reference Example 2 except that the reaction was carried out at 240 ° C. for 240 minutes. Was done. The (X) polyphenylene sulfide produced by such a method is designated as X-3.

[Reference Example 4] Here, a general-purpose method for producing polyarylene sulfide will be described.

The amount of p-dichlorobenzene (p-DCB) used during the polymerization was 10.39 kg (70.66 mol), the amount of 96% sodium hydroxide was 2.94 kg (70.7 mol), and 4-chlorophthalic acid was used. Polymerization and washing were carried out in the same manner as in Reference Example 1 except that no anhydride was added. The (X) polyphenylene sulfide produced by such a method is designated as X-4.

[Reference Example 5] Here, a method for producing polyarylene sulfide having a carboxyl group as a reactive functional group at the end will be described according to the method described in International Publication No. 2015-151921. The amount of p-dichlorobenzene (p-DCB) used during the polymerization was 9.68 kg (65.86 mol), the amount of 96% sodium hydroxide was 3.17 kg (76.1 mol), and 4-chlorophthalanhydride was used. Polymerization and washing were carried out in the same manner as in Reference Example 1 except that 4-chlorobenzoic acid was 1.07 kg (6.86 mol) instead of the substance. The (X) polyphenylene sulfide produced by such a method is designated as X-5.

[Reference Example 6] Here, a method for producing a polyarylene sulfide oligomer having a reactive functional group at the end will be described according to the method described in JP-A-64-45433.

9.37 g (0.12 mol) of anhydrous sodium sulfide, 35.7 g (0.14 mol) of 4,4-dichlorodiphenyl sulfide, N-methyl-2 in an eggplant-shaped flask equipped with a reflux tube and a stirrer. -Pyrrolidone (NMP) 102.8 g (1.04 mol) was charged and refluxed by heating at 200 ° C. for 3 hours in a nitrogen atmosphere.

Then, the reaction mixture was poured into water to obtain a crude product by filtration, and then extracted with 300 ml of high-temperature toluene. As a result, 27.2 g of a polyphenylene sulfide oligomer insoluble in toluene was obtained.

Next, 11.64 g (0.065 mol) of the polyphenylene sulfide oligomer, 4.0 g (0.03 mol) of p-aminothiophenol, and 5.3 g (0.038 mol) of anhydrous potassium carbonate were placed in an autoclave equipped with a stirring tip. Mol), 102.8 g (1.04 mol) of N-methyl-2-pyrrolidone (NMP) was charged, and the mixture was stirred at 130 ° C. for 1 hour and then at 140-150 ° C. for 1.5 hours in a nitrogen atmosphere. .. The reaction mixture was then heated at 220 ° C. for 15 minutes and kept at 200 ° C. for 20 minutes. After cooling the resulting solution, 400 ml of water was poured and the precipitated crude product was obtained by filtration. The crude product was washed with methanol and then dried under reduced pressure. As a result, 12.15 g of polyphenylene sulfide was obtained. The (X) polyphenylene sulfide produced by such a method is designated as X-6.

Table 1 shows the polymerization conditions of the obtained (X) polyphenylene sulfide and the measurement results of the polymer physical properties.

[Reference Example 7] (Y) polydimethylsiloxane having an amino group and / or an isocyanate group As a commercially available amino group-modified polydimethylsiloxane, "X-22-161A" functional group content 1,250 μmol / g manufactured by Shinetsu Silicone was used. Using. Let this (Y) polydimethylsiloxane be Y-1.

[Reference Example 8] Other (Y) Polydimethylsiloxane with Functional Group As a commercially available epoxy group-modified polydimethylsiloxane, "KF-105" functional group content of 2,041 μmol / g manufactured by Shinetsu Silicone was used. Let this (Y) polydimethylsiloxane be Y-2 [Example 1]
A reaction mixture was prepared by adding 50.0 g of (X-1) polyphenylene sulfide, 138 g of NMP, and 14.4 g of (Y-1) polydimethylsiloxane to a 100 ml autoclave with a stirring blade. At this time, the ratio of the amount of functional groups of (Y-1) polydimethylsiloxane to the amount of functional groups of (X-1) polyphenylene sulfide (hereinafter referred to as the functional group ratio) was 1.5 equivalents. After sealing the inside of the autoclave and substituting with nitrogen three times, the reaction mixture was heated to 250 ° C. over about 15 minutes using a heat jacket while stirring at 240 rpm. Then, after reacting at a reaction temperature of 250 ° C. for 60 minutes, the autoclave was rapidly cooled to obtain a product.

In order to recover the obtained product, the polymer was washed with hexane at 50 ° C. for 15 minutes and filtered twice, and further washed with methanol at 50 ° C. for 15 minutes and filtered twice at 70 ° C. A polyphenylene sulfide block copolymer was obtained by washing with water for 15 minutes and performing a filtration operation once. By this washing step, (Y-1) polydimethylsiloxane having a functional group that did not react with (X-1) polyphenylene sulfide was removed.

[Example 2]
Except for the fact that the (X) polyphenylene sulfide species used during the copolymerization was X-2 and the amount of (Y-1) polydimethylsiloxane was 27.6 g (the functional group ratio was 1.5 at this time). Copolymerization and washing were carried out in the same manner as in Example 1.

[Example 3]
Except for the fact that the (X) polyphenylene sulfide species used during the copolymerization was X-3 and the amount of (Y-1) polydimethylsiloxane was 36.0 g (the functional group ratio was 1.5 at this time). Copolymerization and washing were carried out in the same manner as in Example 1.

[Comparative Example 1]
The (X) polyphenylene sulfide species used during the copolymerization was X-4, the (Y) polyorganosiloxane species was (Y-2), and the amount was 7.3 g (at this time, the functional group ratio was 5.0). Copolymerization and washing were carried out in the same manner as in Example 1 except for the above.

[Comparative Example 2]
Except for the fact that the (X) polyphenylene sulfide species used during the copolymerization was X-5 and the amount of (Y-2) polydimethylsiloxane was 58.6 g (the functional group ratio was 5.0 at this time). Copolymerization and washing were carried out in the same manner as in Comparative Example 1.

[Comparative Example 3]
Except for the fact that the (X) polyphenylene sulfide species used during the copolymerization was X-6 and the amount of (Y-2) polydimethylsiloxane was 36.8 g (the functional group ratio was 5.0 at this time). Copolymerization and washing were carried out in the same manner as in Comparative Example 1.

[Comparative Example 4]
Here, the copolymerization of polyarylene sulfide having an amino group at the end and polyorganosiloxane copolymer having an amino group at the end will be described according to the method described in JP-A-64-45433.

In a 100 ml autoclave with a stirring blade, 50.0 g of (X-6) polyphenylene sulfide, 138 g of NMP, 3.05 g of (Y-1) polydimethylsiloxane having the functional group described in Reference Example 7, and bisphenol A dianhydride 5 .09 g was added to prepare a reaction mixture, which was heated to reflux. After azeotropically removing the water, the inside of the autoclave was sealed and replaced with nitrogen three times, and then the reaction mixture was heated to 250 ° C. over about 15 minutes using a heat jacket while stirring at 240 rpm. Then, after reacting at a reaction temperature of 250 ° C. for 60 minutes, the autoclave was rapidly cooled to obtain a product.

In order to recover the obtained product, the polymer was washed with hexane at 50 ° C. for 15 minutes and filtered twice, and further washed with methanol at 50 ° C. for 15 minutes and filtered twice at 70 ° C. A polyphenylene sulfide block copolymer was obtained by washing with water for 15 minutes and performing a filtration operation once.

Table 2 shows the polymerization conditions of the obtained polyphenylene sulfide block copolymer and the measurement results of the polymer physical properties.

The results of the above-mentioned Examples and Comparative Examples will be compared and described.

In Examples 1 to 3 of Table 2, the polyphenylene sulfides of (X-1), (X-2), and (X-3) having an acid anhydride group at the terminal are used and having an amino group (Y-1). As a result of copolymerization with polydimethylsiloxane, a polyphenylene sulfide block copolymer having a high weight average molecular weight and PDMS unit content and a glass transition temperature of 80 ° C. or lower was obtained. Further, even after long-term heat treatment at 180 ° C. for 300 hours, a high molecular weight retention rate of 85% or more was obtained. As a result, the obtained press film was flexible and had good self-supporting property, and not only had excellent tensile elastic modulus and tensile elongation, but also maintained a flexible and self-supporting film shape even after a long-term heat treatment at 180 ° C. × 300 h.

On the other hand, in Comparative Example 1, since (X-4) polyphenylene sulfide produced by a general-purpose method was copolymerized with (Y-2) polydimethylsiloxane having an epoxy group, the amount of functional groups of polyphenylene sulfide was increased. The block copolymerization did not proceed sufficiently. Therefore, the PDMS unit content and the weight average molecular weight of the obtained polyphenylene sulfide block copolymer were both low, and the obtained press film showed brittleness.

In Comparative Example 2, as a result of copolymerizing with (Y-2) polydimethylsiloxane having an epoxy group using polyphenylene sulfide having many carboxyl groups at the terminal (X-5), the weight average molecular weight and PDMS units were contained. A polyphenylene sulfide block copolymer having a high amount and a glass transition temperature of 80 ° C. or lower was obtained. However, since the heat resistance of the bond composed of the carboxyl group and the epoxy group is low, the molecular weight retention rate was as low as 43% after long-term heat treatment at 180 ° C. × 300 h. As a result, the obtained press film was flexible and self-supporting before the long-term heat treatment, and had excellent tensile elastic modulus and tensile elongation, but embrittlement of the film was observed after the long-term heat treatment at 180 ° C. × 300 h. ..

In Comparative Example 3, as a result of copolymerizing with (Y-2) polydimethylsiloxane having an epoxy group using (X-6) polyphenylene sulfide having many amino groups at the terminal, the PDMS unit content was high. Although the glass transition temperature was 80 ° C. or lower, the molecular weight of the obtained polyphenylene sulfide block copolymer was low because the original molecular weight of the polyphenylene sulfide of (X-6) was low. Further, since the heat resistance of the bond composed of the amino group and the epoxy group is low, the molecular weight retention rate was as low as 31% after long-term heat treatment at 180 ° C. × 300 h. As a result, not only the obtained press film had only a certain degree of independence, but also embrittlement of the film was observed after a long-term heat treatment at 180 ° C. × 300 h.

In Comparative Example 4, as a result of copolymerizing (X-6) polyphenylene sulfide having many amino groups at the terminal, (Y-2) polydimethylsiloxane having an amino group, and bisphenol dianhydride, (X-). Since the original molecular weight of the polyphenylene sulfide in 6) was low, the molecular weight of the obtained polyphenylene sulfide block copolymer was low, and the rigid bisphenol component was introduced into the polymer main chain, so that the glass transition temperature was as high as 108 ° C. , Flexibility was not obtained. Further, when the long-term heat treatment at 180 ° C. × 300 h was carried out, the molecular weight retention rate was as low as 50% as a result of some decomposition derived from the bisphenol dianhydride skeleton. As a result, not only the obtained press film had only a certain degree of independence, but also embrittlement of the film was observed after a long-term heat treatment at 180 ° C. × 300 h.

Claims (6)

A method for producing a polyarylene sulfide block copolymer, which comprises reacting (X) polyarylene sulfide having an acid anhydride group at the terminal with (Y) polyorganosiloxane containing an amino group. The method for producing a polyarylene sulfide block copolymer according to claim 1, wherein the content of the acid anhydride group contained in the (X) polyarylene sulfide is 180 μmol / g or more. For at least (i) sulfur source, (ii) dihalogenated aromatic compound, (iii) organic polar solvent, and 1 mol of sulfur atom in the reaction system, the following general formula (Ia) and / or the following general formula (I) The mixture containing 0.01 to 40 mol% of the monohalogenated compound having the (iv) reactive functional group represented by (b) is heated to obtain the (X) polyarylene sulfide, which is then contained with an amino group. (Y) The method for producing a polyarylene sulfide block copolymer according to any one of claims 1 and 2, wherein the polyorganosiloxane is reacted.
(In formulas (Ia) and (Ib), V represents a halogen and W represents a carboxyl group or a metal salt thereof.) Assuming that the sum of (x) and (y) is 100% by weight,
(X) Polyarylene sulfide unit 1 to 99% by weight,
(Y) Containing 99 to 1% by weight of polyorganosiloxane unit ,
It has a structure in which (x) polyarylene sulfide unit and (y) polyorganosiloxane unit are bonded via an imide group, has a glass transition temperature of 80 ° C. or lower, and has a molecular weight retention rate of 70 as defined below. A polyarylene sulfide block copolymer characterized by being% or more.
Molecular weight retention rate (%) = ( 180 ° C x 300h weight average molecular weight after heat treatment) / (weight average molecular weight before heat treatment ) x 100 (%) The polyarylene sulfide block copolymer according to claim 4, which comprises 40 to 85% by weight of the (x) polyarylene sulfide unit and 15 to 60% by weight of the (y) polyorganosiloxane unit. A molded product comprising the polyarylene sulfide block copolymer according to any one of claims 4 to 5 or a composition containing the polyarylene sulfide block copolymer.