JPH08253587A - Reactive polyarylene sulfide - Google Patents

Abstract

PURPOSE: To prepare a polyarylene sulfide which is highly reactive with epoxy silane coupling agents and the addition of which in a small amount increases mechanical strength by making an alkaline metal sulfide react with a dihaloaromatic compound in a specific solvent. CONSTITUTION: This polyarylene sulfide contains 0.7 or less wt% of a methylenechloride extract, has a melt viscosity V6 of 20-15000 P and 15μmol/g or more of SH group (X: an alkaline metal or H). The polyarylene sulfide is prepared by making an alkaline metal sulfide react with a dihaloaromatic compound in an organic amide solvent, while a part of the gas phase in the reaction vessel is condensed by cooling and refluxed to the liquid phase during the reaction. Preferably, the polyarylene sulfide thus obtained is washed first by an organic solvent and then by water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide highly reactive with an epoxy silane coupling agent and a resin composition containing the same.

[0002]

2. Description of the Related Art As a conventional method for producing polyarylene sulfide (hereinafter sometimes abbreviated as PAS), Japanese Patent Publication No. 45-3368 discloses a method for producing an alkali metal sulfide and a dihaloaromatic in an organic amide solvent. A method of reacting a compound to produce PAS is described. However, it was not possible to produce high molecular weight PAS by this method.

Therefore, it has been practiced to produce a high molecular weight PAS by subjecting the above low molecular weight PAS to thermal oxidation treatment and crosslinking. However, such a cross-linked PAS has a drawback that it is inferior in mechanical strength such as impact strength, and further in moldability. Therefore, in order to improve mechanical strength such as impact resistance, some methods have been proposed so far.

Japanese Patent Publication No. 52-12240 discloses a method of carrying out polymerization in the presence of a carboxylic acid metal salt such as sodium acetate or lithium acetate in order to produce a high molecular weight PAS. However, the above compounds are expensive, and a large amount of incidental equipment, technology, and cost are required to separate, recover, and treat the compounds from the product in a pollution-free manner, which is also a significant disadvantage. . Further, the reactivity with the epoxy-based silane coupling agent was not sufficient, and it was not possible to sufficiently improve the mechanical strength such as impact strength by adding the epoxy-based silane coupling agent.

Japanese Patent Publication No. 6-39113 discloses PA
A resin composition containing S, a silane compound such as epoxyalkoxysilane, and an inorganic filler is disclosed. However, the reactivity between PAS and the silane compound was not sufficient, and the effect of improving mechanical strength such as impact strength was not sufficient.

JP-A-6-256517 discloses a PAS having a predetermined melt flow rate and a predetermined degree of increase in melt viscosity when 1.0% of γ-glycidoxypropyltrimethoxysilane is added. It is disclosed. However, it is necessary to add an alkali metal hydroxide in the production of the PAS. Therefore, PAS
However, the manufacturing cost is increased, which is very disadvantageous for industrialization. In addition, the above compounds can be separated from products without pollution,
A large amount of incidental equipment, technology and cost are required to carry out the recovery process, which is also a significant disadvantage in this respect.

[0007]

DISCLOSURE OF THE INVENTION The present invention does not require an expensive polymerization aid as described above, is therefore inexpensive, and is highly reactive with an epoxy silane coupling agent.
Therefore, it is an object of the present invention to provide a novel PAS that can achieve a sufficient improvement in mechanical strength such as impact strength by adding a small amount of the agent.

[0008]

According to the present invention, the extraction amount with methylene chloride is 0.7% by weight or less, and the melt viscosity V ₆
Is 20 to 15,000 poise, and the -SX group (X is an alkali metal or hydrogen atom) is 15 μmol / g
The above is polyarylene sulfide. The PAS of the present invention has many —SX groups. Therefore, it reacts with many epoxy silane coupling agents. In addition, the PA of the present invention
The amount of S extracted with methylene chloride is small. Therefore, almost no oligomer having a relatively small molecular weight is present, and the epoxy silane coupling agent is not wasted. From the above, the PAS of the present invention has high reactivity with an epoxy silane coupling agent, and high mechanical strength can be obtained by adding a small amount of the agent.

The PAS of the present invention has an extraction amount with methylene chloride of 0.7% by weight or less, preferably 0.6% by weight or less, and particularly preferably 0.5% by weight or less. The above range is preferable because there are no oligomers having a relatively low molecular weight in PAS. When the amount of extraction exceeds the upper limit, the effect of improving mechanical strength such as impact resistance by the epoxy-based silane coupling agent becomes low, which is not preferable. Here, the extraction amount with methylene chloride is a value obtained as follows. 4 g of PAS powder is added to 80 g of methylene chloride, Soxhlet extraction is carried out for 4 hours, then cooled to room temperature, and the methylene chloride solution after extraction is transferred to a weighing bottle. In addition, the container used for the above extraction should be 60 methylene chloride in total.
using g, washed in three times, after collecting the washing solution,
Collect in the weighing bottle. Then heat to about 80 ° C. to evaporate and remove the methylene chloride in the weighing bottle,
It is determined by weighing the residue.

The PAS of the present invention has a -SX group (X is an alkali metal or hydrogen atom) of 15 μmol / g or more,
Preferably 18 to 35 μmol / g, particularly preferably 2
It is 0 to 30 mol / g. When the group is less than the above lower limit,
The reactivity between PAS and the epoxy silane coupling agent is reduced. Here, the quantification of the -SX group was performed as follows. After drying the PAS powder at 120 ° C. for 4 hours in advance,
20 g of the PAS powder was added to N-methyl-2-pyrrolidone 15
0 g and 30 at room temperature to eliminate powder agglomerates
Stir vigorously for 1 minute. Next, after filtering the slurry, washing is repeated 7 times using 1 liter of warm water at about 80 ° C. each time. The obtained filter cake is slurried again in 200 g of pure water, and 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Then, the mixture is stirred at 25 ° C. for 30 minutes, filtered, and washed 6 times with 1 liter of warm water at about 80 ° C. each time. The resulting filter cake is purified with pure water 2
Reslurry in 00 g and then titrate and quantitate with 1N sodium hydroxide.

Further, the PAS of the present invention has a melt viscosity V ₆ of 20 to 15,000 poise, preferably 100 to 1,000.
0 poise, particularly preferably 400 to 5000 poise. If it is less than the above lower limit, the original properties of PAS such as mechanical strength cannot be obtained, and the reactivity with an epoxy silane coupling agent is not sufficient, and the improvement of mechanical strength, which is the object of the present invention, can be achieved. Can not. Exceeding the above upper limit is not preferable because the molding processability decreases. here,
The melt viscosity V ₆ was 300 ° C. using a flow tester.
It is a value measured after holding for 6 minutes with a load of 20 kgf / cm ² and L / D = 10/1.

In the present invention, the above PAS is obtained by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, and cooling the gas phase portion of the reaction vessel during the reaction. The polyarylene sulfide (a) produced by condensing a part of the gas phase and refluxing it in the liquid phase can be obtained by washing with an organic solvent and then with water.

Here, the above-mentioned PAS (a) is disclosed in Japanese Patent Laid-Open No.
It can be manufactured by the method described in JP-A-222196.

In this polymerization method, the refluxed liquid has a higher water content than the liquid-phase bulk because of the vapor pressure difference between water and the amide solvent. This reflux liquid having a high water content forms a layer having a high water content on the reaction solution. As a result, residual alkali metal sulfides (eg Na ₂ S),
Alkali metal halides (eg, NaCl), oligomers, etc. will be contained in large amounts in the layer. In the conventional method, PAS and N
In the state where the raw materials such as a ₂ S and the by-products are uniformly mixed, not only high molecular weight PAS cannot be obtained, but also
Depolymerization of PAS produced with great care also occurs, and thiophenol by-product is observed. However, in the present invention, by positively cooling the gas phase part of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper part of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. It seems that these factors can be eliminated with high efficiency and high molecular weight PAS can be obtained. However, the present invention is not limited only to the effects due to the above-mentioned phenomenon, and due to various influences caused by cooling the gas phase portion, high molecular weight PAS
Is obtained.

In this polymerization method, it is not necessary to add water during the reaction unlike the conventional method. However, the addition of water is not excluded at all. However, some of the advantages of the present invention are lost if the operation of adding water is performed. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The gas phase portion of the reaction can can be cooled by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium into an internal coil installed in the upper part of the reaction can, a method of flowing a cooling medium into an external coil or jacket wound around the upper part of the outside of the reaction can, and a reflux condenser installed in the upper part of the reaction can are used. The method may be such as sprinkling water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction can. Any method is effective as long as it has the effect of increasing the reflux amount in the can. May be used. If the outside air temperature is relatively low (for example, room temperature), it is also possible to perform appropriate cooling by removing the heat insulating material conventionally provided on the upper part of the reaction can. In the case of external cooling, water condensed on the reactor wall surface
The amide-based solvent mixture enters the liquid phase along the wall of the reaction vessel. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels along the surface of the cooling device or the wall of the reaction vessel into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230 to 275 for constant temperature
It is preferable to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C. and the time is 1 to 6 hours. To obtain higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. This 2
When carrying out the stepwise operation, the first step is preferably carried out at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too slow, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too fast, PAS having a sufficiently high molecular weight cannot be obtained, and the side reaction rate remarkably increases. The end of the first stage is
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out at a time of mol% and a molecular weight in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo-aromatic compound in the polymerization reaction system is 2 mol% to 15 mol% and the molecular weight is 5,000 to 15,000. Residual rate is 40 mol%
When it is more than 1, the side reaction such as depolymerization is likely to occur in the second step reaction, while when it is less than 1 mol%, the high molecular weight P is finally obtained.
It is difficult to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
At a temperature higher than 270 ° C., side reactions such as depolymerization are likely to occur, making it difficult to stably obtain a high molecular weight product.

As a practical operation, first, dehydration or water addition is carried out in an inert gas atmosphere so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount, if necessary. The water content is preferably alkali metal sulfide 1
The amount is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol per mol. If it exceeds 2.5 mols, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction and the degree of polymerization will not increase. If it is less than 0.5 mol, the reaction rate is too fast to obtain a sufficiently high molecular weight product, and unfavorable reactions such as side reactions occur.

In the case of the one-step reaction at a constant temperature, the cooling of the gas phase portion during the reaction is preferably performed from the start of the reaction, but it must be performed at least during the temperature increase of 250 ° C. or less. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest after the completion of the first-stage reaction. Regarding the degree of cooling effect, the pressure inside the reaction vessel is usually the most suitable index. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the water content in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, as compared with the case of not cooling under the same reaction conditions, if the reactor pressure is decreased, the amount of reflux liquid is increased, which means that the temperature at the reaction solution gas-liquid interface is decreased. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer having no water content. Therefore, it is preferable to cool the reactor so that the internal pressure of the reactor becomes lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.

The organic amide solvent used here is PA
Known for S polymerization, for example N-methylpyrrolidone (NMP), N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with NMP being preferred. They all have a lower vapor pressure than water.

Alkali metal sulphides are also known, for example lithium sulphide, sodium sulphide, potassium sulphide, rubidium sulphide, cesium sulphide and mixtures thereof. These hydrates and aqueous solutions may be used. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

The dihalo aromatic compound is, for example, Japanese Patent Publication No.
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using a small amount (20 mol% or less) of one or more kinds of para, meta or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl. For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'-dichlorodiphenyl sulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
It is dichlorobiphenyl.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
A polyhalo compound such as trichlorobenzene can also be used in a concentration of preferably 5 mol% or less based on the total amount of para and metadihalo aromatic compounds.

Further, as a small amount of other additives, a terminal terminating agent and a monohalo compound as a modifying agent can be used in combination.

Next, washing of PAS with an organic solvent is preferably carried out by the following method. That is, it is a method of filtering the slurry of PAS (a) produced in the above step and then dispersing the obtained filter cake in an organic solvent. The washing is preferable because the oligomer component having a relatively low molecular weight present in PAS (a) can be removed well.

In one embodiment of washing, first, the PAS (a) slurry produced in the above step is filtered to obtain a PAS cake. Next, the PAS cake is put into an organic solvent that is preferably 0.5 to 10 times by weight, stirred and mixed at room temperature to 180 ° C. for preferably 10 minutes to 10 hours, and then filtered. The stirring and mixing and filtering operations are preferably repeated 1 to 10 times. Examples of the organic solvent used for the washing include the organic amide-based solvent described in the description of the manufacturing process of PAS (a) above, xylene and the like. An organic amide solvent is preferably used. The organic amide-based solvent may be the same as or different from the one used in the PAS (ii) production process. Particularly preferably, N-methylpyrrolidone is used as the organic amide solvent.

The subsequent washing with water can be carried out according to a known method. However, it is preferably carried out by dispersing the filter cake obtained after washing with the above organic solvent in water. For example, the above filter cake is put into water, preferably 1 to 5 times by weight, stirred and mixed at room temperature to 90 ° C. for preferably 5 minutes to 10 hours, and then filtered. The stirring and mixing and filtering operations are preferably 2
By repeating 10 times, the solvent adhering to PAS and the by-product salt are removed, and the washing with water is completed. By performing water washing as described above, it becomes possible to perform efficient washing with a small amount of water as compared with the washing method in which water is poured into the filter cake. Further, the present inventor has found that the conventional solvent removal by drying reduces the reactivity between PAS and the epoxy-based silane coupling agent.
However, if solvent removal by washing with water is used as in the present invention, high reactivity between PAS and the epoxy-based silane coupling agent can be maintained.

In the present invention, the PAS obtained as described above may be further acid-treated. The acid treatment is carried out at a temperature of 100 ° C. or lower, preferably 40 to 80 ° C. If the temperature exceeds the above upper limit, the PAS molecular weight after acid treatment decreases, which is not preferable. On the other hand, if the temperature is lower than 40 ° C., the remaining inorganic salt is deposited to reduce the fluidity of the slurry and hinder the continuous treatment process, which is not preferable. The concentration of the acid solution used for the acid treatment is preferably 0.01 to 5.0% by weight. The pH of the acid solution is preferably 4.0 to 5.0 after the acid treatment. By adopting the above concentration and pH, it is possible to convert most of -SY (Y represents an alkali metal) terminal in PAS which is the object to be processed to -SH terminal and to corrode plant equipment. Is preferable because it can prevent The time required for the acid treatment depends on the acid treatment temperature and the concentration of the acid solution, but is preferably 5
It is at least 10 minutes, particularly preferably at least 10 minutes. If it is less than the above, the -SY end in PAS cannot be sufficiently converted to the -SH end, which is not preferable. For the acid treatment, for example, acetic acid,
Formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid, carbonic acid and the like are used, and acetic acid is particularly preferable. By performing the treatment, the alkali metal, such as sodium, which is an impurity in PAS can be reduced. Therefore, it is possible to suppress elution of alkali metal such as sodium and deterioration of electric insulation during use of the product.

The present invention also includes (A) the PA of the present invention.
S 100 parts by weight, (B) epoxy-based silane coupling agent 0.01 to 5.0 parts by weight and (C) inorganic filler
It is a PAS resin composition containing 0 to 400 parts by weight.

The lower limit of the component (B) epoxy silane coupling agent is 0.01 part by weight, preferably 0.05 part by weight, and particularly preferably 0 part by weight, relative to 100 parts by weight of the component (A) PAS. 0.1 parts by weight, and the upper limit is 5.
It is 0 part by weight, preferably 3.0 parts by weight, particularly preferably 2.0 parts by weight. If the component (B) is less than the above lower limit, mechanical strength such as impact strength and tensile strength is low. It is not preferable because it causes up.

The upper limit of the component (C) inorganic filler is 400 parts by weight, preferably 200 parts by weight, particularly preferably 100 parts by weight, per 100 parts by weight of the component (A) PAS. When the component (C) exceeds the above upper limit, moldability is deteriorated, which is not preferable.

The component (B) epoxy silane coupling agent in the present invention is preferably γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and the like can be mentioned.

As the inorganic filler as the component (C), a conventional one can be used. For example, silica, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium carbonate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite. , Granular zirconium oxide,
Examples thereof include powdery or scaly ones, and fibrous ones such as glass fibers, potassium titanate fibers, carbon fibers, mica ceramic fibers and metal fibers. These inorganic fillers can be used alone or in combination of two or more.

Further, if necessary, additives such as an antioxidant, a heat stabilizer, a lubricant, a release agent and a coloring agent may be added.

The method of mixing the above components is not particularly limited. A generally widely used method, for example, a method of mixing each component with a mixer such as a Henschel mixer can be used.

The resin composition of the present invention is usually melt-kneaded in an extruder and pelletized, and then, for example, injection-molded or compression-molded into a desired shape.

The PAS resin composition of the present invention has impact strength,
It has excellent mechanical strength such as tensile strength and is useful as electric / electronic parts, automobile parts, etc.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0039]

EXAMPLES Each characteristic value in the examples was measured as follows. <Reactivity with Epoxy-Based Silane Coupling Agent> The reactivity was compared by the thickening rate α. The thickening rate α is defined by the following equation.

[0040]

[Number 1] α (%) = {(V S -V B) / V B} × 100 where, V _B represents the melt viscosity V ₆ of the PPS prior to reaction with the epoxy silane coupling agent, V _S represents the melt viscosity V ₆ of PPS after the reaction with the epoxy silane coupling agent. The melt viscosity V ₆ was 300 ° C. using a flow tester CFT-500C manufactured by Shimadzu Corporation.
It is the viscosity (poise) measured after holding for 6 minutes with a load of 20 kgf / cm ² and L / D = 10/1. P after reaction
The melt viscosity V _S of the PS, PP amounts shown in Table 1 (parts by weight)
After blending S with an epoxy-based silane coupling agent, the mixture was placed in the flow tester and measured. Here, γ-glycidoxypropyltrimethoxysilane (A187, trademark, manufactured by Nippon Unicar Co., Ltd.) was used as the epoxy silane coupling agent. However, Table 1
For * 1, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (A186, trademark,
Nippon Unicar Co., Ltd.) was used. <Impact resistance> Izod impact strength was measured and evaluated according to ASTM D256. <Tensile Strength and Tensile Elongation at Break> Measured in accordance with ASTM D638.

[0041]

Example 1 Flake-shaped sodium sulfide (61.0 wt% Na ₂ S) 19.28 was placed in a 150 liter autoclave.
6 kg and 45.0 kg of NMP were charged. The temperature was raised to 204 ° C. with stirring under a nitrogen stream, and 4.157 kg of water was distilled off (the residual water content was 1.21 mol per mol of sodium sulfide). Then, close the autoclave 1
After cooling to 80 ° C, paradichlorobenzene (below p
-May be abbreviated as DCB) 22.05 kg and NMP1
8.0 kg was charged. The temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. Liquid temperature 2
While stirring at 15 ° C. for 5 hours, a cooling medium of 80 ° C. was flowed around the coil wound around the upper part of the autoclave to cool it. Then, the temperature was raised, the reaction was allowed to proceed with stirring at a liquid temperature of 260 ° C. for 3 hours, then the temperature was lowered, and the cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop.

Then, it was further cooled to room temperature to obtain a polymerized slurry (S1).

Part (4 kg) of the polymerized slurry (S1)
And then filter the resulting filter cake to remove the unused NMP
(2 kg) was slurried. Then 3 at 120 ℃
Stir for 0 minutes, filter to remove NMP, then pour the filter cake into warm water at about 80 ° C. (about twice the weight of the filter cake by weight) and stir thoroughly for about 30 minutes before filtering. . This operation of washing with water and filtration was repeated 7 times. Then, the obtained filter cake was dried in a hot air circulation dryer at 120 ° C. for 6 hours to obtain white powdery PPS. The obtained PPS
The V _B of (P-1) was 1250 poise.

[0044]

Example 2 Polymerization Polymerized slurry obtained in Example 1 (S1)
After filtering a portion (4 kg) of the above, the resulting filter cake was slurried in virgin NMP (2 kg). Then, the mixture is stirred at 120 ° C. for 30 minutes, filtered to remove NMP, and then the filter cake is put into warm water at about 80 ° C. (about twice as much as the filter cake by weight), and stirred sufficiently for about 30 minutes. And then filtered. This operation of washing with water and filtration was repeated twice. The obtained filter cake is slurried in pure water and acetic acid is added to the slurry to adjust the pH to 5.0.
The mixture was stirred for 5 minutes and acid-treated. After the acid treatment, washing with water was repeated 4 times. Next, the obtained filter cake is treated with 12
It was dried in a hot air circulation dryer at 0 ° C. for 6 hours to obtain white powdery PPS. V _B of the resulting PPS (P-2) is 11
It was 10 poise.

[0045]

[Comparative Example 1] The same procedure as in Example 1 was carried out except that cleaning with unused NMP was not carried out. The obtained PPS
The V _B of (P-3) was 1080 poise.

[0046]

Comparative Example 2 After filtering a part (4 kg) of the polymerized slurry (S1) obtained in Example 1, the cake was subjected to NMP in an oil bath at 200 ° C. under a reduced pressure of 10 torr with an evaporator.
It was dried for about 1 hour until no more distilled. Then, the mixture was cooled, poured into warm water of about 80 ° C. (about twice the weight of the filter cake by weight), sufficiently stirred for about 30 minutes, and then filtered. This operation of washing with water and filtration was repeated 7 times. Then, the filter cake was dried at 120 ° C. for 6 hours in a hot air circulation dryer to obtain a brown powder product. Obtained PPS (P-
4 V _B of) was 1380 poise.

[0047]

Comparative Example 3 Sodium acetate trihydrate as a polymerization aid 8.
Polymerization was carried out under the same conditions as in Polymerization Example 1 except that 0 kg was added, 22.612 kg of p-DCB was charged, and cooling of the upper part of the autoclave was not carried out. Obtained P
The V _B of PS (P-5) was 1470 poise.

Each PP produced in the above Examples and Comparative Examples
The properties of S are shown in Table 1. Here, for P-2 (Example 2), the viscosity increase rate was measured by changing the addition amount and type of the epoxy silane coupling agent.

[0049]

[Table 1] P-1 and P2 are both PPS of the present invention. The addition amount of the epoxy-based silane coupling agent was 0.5 parts by weight, and all showed a high thickening rate. Regarding P-2, the one in which the amount of the epoxy silane coupling agent added was increased to 0.8 parts by weight showed a higher viscosity increase rate. As described above, it was found that the PPS of the present invention has high reactivity with the epoxy silane coupling agent. Further, with respect to P-2, the thickening rate was measured for the epoxy silane coupling agents of different types. Each coupling agent showed a high thickening rate.

On the other hand, P-3 was manufactured without cleaning with unused NMP. The amount of methylene chloride extracted is large, and the thickening rate is extremely low. P-4 is an unused NM
It was manufactured by performing NMP heat drying without washing with P and then washing with water. The amount of methylene chloride extracted is large, and the thickening rate is extremely low. P-5 was manufactured without cooling the upper part of the autoclave. The obtained PP
The amount of -SX group of S is small and the thickening rate is extremely low.

[0051]

Examples 3 to 6 and Comparative Examples 4 to 7 The amounts (parts by weight) of each PPS and glass fiber (CS 3J-96) shown in Table 2 were used.
1S, trademark, manufactured by Nitto Boseki Co., Ltd.) and an epoxy-based silane coupling agent, and then mixed and extruded at a barrel setting temperature of 320 ° C. using a 20 mmφ biaxial counter-rotating extruder to prepare pellets. . The obtained pellets were injection-molded under the conditions of a cylinder temperature setting of 320 ° C. and a mold temperature of 130 ° C. to prepare test pieces, which were then subjected to an evaluation test.

Here, the epoxy silane coupling agent used in Examples 3 to 5 and Comparative Examples 4 to 6 was γ-glycidoxypropyltrimethoxysilane (A187, trademark, manufactured by Nippon Unicar Co., Ltd.). The epoxy silane coupling agent used in Example 6 was β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane (A186, trademark, manufactured by Nippon Unicar Co., Ltd.).

The above results are shown in Table 2.

[0054]

[Table 2] Examples 3 to 6 are resin compositions of the present invention. All of the molded products exhibited high impact strength, tensile strength and tensile breaking elongation.

On the other hand, Comparative Examples 4 to 6 are respectively the above Comparative Example 1
It is a resin composition which used PPS manufactured by ~ 3. All of the molded products were inferior to those of Examples 3 to 6 in impact strength, tensile strength and tensile breaking elongation. The resin composition of Comparative Example 7 was obtained by using the PPS (P-1) of the present invention and adding no epoxy silane coupling agent. Compared with Example 3, the impact strength, the tensile strength and the tensile elongation at break were inferior.

[0056]

INDUSTRIAL APPLICABILITY The present invention does not require an expensive polymerization aid, is therefore inexpensive, and is highly reactive with an epoxy silane coupling agent. Therefore, addition of a small amount of the agent can reduce impact strength and the like. Provided is a novel PAS capable of achieving a sufficient improvement in mechanical strength.

Claims (6)

[Claims] 1. The amount of extraction with methylene chloride is 0.7% by weight or less, the melt viscosity V ₆ is 20 to 15,000 poise, and the —SX group (X is an alkali metal or hydrogen atom) is 15 μmol / A polyarylene sulfide that is greater than or equal to g. 2. A part of the gas phase in the reaction can is removed by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent and cooling the gas phase part of the reaction can during the reaction. The method for producing polyarylene sulfide according to claim 1, wherein the polyarylene sulfide (a) produced by condensing and refluxing it in a liquid phase is washed with an organic solvent and then with water. 3. The production according to claim 2, wherein the washing with the organic solvent is carried out by filtering the slurry produced in the production step of polyarylene sulfide (a) and then dispersing the obtained filter cake in the organic solvent. Law. 4. The production method according to claim 2, wherein the washing with water is performed by dispersing the filter cake obtained after washing with an organic solvent in water. 5. The production method according to claim 2, wherein the organic solvent is an organic amide solvent. 6. (A) 100 parts by weight of the polyarylene sulfide according to claim 1, 0.01 to 5.0 parts by weight of (B) epoxy silane coupling agent, and 0 to 400 parts by weight of (C) inorganic filler. A polyarylene sulfide resin composition containing: