JPH09157524A - Modified polyarylene sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified polyarylene sulfide which, when compounded with a thermoplastic resin, can give a resin compsn. having very high mechanical strengths such as impact and tensile strengths by compounding a polyarylene sulfide with a specific compd. SOLUTION: A hurdred (100) pts.wt. polyarylene sulfide having a methylene chloride extractable content of 0.7wt.% or lower, a melt viscosity V6 of 20-15,000P, and a content of SX groups (wherein X is H or an alkali metal) of 15μmol or higher is compounded with 0.01-20 pts.wt. compd. represented by the formula (wherein Ar is a 6-20C mono-to tetravalent arom. hydrocarbon group having at least one glycidyloxy group bonded to the arom. ring; R is H or methyl; and (n) is 1-4). Thus, giving a modified polyarylene sulfide, which is highly compatible with a thermoplastic resin and is compounded with a thermoplastic resin in an amt. of 10-900wt.% of the modified polyarylene sulfide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polyarylene sulfide.

[0002]

2. Description of the Related Art In recent years, a thermoplastic resin having high heat resistance and chemical resistance has been required as a material for electric / electronic equipment parts, automobile equipment parts, chemical equipment parts and the like. . Polyarylene sulfides (hereinafter sometimes abbreviated as PAS) represented by polyphenylene sulfides (hereinafter sometimes abbreviated as PPS) have recently attracted attention as one of the resins that meet this demand.

As a conventional method for producing polyarylene sulfide, Japanese Patent Publication No. 45-3368 discloses a method for producing PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent. Has been done.
However, this method could not produce high molecular weight PAS.

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. To improve mechanical strength,
High molecular weight P only by polymerization without thermal oxidative crosslinking treatment
Various improved methods for making AS have been proposed.

For example, a sulfur source, p-dihalobenzene, an organic amide, a base and an alkali metal carboxylate described in JP-B-52-12240 are contacted to form a composition, and the composition is polymerized under polymerization conditions. To produce a polymer, or in the production of PAS by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent as described in JP-A-61-7332. In one stage, 0.5 per mol of alkali metal sulfide
The reaction is carried out at 180 to 235 ° C. in the presence of ˜2.4 mol of water to produce PAS having a conversion of dihaloaromatic compound of 50 to 98 mol% and a melt viscosity of 5 to 300 poise. It is known that the reaction is further carried out at 245 to 290 ° C. in the presence of 2.5 to 7.0 mol of water.
However, in the former method, the alkali metal carboxylate is expensive, and in order to separate the compound from the product in a pollution-free manner, recover and treat it, a great amount of incidental equipment, technology and cost are required, This was also a significant disadvantage. In addition, the latter method requires a step of adding water during the reaction and requires equipment with high pressure resistance, which is disadvantageous in terms of equipment, economy and operation.

Further, in order to improve mechanical strength, PAS
And polymer alloys with other thermoplastics have also been proposed. However, PAS has a problem that it is difficult to obtain a polymer alloy having excellent mechanical properties and a good balance of physical properties, because PAS has extremely poor compatibility with other thermoplastic resins.

Various attempts have been made to improve the compatibility of PAS. For example, JP-A-59-155462 discloses that 1 to 99 parts by weight of PPS and 99 to 1 of polyamide are used.
A thermoplastic resin composition comprising 1 to 20 parts by weight of an epoxy resin with respect to 100 parts by weight of a mixture consisting of parts by weight, or (A) Thermoplastic composition in JP-A-59-64657. Polyester 99-60 parts by weight,
(B) 1 to 40 parts by weight of PPS, and (C) 0.1 to 20 parts by weight of novolac type epoxy resin (based on 100 parts by weight of (A) and (B) in total). A thermoplastic polyester resin composition is disclosed. However, in any case, the improvement in compatibility was not sufficient, and the improvement in mechanical strength was not satisfactory.

Further, JP-A-7-126527 and JP-A-7-126528 disclose a mixture of PPS and an epoxy compound having the same structure as that of the present invention.
A PPS resin composition having improved compatibility with polyamide and a method for producing the same are described. However, the PPS used in the present invention is Ryton M2588 (manufactured by Philips, Toray) as used in Examples, and is manufactured by using sodium acetate trihydrate as a cocatalyst. The PPS had insufficient reactivity with the epoxy compound, the compatibility was not sufficiently improved, and the improvement in mechanical strength was not satisfactory.

[0009]

DISCLOSURE OF THE INVENTION The present invention is remarkably excellent in compatibility with a thermoplastic resin, and therefore is blended with a thermoplastic resin to give a resin composition having remarkably high mechanical strength such as impact strength and tensile strength. The object is to provide a modified PAS capable of giving a product.

[0010]

Means for Solving the Problems The present inventor has conducted extensive studies in order to solve the above problems. As a result, they have found that the above problem can be effectively solved by using a modified PAS containing the following predetermined PAS and a compound having a predetermined structure, and have completed the present invention.

That is, according to the present invention, (1) the extraction amount with (A) methylene chloride is 0.7% by weight.
100 parts by weight of a polyarylene sulfide having a melt viscosity V ₆ of 20 to 15,000 poise and an -SX group (X is an alkali metal or a hydrogen atom) of 15 μmol / g or more, and (B ) Compound represented by the following formula (I) 0.01 to 20
Parts by weight

[0012]

Embedded image (Here, Ar has 6 to 20 carbon atoms having at least one glycidyloxy group bonded to an aromatic ring (however,
The number of carbon atoms in the glycidyloxy group is not included), a monovalent to tetravalent aromatic hydrocarbon group is shown, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 4). It is a sulfide.

In a preferred embodiment of the present invention, (2) the polyarylene sulfide (A) reacts an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, and during the reaction, the gas phase of the reaction can Part of the gas phase in the reaction vessel is condensed by cooling the part, and the polyarylene sulfide (a) produced by refluxing this in the liquid phase is obtained by washing with an organic solvent and then with water. The modified polyarylene sulfide described in (1) above can also be mentioned.

The PAS of the present invention has many —SX groups. Therefore, it is very easy to react with the two functional groups of the compound represented by the formula (I), that is, the epoxy group and the CH ₂ ═C (R) -group. Further, the PAS of the present invention has a small amount of extraction with methylene chloride. Therefore, there are almost no oligomers having a relatively small molecular weight, and the above compounds are not wasted. From the above, by adding a small amount of the above compound,
It has a remarkably high compatibility with a thermoplastic resin such as a polyester resin and a polyamide resin, and therefore can be blended with the thermoplastic resin to give a resin composition having a remarkably high mechanical strength such as impact strength and tensile strength. A modified PAS can be obtained.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION (A) P used in the present invention
As for AS, the extraction amount with methylene chloride is 0.7% by weight or less, preferably 0.6% by weight or less, particularly preferably 0.1% or less.
5% by weight or less. The above range is preferable because there are no oligomers having a relatively low molecular weight in PAS. If the amount of extraction exceeds the above upper limit, the effect of improving mechanical strength such as impact resistance and tensile strength by the compound (B) represented by the formula (I) becomes low, which is not preferable. Here, the extraction amount with methylene chloride is a value determined 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. Further, the container used for the above extraction is washed with a total of 60 g of methylene chloride in three times, and the washing liquid is collected and then collected in the weighing bottle. Next, it is determined by heating to about 80 ° C. to evaporate and remove the methylene chloride in the weighing bottle, and weighing the residue.

The lower limit of the amount of -SX group (X is an alkali metal or hydrogen atom) of (A) PAS of the present invention is 15
μmol / g, preferably 18 μmol / g, particularly preferably 20 μmol / g, and the upper limit is preferably 35.
μmol / g, particularly preferably 30 mol / g.
When the amount of the group is less than the above lower limit, the reactivity between (A) PAS and (B) the compound represented by the formula (I) decreases. Here, the quantification of the -SX group was performed as follows. After the PAS powder was previously dried at 120 ° C. for 4 hours, the PAS powder 2
0 g was added to 150 g of N-methyl-2-pyrrolidone,
Stir vigorously for 30 minutes at room temperature to eliminate powder agglomerates. Then, after filtering the slurry, each time about 80
Repeat the washing 7 times with 1 liter of warm water at ℃. The obtained filter cake is slurried again in 200 g of pure water,
Then add 1N hydrochloric acid to adjust the pH of the slurry to 4.5.
Adjust to Next, after stirring at 25 ° C. for 30 minutes and filtering, washing is repeated 6 times using 1 liter of hot water at about 80 ° C. each time. The obtained filter cake is reslurried in 200 g of pure water, and then titrated with 1N sodium hydroxide to quantify.

Further, in the (A) PAS of the present invention, the lower limit of the melt viscosity V ₆ is 20 poise, preferably 100 poise, particularly preferably 400 poise, and the upper limit is 15,000.
Poise, preferably 10,000 poise, particularly preferably 5,000 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 the compound (B) represented by the formula (I) is not sufficient, and the improvement of the mechanical strength which is the object of the present invention. Can not be achieved. Exceeding the above upper limit is not preferable because the molding processability decreases. Here, the melt viscosity V ₆ was 300 ° C., load was 20 kgf / cm ² , L using a flow tester.
/ D = 10/1 and a value measured after holding for 6 minutes.

In the present invention, the above-mentioned (A) PAS is reacted 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. Part of the gas phase in the can is condensed,
The polyarylene sulfide (a) produced by refluxing this in a liquid phase is preferably obtained by washing with an organic solvent and then with water.

Here, the above PAS (a) can be preferably produced by the method described in JP-A-5-222196.

In this polymerization method, the refluxed liquid has a higher water content than the liquid bulk because of the difference in vapor pressure between water and the amide solvent. The reflux liquid having a high water content forms a layer having a high water content at the upper portion of the reaction solution. As a result, residual alkali metal sulfides (eg Na ₂ S),
Alkali metal halides (eg, NaCl), oligomers, and the like are included in the layer in large amounts. In the conventional method, PAS and N
In a state where the raw materials such as a ₂ S and by-products are uniformly mixed, not only a 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, the above disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of the water-rich reflux liquid to the upper part of the liquid phase so as to inhibit the reaction. It can be considered that such factors can be effectively eliminated and a high molecular weight PAS can be obtained. However, the present invention is not limited only by the effect of the above phenomenon, but by various effects caused by cooling the gas phase part, 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, this does not preclude the addition of water at all. However, if the operation of adding water is performed, some of the advantages of the present invention are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The vapor 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 through an internal coil installed at an upper part in a reaction can, a method of flowing a cooling medium through an external coil or a jacket wrapped around the upper part of the reaction can, and using a reflux condenser installed at the upper part of the reaction can A method such as spraying water or blowing a gas (air, nitrogen, etc.) on the upper portion of the outside of the reaction vessel is conceivable, but any method can be used as long as it has the effect of increasing the amount of reflux in the vessel as a result. May be used. If the outside air temperature is relatively low (for example, normal temperature), appropriate cooling can be performed by removing a heat insulating material conventionally provided on the upper part of the reaction vessel. In the case of external cooling, water condensed on the reactor wall
The amide-based solvent mixture enters the liquid phase along the reaction vessel wall. 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 down the cooling device surface or the reactor wall and 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 preferred 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 for 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 low, 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 phase,
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out the reaction at a time point when the molar% is within the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo aromatic compound in the polymerization reaction system is in the range of 2 mol% to 15 mol%, and the molecular weight is in the range of 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 hard 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
When the temperature is higher than 270 ° C., side reactions such as depolymerization are liable to occur, making it difficult to stably obtain a high molecular weight product.

In actual 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. The water content is preferably the alkali metal sulfide 1
It is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol, per mol. If it exceeds 2.5 moles, 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 the amount is less than 0.5 mol, the reaction rate is too high to obtain a product having a sufficient high molecular weight, and undesirable 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. The degree of the cooling effect is usually the most suitable index of the pressure in the reactor. 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, when the pressure in the reaction vessel is reduced as compared with the case where the reaction vessel is not cooled under the same reaction conditions, the amount of the reflux liquid increases, which means that the temperature at the gas-liquid interface of the reaction solution decreases. It is considered that the relative degree of decrease indicates the degree of separation between a layer having a high water content and a layer having no water content. Therefore, it is preferable to perform cooling to such an extent that the internal pressure of the reaction vessel is 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, such as 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. 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 one or more kinds of para-, meta- or ortho-dihalides of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenylsulfone, m, p'-dichlorodiphenylsulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
Dichlorobiphenyl.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
Polyhalo compounds such as trichlorobenzene can also be used, preferably in a concentration of 5 mol% or less, based on the total amount of the 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 (ii) 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, efficient washing can be performed with a smaller amount of water than in a washing method in which water is poured into a filter cake. The present inventor has also found that the conventional solvent removal by drying reduces the reactivity between PAS and the compound represented by the formula (I). However, if solvent removal by water washing is used as in the present invention, PAS
It is possible to maintain high reactivity with the compound represented by the formula (I).

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 the 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. Further, the pH of the acid solution after the acid treatment is preferably 4.0 to 5.0. 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 temperature of the acid treatment and the concentration of the acid solution.
Minutes or more, particularly preferably 10 minutes or more. If it is less than the above, the -SY end in PAS cannot be sufficiently converted to the -SH end, which is not preferable. In 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 preferred. By performing the treatment, an alkali metal such as sodium which is an impurity in the PAS can be reduced. Therefore, elution of alkali metal such as sodium during use of the product and deterioration of electrical insulation can be suppressed.

The compound represented by the chemical formula (I) of the component (B) used in the present invention is known, and is disclosed in, for example, JP-A-7-126527 or JP-A-7-126528.
No., etc.

The component (B) is, for example, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N.
-Methylol acrylamide or N-methylol methacrylamide, or obtained by condensing an alkyl ether derivative of N-methylol acrylamide or N-methylol methacrylamide (hereinafter sometimes referred to as N-methylol acrylamides) with an acid catalyst. To be

For example, when 2,6-xylenol and N-methylolacrylamides are used as starting materials, a glycidyl compound represented by the following formula (II)

[0038]

Embedded image (Wherein R represents a hydrogen atom or a methyl group) can be obtained.

When orthocresol and N-methylolacrylamides are used as starting materials, the following formula
Glycidyl compound represented by (III)

[0040]

Embedded image (Wherein R represents a hydrogen atom or a methyl group, and n is 1 or 2).

In the present invention, the blending amount of the component (B) is
The lower limit is 0.01 parts by weight, preferably 0.1 parts by weight, particularly preferably 0.5 parts by weight, and the upper limit is 20 parts by weight, preferably 15 parts by weight, relative to 100 parts by weight of the component (A) PAS. And particularly preferably 10 parts by weight. When the component (B) is less than the above lower limit, the compatibility with a thermoplastic resin such as a polyester resin or a polyamide resin cannot be improved, and therefore, the impact strength and tensile strength of the resin composition containing the thermoplastic resin cannot be improved. Low mechanical strength. If the upper limit is exceeded, the moldability and the heat resistance and chemical resistance inherent to PAS will decrease due to thickening.

Further, the modified PAS of the present invention may further contain PAS within a range not impairing the effects of the present invention. The mixing ratio of the components (A) and (B)
Is preferably less than 900 parts by weight, particularly preferably 400 parts by weight or less based on 100 parts by weight. When the amount exceeds the upper limit, compatibility with the thermoplastic resin becomes low when blended with the thermoplastic resin, and mechanical strength such as impact strength and tensile strength cannot be improved. Further, the lower limit is not particularly limited, but the improvement in the effect is less than the increase in the cost due to the increase in the compounding amounts of the components (A) and (B), and therefore 10
It is preferable to use more than parts by weight. The PAS used here is not particularly limited, and includes, for example, (A) PAS of the present invention or other known PAS such as JP-B-45-3368, JP-B-52-12240 or JP-B-52-12240. PAS described in Japanese Laid-Open Publication No. 61-7332
Can be used.

The modified PAS of the present invention may further contain an inorganic filler as an optional component. The inorganic filler is not particularly limited, but powdery / scaly fillers, fibrous fillers and the like can be used. Examples of the powdery / scaly filler include silica, alumina, talc, mica, kaolin, clay, silica-alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, Examples thereof include silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads, carbon black and the like. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition to this, a filler such as ZnO tetrapot, metal salt (eg, zinc chloride, lead sulfate, etc.), oxide (eg, iron oxide, molybdenum dioxide, etc.), metal (eg, aluminum, stainless steel, etc.) may be used. it can. These can be used alone or in combination of two or more. Further, the surface of the inorganic filler may be treated with a silane coupling agent or a titanate coupling agent. The inorganic filler is 400 parts by weight or less based on 100 parts by weight of (A) and (B) in total,
It is preferably used in an amount of 300 parts by weight or less. If the amount of the inorganic filler exceeds the above value, the change in viscosity becomes large and molding may not be possible. In order to increase the mechanical strength, it is preferable to add 0.01 parts by weight or more.

Furthermore, if necessary, in addition to the above components,
Known additives and fillers such as antioxidants, ultraviolet absorbers, release agents, heat stabilizers, lubricants, colorants, and the like can be added.

The thermoplastic resin to which the modified PAS of the present invention is added is not particularly limited. Preferred are nylon 6, polyamide such as nylon 6.6, polyester such as polyethylene terephthalate and polybutylene terephthalate, ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride. , Acrylic acid esters, homopolymers and copolymers such as (meth) acrylonitrile, polyesters, polyurethanes, polyacetals,
Polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyphenylene oxide, polyetheretherketone, polyimide, silicone resin, phenoxy resin, fluororesin,
Homopolymers such as polyaryl ethers and polysulfides, random copolymers, block copolymers, graft copolymers and the like are used. The upper limit of the thermoplastic resin is preferably 900 parts by weight, particularly preferably 400 parts by weight, and the lower limit is preferably 10 parts by weight, particularly preferably 30 parts by weight, based on 100 parts by weight of the total of (A) and (B). Blended in parts. When the amount exceeds the upper limit, the effect of improving the compatibility is lowered, and therefore the mechanical strength such as impact strength and tensile strength of the obtained resin composition is lowered. Below the above lower limit, the mechanical strength such as impact strength and tensile strength of the resin composition is low.

The method for producing the modified PAS of the present invention is not particularly limited, and for example, the method described in JP-A-7-126527 can be used.

For example, after the components (A) and (B) are premixed by a mixer such as a Henschel mixer, they are melt-kneaded and extruded by a conventional apparatus such as an extruder, pelletized and PAS.
Denature. Next, a thermoplastic resin and, if desired, PAS, an inorganic filler, known additives and fillers are added to the pellets and mixed with a mixer such as a Henschel mixer, and then a conventional device such as an extruder. Can be melt-kneaded, extruded, and pelletized.

The modification of PAS can also be carried out by adding the component (B) to the reaction vessel in the above PAS production process. The component (B) may be added immediately after the completion of the reaction, or may be added after the reaction solution has cooled sufficiently long after the completion of the reaction. The component (B) is preferably dissolved in an organic solvent and added as a solution. The organic solvent is preferably a polar organic solvent used in the PAS polymerization reaction, for example, N-methylpyrrolidone (N
MP), N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, dimethylsulfoxide, and the like, and mixtures thereof. The denaturing temperature is preferably room temperature to 300 ° C., particularly preferably 100 to 280 ° C., and the denaturing time can be selected preferably in the range of 10 minutes to 20 hours.
The modified PAS slurry is post-treated in the same manner as above,
A modified PAS is obtained.

The modified PAS of the present invention is preferably blended with the above-mentioned thermoplastic resin, for example, automobile equipment parts,
It can be used as a material for electric / electronic device parts, chemical device parts and the like.

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

[0051]

EXAMPLES In the examples, the flow tester used for measuring the melt viscosity V _{6 of} PPS is a flow tester CFT-500C manufactured by Shimadzu Corporation.

Synthesis Example 1 19.381 kg of flaky sodium sulfide (60.4 wt% Na ₂ S) and NM were placed in a 150-liter autoclave.
P45.0kg was charged. While stirring under nitrogen stream 2
The temperature was raised to 04 ° C., and 4.892 kg of water was distilled off.
Then, the autoclave was sealed and cooled to 180 ° C., and 22.161 kg of paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) and 18.0 kg of NMP were charged. 1 kg / c at a liquid temperature of 150 ° C using nitrogen gas
Pressurization to m ² G was started to raise the temperature. While stirring at a liquid temperature of 225 ° C. for 4 hours, water was sprinkled with a water sprinkler attached to the outside of the upper part of the autoclave to cool the upper part of the autoclave. Then, the temperature was raised to a liquid temperature of 250 ° C., and then the reaction was allowed to proceed while stirring at that temperature for 3 hours. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the 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.

After filtering the polymerized slurry, the obtained filter cake was slurried in unused NMP (slurry concentration 15%). Then, stir at 120 ° C. for 30 minutes,
Filter to remove NMP, then pour the filter cake into warm water at about 80 ° C. (about twice the filter cake by weight) to about 3
After thoroughly stirring for 0 minutes, it was filtered. 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 about 5 hours to obtain PPS in the form of white powder. The V ₆ of the obtained PPS (P-1) was 920 poise.

Synthesis Example 2 The polymer slurry obtained in the same manner as in Synthesis Example 1 was filtered, and the obtained filter cake was slurried in unused NMP (slurry concentration 15%). 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 twice. The obtained filter cake was slurried in pure water, acetic acid was added to the slurry to adjust the pH to 5.0, and the mixture was stirred at 50 ° C. for 30 minutes for acid treatment. Next, the operation of filtering the resin, adding pure water, stirring and filtering was repeated 4 times. The obtained filter cake was dried at 120 ° C. for about 5 hours in a hot air circulation dryer to obtain white powdery PPS. Obtained PPS (P-
V ₆ of 2) was 860 poise.

Synthesis Comparative Example 1 The same procedure as in Synthesis Example 1 was carried out except that in the post-treatment step, washing with unused NMP was not carried out. The V ₆ of the obtained PPS (P-3) was 810 poise.

Synthesis Comparative Example 2 Polymerization was carried out in the same manner as in Synthesis Example 1 to obtain a polymerized slurry.

After filtering the polymerized slurry, the obtained filter cake was dried with an evaporator under reduced pressure of 10 torr for 2 minutes.
It was dried in an oil bath at 00 ° C. for about 1 hour until NMP did not distill. 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 5 hours in a hot air circulation dryer to obtain a brown powder product. The V ₆ of the obtained PPS (P-4) was 1,030 poise.

Synthesis Comparative Example 3 Same as Synthesis Example 1 except that 8.0 kg of sodium acetate trihydrate as a polymerization aid was added, 22.500 kg of p-DCB was charged, and the upper part of the autoclave was not cooled. It carried out on condition of. Obtained PPS (P-
V ₆ of 5) was 1,220 poise.

[0060]

Examples 1 to 20 and Comparative Examples 1 to 20 The substances used in Examples and Comparative Examples are as follows. <Component (B)> N- [4- (2,3-epoxypropoxy) -3,5
-Dimethylbenzyl] acrylamide (AXE, manufactured by Kanegafuchi Chemical Industry Co., Ltd., R in the chemical formula (II) is hydrogen) <Thermoplastic resin> Polyethylene terephthalate (PET, trademark, RE-
530, manufactured by Toyobo Co., Ltd.)-Nylon 6 (trademark, A28, manufactured by EMS) In each Example and Comparative Example, first, the components (A) and (B).
Were blended in the amounts (parts by weight) shown in Tables 1 to 4 and pre-mixed for 5 minutes using a Henschel mixer to make them uniform, and then 2
Using a 0 mmφ twin-screw counter-rotating extruder, temperature 300
Pellets were prepared by melt-kneading at ℃ and rotation speed of 400 rpm.

With respect to the pellets (modified PPS), the addition rate of component (B) AXE and the melt viscosity V ₆ were measured. The addition rate was measured as follows. In addition, V ₆ was the same as that of PPS. <Addition Rate of Component (B) AXE> Pellets were crushed into a powder and then sufficiently washed with acetone to remove unreacted AXE. After drying, make a film and IR
The measurement was carried out.

Component (B) Addition rate of AXE [(combined AXE
(Weight / PPS weight) × 100 (%)] is obtained by previously blending (A) PPS and (B) AXE before modification used in various proportions by using IR spectrum (film method). Using the created calibration curve, (B) 1648 cm ^-1 based on AXE and 1580 cm based on (A) PPS
It is a value obtained from the absorbance ratio of ^-1 .

Then, the modified PPS obtained as described above
And PPS and a thermoplastic resin in an amount (parts by weight) shown in Tables 1 to 4 and mixed with a Henschel mixer to give 5
After premixing for 2 minutes to homogenize, use a 20 mmφ twin-screw counter-rotating extruder at a temperature of 300 ° C. and a rotation speed of 400 rp.
Melt kneading was performed to prepare pellets.

The impact strength, tensile strength and tensile elongation at break of the resin composition were measured as follows. <Impact strength> The pellets obtained as described above are supplied to an injection molding machine, and the cylinder temperature is 320 ° C and the mold temperature is 1
A dumbbell piece was molded at 30 ° C., and Izod impact strength was measured and evaluated according to ASTM D256. <Tensile Strength and Tensile Elongation at Break> A dumbbell piece was molded under the same conditions as the impact strength, and measured according to ASTM D638.

The above results are shown in Tables 1 to 4.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4] Examples 1 to 4 relate to modified PPS produced by using the same (A) PPS (P-1) and changing the compounding amount of (B) AXE within the scope of the present invention. The modified PP
The resin compositions containing S, PPS and PET all had high Izod impact strength, tensile strength and tensile breaking elongation. Moreover, when the compounding amount of (B) was increased, the Izod impact strength, the tensile strength and the tensile elongation at break of the resin composition tended to increase. Example 5 is the same as Example 3 except that the type of (A) PPS is changed. The Izod impact strength, tensile strength, and tensile elongation at break of the resin composition were all higher and good.

On the other hand, Comparative Example 1 does not contain (B). The Izod impact strength, the tensile strength and the tensile elongation at break of the resin composition all showed remarkably low values. In Comparative Example 2, the blending amount of (B) exceeds the range of the present invention. The modified PPS thus obtained had a very high melt viscosity V _{6 and} was difficult to mold. Moreover, the resin composition had an Izod impact strength, a tensile strength and a tensile elongation at break which were all extremely low values. In Comparative Examples 3 and 4, under the same blending ratio as in Example 3, the amount of methylene chloride extracted exceeded the range of the present invention in place of (A) PPS of the present invention.
(P-3 and P-4) are used. In each case, the resin compositions exhibited remarkably low values in Izod impact strength, tensile strength and tensile elongation at break, as compared with Example 3. In Comparative Example 5, under the same compounding ratio as in Example 3, PPS (P-5) having an -SX group content less than the range of the present invention was used in place of (A) PPS of the present invention. The PP
S is produced by using sodium acetate trihydrate as a polymerization aid, and is disclosed in Japanese Patent Laid-Open No. 7-1.
It corresponds to the PPS described in Japanese Patent No. 26527 and Japanese Patent Laid-Open No. 7-126528. In the modified PPS, the addition rate of (B) was low, and the Izod impact strength, the tensile strength and the tensile elongation at break of the resin composition all showed extremely low values.

Examples 6 to 10 and Comparative Examples 6 to 10 were modified P under the same conditions as Examples 1 to 5 and Comparative Examples 1 to 5, respectively.
In a resin composition containing PS, the compounding amount of modified PPS is increased. In each of the examples and comparative examples, the same tendency as in Examples 1-5 and Comparative Examples 1-5 was shown. Further, in Examples 6 to 10, the Izod impact strength, the tensile strength and the tensile elongation at break of the resin composition were all higher than those of Examples 1 to 5, and the modified PPS was shown.
It was found that the Izod impact strength, tensile strength, and tensile elongation at break can be increased by increasing the compounding amount of.

Examples 11 to 15 and Comparative Examples 11 to 15
Under the same conditions as in Examples 1 to 5 and Comparative Examples 1 to 5, respectively.
A resin composition was produced by using nylon 6 instead of PET. In any of the examples and comparative examples,
The same tendency as in Examples 1 to 5 and Comparative Examples 1 to 5 was shown.
The resin composition using nylon 6 has a higher tensile strength than the resin composition using PET. Although the Izod impact strength and the tensile elongation at break were slightly lowered, the effects of the present invention could be sufficiently achieved.

Examples 16 to 20 and Comparative Examples 16 to 20
In the resin composition containing the modified PPS under the same conditions as in Examples 11 to 15 and Comparative Examples 11 to 15, respectively.
The amount of PS blended is increased. In any of the Examples and Comparative Examples, Examples 11 to 15 and Comparative Example 11
The same tendency as ~ 15 was shown. In addition, Examples 16 to 20
Shows higher values of Izod impact strength, tensile strength, and tensile elongation at break of the resin composition than in Examples 11 to 15, and when the compounded amount of the modified PPS is increased,
It has been found that Izod impact strength, tensile strength and tensile elongation at break can be increased.

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, the compatibility with a thermoplastic resin is remarkably excellent, and therefore, a resin composition having a remarkably high mechanical strength such as impact strength and tensile strength by blending with a thermoplastic resin is provided. A modified PAS capable of

Claims (2)

[Claims] 1. The amount of (A) methylene chloride extracted is 0.7.
% By weight and a melt viscosity V ₆ of 20 to 15,000.
100 parts by weight of a polyarylene sulfide which is a poise and has an -SX group (X is an alkali metal or a hydrogen atom) of 15 μmol / g or more, and (B) a compound represented by the following formula (I) 0.01 to 20
Parts by weight (Here, Ar has 6 to 20 carbon atoms having at least one glycidyloxy group bonded to an aromatic ring (however,
The number of carbon atoms in the glycidyloxy group is not included), a monovalent to tetravalent aromatic hydrocarbon group is shown, R is a hydrogen atom or a methyl group, and n is an integer of 1 to 4). Sulfide. 2. A polyarylene sulfide (A) reacts an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, and cools the gas phase portion of the reaction can during the reaction. Part of the gas phase inside is condensed,
The modified polyarylene sulfide according to claim 1, which is obtained by washing the polyarylene sulfide (a) produced by refluxing this in a liquid phase with an organic solvent and then with water.