JPH06256517A - Polyarylene sulfide having high reactivity with epoxysilane and resin composition containing the resin - Google Patents

Abstract

PURPOSE:To obtain the subject polyarylene sulfide having respective specific melt flow rate and melt viscosity, exhibiting excellent moisture resistance, thermal stability and mechanical properties and useful for injection molding, sealing, etc. CONSTITUTION:This polyarylene sulfide has a melt flow rate of >=600g/10min at 316 deg.C and a melt viscosity increasing degree of 4.0-12.0 caused by the kneading at 320 deg.C for 5min in a state mixed with 1.0wt.% (based on the polyarylene sulfide) of gamma-glycidoxypropyltrimethoxysilane. A resin composition is produced by using this polyarylene sulfide, a silane compound having epoxy group and a filler as essential components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyarylene sulfide which has a high reactivity with an epoxysilane and whose addition significantly improves mechanical properties, moisture resistance, thermal stability and the like, and such a polyarylene sulfide. The present invention relates to a resin composition containing a sulfide and is used in various fields of molding and processing.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter referred to as PA
(Abbreviated as S) is a thermoplastic polymer having excellent heat resistance and chemical resistance, and is used in various molding processing fields. Usually, in order to obtain a sufficient mechanical strength of a molded product, PAS whose molecular weight is increased by a thermal crosslinking treatment is often used, but such treatment gives a drawback that strength is obtained but brittleness occurs. . As one of the means for solving such a problem, there is a method of adding a silane coupling agent such as epoxysilane, but since the boiling point is low, the addition amount is limited, and a sufficient effect has not been obtained. There wasn't.

[0003]

For the above reasons, it is necessary to achieve sufficient improvement in physical properties with a limited amount of addition when producing a PAS resin composition containing epoxysilane. For that purpose, it becomes indispensable to improve the reactivity between PAS and epoxysilane. That is, if PAS having high reactivity with epoxysilane is synthesized, a sufficient physical property improving effect can be obtained within the limit. Further, when such PAS is used, the amount of epoxysilane added for obtaining the same effect is reduced, which is highly desirable not only in terms of quality but also in terms of safety and economy.

The present inventors have paid attention to this point, and as a result of repeated studies, have succeeded in synthesizing a novel PAS having a higher reactivity with epoxysilane than conventional PAS.
That is, the present invention provides a novel PAS having high reactivity with epoxysilane and a resin composition containing such PAS.

[0005]

Generally, a polyarylene sulfide is produced by polymerizing an alkali metal sulfide and a polyhaloaromatic compound in the presence of an organic polar solvent. -3368, USP3
919177, USP4415729, USP4645.
826 and the like.
The present inventors have found that by adding a certain amount or more of alkali metal hydroxide to alkali metal sulfide, and further devising a treatment method after completion of the polymerization reaction, PAS having high reactivity with epoxysilane can be obtained. I found that I could get it.

That is, in the present invention, the melt flow rate at 316 ° C. is 600 g / 10 minutes or more, and γ-
When 1.0% of glycidoxypropyltrimethoxysilane (weight ratio to polyarylene sulfide) is added, 3
The degree of increase in melt viscosity after kneading at 20 ° C. for 5 minutes is 4.0 to 1
The polyarylene sulfide is characterized by having a range of 2.0.

The method for producing the PAS of the present invention having a high reactivity with epoxysilane includes, for example, the reaction with an alkali metal sulfide and a polyhaloaromatic compound in a polar organic solvent, with respect to the alkali metal sulfide used. And adding a certain amount or more of alkali metal hydroxide, that is, 3 to 20%,
There is preferably a method in which it is essential to add 4 to 10% (molar ratio) of an alkali metal hydroxide. In addition, since alkali metal hydrosulfides and alkali metal thiosulfides are usually present in trace amounts in alkali metal sulfides, in order to react with them and replace the total amount with alkali metal sulfides, a very small amount (1 mole ratio is used). %) Of alkali metal hydroxide is already a general means at the time of production, as is known from JP-A-62-177027. However, in order to obtain PAS having a high reactivity with epoxysilane, which is the object of the present invention, a certain amount of alkali metal hydroxide in excess of the amount for the above purpose is added to the alkali metal sulfide ( The molar ratio is required to be 3 to 20%, preferably 4 to 10%), and the present invention is mainly based on such findings.

The alkali metal sulfides used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. Examples of such alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and mixtures thereof.

The above-mentioned alkali metal sulfide may be synthesized from the alkali metal hydrosulfide and the alkali metal hydroxide during the reaction. In this case, the alkali metal hydroxide is added in an amount necessary for reacting with the alkali metal hydrosulfide to generate the alkali metal sulfide, and is 3 to 20% with respect to the generated alkali metal sulfide, Preferably 4 to
10% (molar ratio) will be added.

Alkali metal hydrosulfides include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and mixtures thereof.
Such alkali metal sulfides, alkali metal hydroxides and alkali metal hydrosulfides can be used in the form of hydrates and / or aqueous mixtures or anhydrous forms, and there is no limitation on their shape, and they can be crystals, flakes or solutions. It may be in a solid state or a molten state.

The polyhaloaromatic compound which is sulfided with an alkali metal sulfide is a halogenated aromatic compound having two halogen atoms directly bonded to an aromatic nucleus, specifically, p-dichlorobenzene and m. -Dichlorobenzene, o-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dichloronaphthalene, trichloronaphthalene, dibromobenzene, tribromobenzene, dibromonaphthalene, diiodobenzene, triiodobenzene, dichlorodiphenylsulfone, dibromodiphenylsulfone, dichlorobenzophenone, Dibromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, dibromobiph Cycloalkenyl, etc., and dihalo aromatic compounds such as these mixtures are used.

The polar organic solvent used in the present invention includes formamide, acetamide, N-methylformamide,
N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, hexamethylphosphor Amides, tetramethylurea, N, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid amidoureas and lactams; sulfolane, dimethylsulfolane, and other sulfones; benzonitrile, and other nitriles; methyl Examples include ketones such as phenyl ketone; polyethylene glycol and the like, and mixtures thereof.

The polyhaloaromatic compound used is in a molar ratio of 0.50 to alkali metal sulfide.
The range is 10.0, preferably 0.80 to 5.0.
The amount of the polar organic solvent used in the present invention is in the range of 10 to 2.0, preferably 8.0 to 3.0 in terms of molar ratio to the alkali metal sulfide.

The reaction temperature during the production of PAS of the present invention is in the range of 80 to 300 ° C., and the temperature can be changed stepwise or continuously during the reaction. In addition, the reaction time depends on the reaction temperature, but is 0.5 to 3
It is in the range of 0 hours, preferably 1 to 15 hours. When the reaction time is shorter than this range, it becomes difficult to obtain a polymer having a sufficient viscosity, and when the reaction time is longer than this range, the productivity is deteriorated. Also, this reaction is preferably
It is performed under an atmosphere of an inert gas.

The amount of water present in the polymerization reaction system is 0.5 to 5 mol, preferably 0.6, relative to the alkali metal sulfide.
˜2.0 mol, more preferably 0.7 to 1.5 molo. When the water content in the reaction system is less than the above range, it is difficult to carry out the polymerization reaction.

The reactor in the PAS production may be a tank type, a tube type or the like, and the reaction may be carried out in any of batch operation, semi-batch operation and flow operation.

The PAS obtained by the above reaction can be obtained by a conventional method, for example, by filtering the reaction mixture after completion of the reaction, followed by washing with water, or diluting the reaction mixture with water.
Subsequently, the reaction mixture can be separated and purified by a method such as filtration and washing with water. Here, when PAS is separated and purified from the reaction mixture, the solvent is first distilled and recovered, a large amount of water is added and filtered, and then 120-
By using the method including the process of washing with hot water at 300 ° C., the reactivity with epoxysilane is further improved.
This is an effective means for obtaining AS.

The PA produced by the above-mentioned method
When the method of treating with S is used as the method of purifying S, the reactivity with epoxysilane is further improved.
It is effective for obtaining AS. The acid used is
It is preferable to use dilute hydrochloric acid, dilute phosphoric acid, dilute acetic acid or the like from the viewpoint of easy handling and economy. The conditions of such acid washing are as follows: for a slurry mixture obtained by adding 2 to 20 parts by weight of warm water at 30 to 95 ° C. to 1 part by weight of the polymer,
An acid is added so that pH = 0.5 to 5.5, preferably 1.0 to 3.5, the mixture is stirred for 10 minutes or more, filtered, and water is further added to adjust the pH of the filtrate to 6.0. It is preferable to repeatedly wash with water until it reaches 8.0. It should be noted that if the stirring time is short or the pH value is too high, the effect of acid washing is small, and if the pH value is too low, the polymer may be deteriorated.

In the PAS of the present invention, it is also essential that the melt flow rate (abbreviated as FR) at 316 ° C. is 600 g / 10 minutes or more, and therefore, the reaction conditions at the time of production so as to fall within the range of the FR. It is necessary to adjust (measured by ASTM method D-1238-74). FR
Is less than 600 g / 10 minutes, the melt viscosity is largely increased by the addition of epoxysilane, resulting in poor flowability and difficulty in molding. However, when the produced PAS is thermally crosslinked, the reactivity with the epoxysilane of the thermally crosslinked PAS may be lower than this value since the reactivity with the epoxysilane is affected.

In order to improve performances such as strength, heat resistance and dimensional stability, it is preferable to use a silane compound having an epoxy group and various fillers in combination with the PAS of the present invention. is there.

Examples of the epoxy group-containing silane compound used as an additive for the PAS of the present invention include γ-glycidoxypropyltrimethoxysilane and γ.
-Glycidoxypropyltriethoxysilane, β-
Examples include (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Further, the addition amount of these epoxysilanes is 0.01 to 100 parts by weight of the resin composition.
The amount is 5.0 parts by weight, preferably 0.05 to 3.0 parts by weight.

Examples of the filler include fibrous filler and inorganic filler. As the fibrous filler, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide,
Fibers such as calcium sulfate and calcium silicate and natural fibers such as wollastonite can be used. Further, as the inorganic filler, barium sulfate, calcium sulfate, clay, biferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like. Can be used. The proportion of the filler in the resin composition is 5 to 100 parts by weight of the resin composition.
From the viewpoint of molding, it is preferable that the amount is within the range of 80 parts by weight.

A typical example of the PAS of the present invention produced is PPS (polyphenylene sulfide). However, P produced by the method described above
The AS is not limited to this, and includes all polymers and copolymers thereof that can be produced by the above-mentioned raw materials. By adding epoxy silane, these PASs are used for injection molding, compression molding, extrusion molded products such as films, fibers, sheets, tubes, tubes and blow molded products, and sealing electronic parts such as transistors, capacitors and ICs. It is possible to impart very excellent properties such as those used for stopping. It goes without saying that it can be used for such an application even when epoxysilane is not added.
Also, regardless of whether or not epoxy silane is added,
In addition to the above-mentioned fillers, it is also suitable to blend pigments, flame retardants, stabilizers, other silane coupling agents, and other polymers with this polymer, if necessary.

[0024]

EXAMPLES The method of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(1) Measurement of melt flow rate (FR) The melt flow rate of PAS at 316 ° C. is AS
Measured according to TM method D-1238-74.

(2) Method for evaluating degree of increase in melt viscosity upon addition of epoxysilane 1.0% γ-glycidoxypropyltrimethoxysilane
(Weight ratio to polymer) Evaluation was performed by the degree of increase in melt viscosity at the time of addition melt kneading. Here, the melt-kneading is performed using a Labo Plastomill (20-200C, using R-60 type mixer, manufactured by Toyo Seiki) at 320 ° C. and 100 rpm.
I went for 5 minutes. The degree of increase in melt viscosity at the time of melt kneading with addition of epoxysilane is represented by the following equation. Degree of increase = (FR when epoxy silane is not added) / (FR after addition)

Example 1 556.1 g (4.2) of sodium sulfide 2.9 hydrate was placed in a 4.5-liter autoclave equipped with a stirrer and having a bottom valve.
71 mol), 1500 g of N-methylpyrrolidone, 48.
21.4 g (0.257 mol (6.0 mol% relative to sodium sulfide)) of 0% sodium hydroxide aqueous solution was charged, and the mixture was heated to 200 ° C. in a nitrogen atmosphere at 150 ° C. for 2 hours.
The temperature was gradually raised while stirring at pm, and a mixture of water and some N-methylpyrrolidone was distilled off. The final distillate was 146.01 g. When the water content and the sulfur content in this distillate were measured, it was found that the water content was 130.94 g (theoretical distillate water amount: 234.007 g) and the sulfur content was 13.5 mmol (0.32% based on the charged sulfur content). Was there.

Next, the system was closed, and 638.41 g (4.343 mol) of p-dichlorobenzene and 348.4 g of N-methylpyrrolidone were added, and polymerization was carried out at 220 ° C. for 4.5 hours. Thereafter, the temperature was raised to 255 ° C. over 30 minutes, and the reaction was continued for another 3 hours. After completion of the reaction, after cooling to room temperature, the reaction mixture slurry was diluted with a large amount of warm water according to a conventional method, washed with water and dried to obtain 445.6 g (yield 96.9%) of a light brown polyphenylene sulfide. . The FR of this polymer was 900 g / 10 minutes, and the degree of increase in melt viscosity was 5.4.

Example 2 After completion of the reaction, the solvent, by-produced water, etc. were distilled off from the reaction mixture slurry, and a large amount of water was added to the reaction mixture to wash it.
Further, add 10 times the weight of water to the polymer, and add 200 ° C.
The same operation as in Example 1 was performed, except that after heating and stirring for 30 minutes, the mixture was filtered, washed with water, and dried. Slightly brown polyphenylene sulfide 445.7 g (yield 96.9)
%) Was obtained. The FR of this polymer is 1000 g / 10 minutes,
The degree of increase in melt viscosity was 7.8.

Example 3 In Example 2, after adding 10 times weight of water to the polymer, heating and stirring at 200 ° C. for 30 minutes and filtering,
Further, 10 times the weight of 80 ° C. warm water was added, pH was adjusted to 2.0 with phosphoric acid while keeping the mixture warm, and the mixture was stirred for 30 minutes, then filtered, washed with water, and dried. The operation was performed. 445.4 g (yield 96.9%) of a light brown polyphenylene sulfide was obtained. The FR of this polymer is 1050 g / 10 minutes, and the degree of increase in melt viscosity is 8.1.
Met.

Example 4 The polymer obtained in Example 3 was treated at 220 ° C. in the presence of air.
It was heat-crosslinked for 6 hours. The FR of this polymer is 412g
/ 10 minutes, the degree of increase in melt viscosity was 7.4.

Example 5 The polymer obtained in Example 3 was treated at 220 ° C. in the presence of air.
It was heated and crosslinked for 12 hours. The FR of this polymer is 202
g / 10 minutes, melt viscosity increase was 7.1.

In the above examples, the amount of sodium hydroxide charged at the time of synthesis was 6.0 mol% with respect to sodium sulfide. On the other hand, in the comparative examples described below, the charged amount of sodium hydroxide is all 2.0 mol%.

Comparative Example 1 Into a 4.5 liter autoclave with a stirrer having a bottom valve, 556.1 g (4.2) of sodium sulfide 2.9 hydrate was added.
71 mol), 1500 g of N-methylpyrrolidone, 48.
7.13 g of 0% aqueous sodium hydroxide solution (0.0856
Mol (2.0 mol% with respect to sodium sulfide)) and charged to 200 ° C. under a nitrogen atmosphere for 150 hours over 2 hours
The temperature was gradually raised while stirring at pm, and a mixture of water and some N-methylpyrrolidone was distilled off. The final distillate was 144.55 g. When the water content and the sulfur content in this distillate were measured, it was found that the water content was 123.60 g (theoretical distillate amount of 226.65 g) and the sulfur content was 13.6 mmol (0.32% based on the charged sulfur content). Was there.

Then, the system was closed, 638.41 g (4.343 mol) of p-dichlorobenzene and 348.4 g of N-methylpyrrolidone were added, and polymerization was carried out at 220 ° C. for 4.5 hours. Thereafter, the temperature was raised to 255 ° C. over 30 minutes, and the reaction was continued for another 3 hours. After completion of the reaction, after cooling to room temperature, the reaction mixture slurry was diluted with a large amount of warm water according to a conventional method, washed with water and dried to obtain 445.8 g (yield 97.0%) of light brown polyphenylene sulfide. . The FR of this polymer was 700 g / 10 minutes, and the degree of increase in melt viscosity was 1.1.

Comparative Example 2 After completion of the reaction, the solvent, by-produced water and the like were distilled off from the reaction mixture slurry, and a large amount of water was added thereto for washing,
Further, add 10 times the weight of water to the polymer and add 200 ℃
The same operation as in Comparative Example 1 was performed, except that the mixture was heated and stirred for 30 minutes, and then filtered, washed with water, and dried. Slightly brown polyphenylene sulfide 446.0 g (yield 97.0
%) Was obtained. The FR of this polymer was 750 g / 10 minutes, and the degree of increase in melt viscosity was 1.9.

Comparative Example 3 In Comparative Example 2, after adding 10 times by weight of water to the polymer and heating and stirring at 200 ° C. for 30 minutes and filtering,
Further, 10 times the weight of 80 ° C. hot water was added, and the pH was adjusted to 2.0 with phosphoric acid while stirring while maintaining the temperature, and the mixture was stirred for 30 minutes, filtered, washed with water, and dried. I went. A slightly brown polyphenylene sulfide (445.6 g, yield 96.9%) was obtained. The FR of this polymer was 760 g / 10 minutes, and the degree of increase in melt viscosity was 2.1.

Comparative Example 4 The polymer obtained in Comparative Example 3 was treated at 220 ° C. in the presence of air.
It was heat-crosslinked for 10 hours. The FR of this polymer is 391
g / 10 minutes, the degree of increase in melt viscosity was 1.8.

Comparative Example 5 The polymer obtained in Comparative Example 3 was treated at 220 ° C. in the presence of air.
It was heat-crosslinked for 21 hours. The FR of this polymer is 207
g / 10 minutes, the degree of increase in melt viscosity was 1.5.

Examples 6-10, Comparative Examples 6-10 60 parts by weight of PPS obtained in Examples 1-5 above, glass fiber (RES03-TP86 manufactured by Nippon Glass Fiber Co., Ltd.)
40 parts by weight and 0.3 part by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.) were mixed, and this mixture was melt-kneaded at 320 ° C. in an extruder,
Pelletized. For comparison, the PPS obtained in Comparative Examples 1 to 5 was used to pelletize in the same manner.

Using an injection molding machine, each of the obtained pellets was used to prepare a test piece for measuring physical properties at a resin temperature of 320 ° C. and a mold temperature of 150 ° C., and the physical properties were measured. The results are shown in Tables 1 and 2 below.

[0042]

[Table 1]

All using γ-glycidoxypropyltrimethoxysilane

[0044]

[Table 2]

All using γ-glycidoxypropyltrimethoxysilane

Examples 11 to 13 Pellets obtained by mixing 60 parts by weight of PPS obtained in Examples 3 to 5, 40 parts by weight of glass fiber and 0.1 part by weight of γ-glycidoxypropyltrimethoxysilane were also pelletized. Turned into

Example 14 60 parts by weight of PPS obtained in Example 3 and 40 glass fibers
Parts by weight and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd.)
Similarly, a mixture of 3 parts by weight was pelletized.

Using an injection molding machine, a test piece for measuring physical properties of each of the obtained pellets was prepared at a resin temperature of 320 ° C. and a mold temperature of 150 ° C., and the physical properties were measured. The results are shown in Table 3 below.

[0049]

[Table 3]

(A): Using β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane All other uses of γ-glycidoxypropyltrimethoxysilane

In Examples 6 to 10 and 14 in which 0.3% of epoxysilane was added, extremely good molding properties were exhibited as compared with Comparative Examples 6 to 10 in which the same amount of epoxysilane was added. Also, in Examples 11 to 13 in which the added amount of epoxysilane was reduced to 0.1%, excellent molding physical properties were maintained as compared with the comparative example having the same level of compound FR.

[0052]

INDUSTRIAL APPLICABILITY The PAS of the present invention has greater reactivity with epoxysilane than conventional PAS, and has a great effect of improving mechanical properties and the like when epoxysilane is added. Therefore, these physical properties are significantly improved when a conventional amount of epoxysilane is added. Further, even with a smaller amount of addition, it is possible to achieve superior physical properties to those of the conventional products, and it is very useful for injection molding, sealing of electronic parts, etc.
It can be an AS molding material.

Claims (3)

[Claims] 1. A melt flow rate at 316 ° C. of 600 g / 10 minutes or more, and 320 ° C. for 5 minutes when 1.0% of γ-glycidoxypropyltrimethoxysilane (weight ratio to polyarylene sulfide) is added. A polyarylene sulfide characterized in that the degree of increase in melt viscosity after kneading is in the range of 4.0 to 12.0. 2. A polyarylene sulfide according to claim 1, (A) a silane compound having an epoxy group (B),
And (C) a filler as an essential component. 3. A resin containing (A ′) a resin obtained by thermally crosslinking the polyarylene sulfide according to claim 1, (B) a silane compound having an epoxy group, and (C) a filler as essential components. And a resin composition.