JPH069850A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the composition composed of a modified olefinic elastomer and a polyarylene sulfide and giving a molded product having remarkably improved impact resistance while keeping excellent heat-resistance and mechanical strength of the base resin. CONSTITUTION:The composition is produced by compounding (A) 2-70wt.% (preferably 10-40wt.%) of a modified olefinic elastomer obtained by grafting a glycidyl compound of formula I (R is H or 1-6C alkyl; Ar is 6-20C aromatic hydrocarbon group having glycidyloxy group; m is 1-4) (preferably the compound of formula II) to an olefinic elastomer (preferably having an ethylene content of 10-90wt.%) with (B) 98-30wt.% (preferably 90-60wt.%) of a polyarylene sulfide having an alkali metal content suppressed to <=900ppm by deionizing treatment.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyarylene sulfide resin composition. More specifically, it relates to a polyarylene sulfide resin composition containing a modified olefin polymer, which is excellent in impact resistance and other mechanical properties and is useful as a structural material or a mechanical part.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as
Polyarylene sulfide (hereinafter referred to as "PAS") represented by "PPS" has higher heat resistance than other general-purpose engineering plastics,
It has chemical resistance and rigidity, but has the drawback of poor impact resistance. Therefore, a large amount of reinforcing material such as glass fiber must be added for use as a structural material and as a mechanical part.

Generally, a method of adding an elastomer to form an alloy for the purpose of improving the impact resistance of a resin having poor impact resistance is used, but in the case of PAS, compatibility with many elastomers is not high. , Alloying with elastomer is insufficient. For the purpose of improving impact resistance and other properties of PAS, it has been proposed to blend PAS with an α-olefin-glycidyl methacrylate copolymer (Japanese Patent Laid-Open No. 61-21156). It is difficult to greatly improve the impact resistance without impairing the properties.

International Publication WO91 / 14717 describes a modified polyolefin obtained by grafting a glycidyl group-containing (meth) acrylamide monomer onto a polyolefin. Further, this document describes this modified polyolefin as polyester, PPS, and the like. Blending with a resin is described. This modified polyolefin is PP
The blends with S retain the good properties inherent to PPS and have improved impact resistance. However, it cannot be said that the impact resistance is sufficiently high, and higher impact resistance is desired.

[0005]

The object of the present invention is to provide a PA
An object of the present invention is to provide a PAS resin composition in which impact resistance is remarkably improved while maintaining the original good heat resistance and mechanical strength of S.

[0006]

The above objects are achieved by the PAS resin composition of the present invention. That is, the present invention relates to an olefin elastomer having the following general formula (1):

[Chemical 2] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and m is 1 to 4
A modified olefin elastomer grafted with a glycidyl compound represented by the formula (B) and (B) a polyarylene sulfide having an alkali metal content reduced to 900 ppm or less by deionization. Provided is a polyarylene sulfide resin composition containing an olefin elastomer.

The PAS used in the present invention has a skeleton composed of an arylene sulfide bond represented by the following formula (2) or contains the arylene sulfide bond (2) as a main component,

[0008]

[Chemical 3]

An ether bond represented by the following formula (3), a sulfone bond represented by the following formula (4), a biphenyl bond represented by the following formula (5), and a substituted phenyl represented by the following formula (6). A sulfide bond (provided that in the formula (6), R ¹ represents an alkyl, nitro, phenyl, alkoxy, or carboxyl group), and a copolymerization group exemplified by the trifunctional bond represented by the following formula (7) The bond derived from the combined component may be contained as a poor component. However, the copolymerization component is
It is preferably less than 30 mol%.

[0010]

[Chemical 4] The PAS having the skeleton as described above is obtained, for example, by reacting an alkali metal sulfide (typically sodium sulfide) with a dihalide. here,
Examples of the dihalide used as a raw material include dihalogenated benzene represented by the following formula.

[0011]

[Chemical 5] (In the formula, R ² represents an alkyl or alkoxy group having 1 to 3 carbon atoms, n represents an integer of 0 to 3, and X represents a halogen atom).

Specific examples of such dihalogenated benzene include compounds represented by the following formula. However, in these formulas, X ₁ is a halogen atom, and examples thereof include Cl or Br. These dihalogenated benzenes are generally used in the form of a mixture,
It is preferable that para dihalide is contained in this mixture in an amount of 85 mol% or more.

[0013]

[Chemical 6]

In the reaction between the alkali metal sulfide and the dihalide, if necessary, a trihalide such as trichlorobenzene may be added to the reaction system within a range of 5 mol% or less based on the dihalide. The polymerization reaction may be carried out in a polar solvent, preferably an amide solvent such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to control the degree of polymerization, it is desirable to add an alkali metal salt of carboxylic acid or sulfonic acid, alkali hydroxide or the like. The preferred polymerization reaction temperature and time are approximately 120 to 300 ° C. and 2 to 10 hours. It is desirable to carry out the reaction in an inert gas atmosphere. After completion of the reaction, the solid product is filtered off, washed thoroughly with deionized water and dried to obtain a PAS resin.

PAS can be crosslinked by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating to make it higher in molecular weight before use. PAS used in the present invention
As described above, various types can be widely used, but as described above, the PAS just purified by a conventional method after the polymerization is generally about 1000 to about 2000 ppm,
Sometimes it contains more Na or other alkali metals. Therefore, in the present invention, further deionization treatment is performed to reduce the content of sodium and other alkali metals to 90%.
It is important to use the one reduced to 0 ppm or less. Particularly, P with an alkali metal content of 500 ppm or less
It is preferable to use AS.

Examples of the deionization treatment include acid treatment. A typical method of acid treatment is to add P to an acid or its aqueous solution.
This is a method of immersing AS. It is also possible to appropriately stir or heat the acid treatment. A specific example of the acid treatment method is a method in which the PAS powder is immersed in an aqueous acetic acid solution having a pH of 4 and stirred for about 30 minutes. The acid-treated PAS needs to be washed several times with water or warm water to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water so as not to impair the denaturing effect of the acid treatment. The acid used for the acid treatment of PAS is not particularly limited as long as it has no action of decomposing PAS, and specific examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propionic acid. Of these, acetic acid and hydrochloric acid are preferable, and nitric acid is not preferable because it decomposes and deteriorates PAS.

The modified olefin-based elastomer used in the present invention is (i) an olefin-based elastomer modified by (ii) a specific glycidyl compound having an acrylamide group and an epoxy group.
The above (i) olefin elastomer is a copolymer of ethylene and one or more α-olefins other than ethylene such as propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene. Means rubber. The copolymer rubber of ethylene and one or more kinds of α-olefins other than ethylene is typically ethylene-butene copolymer rubber (EBR), ethylene-propylene copolymer rubber (EPR). And ethylene-propylene-diene copolymer rubber (EPDM). Ethylene-propylene-diene copolymer (EPD
The diene in M) is dicyclopentadiene, 1,
Non-conjugated dienes such as 4-hexadiene, cyclooctadiene, methylene norbornene or conjugated dienes such as butadiene and isoprene can be used.

The content of ethylene in the above olefin elastomer is generally 5 to 95% by weight, preferably 10 to 90% by weight. If the ethylene content is less than 5% by weight or more than 95% by weight, it becomes difficult to exhibit properties as an elastomer. The crystallinity of such an olefin elastomer is usually 40% by weight or less.

The ethylene-propylene copolymer rubber (EPR), which is a typical example of the olefin elastomer used in the present invention, has a repeating unit content of ethylene of 50 to 80 mol%, and is derived from propylene. The content of the repeating unit is preferably 20 to 50 mol%. A more preferable range is 60 to 70 mol% of ethylene-based repeating units and 30 to 40 mol% of propylene-based repeating units. Also, EPR melt flow rate (MFR, 230 ° C, 2.16 kg load)
Is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes.

Ethylene-butene copolymer rubber (EBR), which is another typical example of the olefin elastomer, is
The content of repeating units derived from ethylene is 50-
It is preferable that the content of the repeating unit derived from butene is 90 mol% and the content thereof is 10 to 50 mol%. A more preferable range is 60 to 80 mol% of ethylene-based repeating units and 20 to 40 mol% of butene-based repeating units.
In addition, the EBR melt flow rate (MFR, 230
(° C, 2.16 kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.5 to 3
It is 0 g / 10 minutes.

The ethylene-propylene-diene copolymer (EPDM), which is another typical example of the olefin elastomer, has a repeating unit content of 40 to 70 mol% derived from ethylene, and is derived from propylene. The content of the repeating unit is 30 to 60 mol%, and the content of the repeating unit derived from a diene is 1 to
It is preferably 10 mol%. More preferable ranges are 50 to 60 mol% of ethylene repeating units, 40 to 50 mol% of propylene repeating units, and 3 to 6 mol% of diene repeating units. Furthermore, E
Melt flow rate of PDM (MFR, 230 ° C, 2.
16 kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 1.
0 minutes.

Ethylene-propylene copolymer (EPR), ethylene-butene copolymer rubber (EBR) and ethylene-propylene-diene copolymer (EPDM), which are typical examples of olefin elastomers, are basically It is composed of the above repeating unit, but may be, for example, 4-methyl-1 within a range that does not impair the properties of these copolymers.
-Other repeating units such as repeating units derived from other α-olefins such as pentene may be contained in a proportion of 10 mol% or less.

In the present invention, if desired, a polyolefin may be added to the above-mentioned (i) olefin elastomer.
It is also possible to use an olefin elastomer composition in which 0% by weight or less is mixed. As the polyolefin that can be used in addition to the olefin elastomer, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1
-Homopolymers of α-olefins such as pentene, non-elastomeric copolymers of ethylene and propylene or other α-olefins, or non-elastomeric copolymers of two or more of these α-olefins, or these The homopolymers, the copolymers, and the blend of the homopolymer and the copolymer can be used.

When the polyolefin is mixed, the mixing amount is 10 olefin elastomer + polyolefin.
0% by weight is 80% by weight or less, preferably 50% by weight or less. When the amount of the polyolefin mixed exceeds 80% by weight, the properties as an elastomer are lost.

In the present invention, the modifying monomer (ii) used for modifying the olefinic polymer is represented by the following general formula (1):

[Chemical 7] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and m is 1 to 4
Represents the integer) of the glycidyl compound.

Preferred glycidyl compounds include those represented by the following general formula (8).

[Chemical 8] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms.)

Such a glycidyl compound can be produced by the following method, as shown in, for example, JP-A-60-130580. First, an aromatic hydrocarbon having at least one phenolic hydroxyl group, N-methylolacrylamide or N-methylolmethacrylamide, or an alkyl ether derivative of N-methylolmethacrylamide (hereinafter, these are referred to as N-methylolacrylamides). By condensation using an acid catalyst, the following general formula (9):

[Chemical 9] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, and Ar ′ is 6 to 6 carbon atoms having at least one hydroxyl group.
20 is an aromatic hydrocarbon group, and n represents an integer of 1 to 4. ) Is produced.

The above-mentioned aromatic hydrocarbon having at least one phenolic hydroxyl group is not particularly limited,
For example, phenol, o-cresol, m-cresol,
p-cresol, 2,6-xylenol, 2,4-xylenol, o-chlorophenol, m-chlorophenol, o-phenylphenol, p-chlorophenol,
Phenolic compounds such as 2,6-diphenylphenol, polyphenolic compounds such as hydroquinone, catechol and phloroglucinol, polycyclic hydroxy compounds such as 1-naphthol, 2-naphthol and 9-hydroxyanthracene, 2,2-bis Examples thereof include bisphenols such as (4-hydroxyphenyl) propane (bisphenol-A) and bis (4-hydroxyphenyl) methane.

Then, the hydroxyl group of the compound represented by the general formula (9) is glycidylated to give the general formula (1).
A glycidyl compound represented by can be obtained. This glycidylation is preferably carried out by performing an addition reaction between the compound represented by the general formula (9) and epihalohydrin, and then dehydrohalogenating with caustic alkali. As the above-mentioned epihalohydrin, epichlorohydrin, epibromhydrin, epiiodohydrin, etc. can be used.

The addition reaction with epihalohydrin is carried out using a phase transfer catalyst. As the phase transfer catalyst, for example, a quaternary ammonium salt such as tetrabutylammonium bromide, trioctylmethylammonium chloride or benzyltriethylammonium chloride, or a quaternary phosnium salt such as tetraphenylphosphonium chloride or triphenylmethylphosphonium chloride is used. be able to. The amount of the phase transfer catalyst used is
When the compound represented by the general formula (9) is 100 mol%,
It is preferably in the range of 0.01 to 100 mol%. A particularly preferable amount of the phase transfer catalyst used is 0.05 to 10 mol%. The reaction temperature and reaction time are 50 to 12
5 minutes to 2 hours at 0 ° C, more preferably 1 to 80 ° C to 110 ° C
0 to 30 minutes.

The addition of epihalohydrin is followed by dehydrohalogenation with caustic. As the caustic alkali, caustic soda, caustic potash, lithium hydroxide and the like can be used. These can be used as solids or as aqueous solutions. As the dehydrohalogenation catalyst, the same one as the above-mentioned phase transfer catalyst can be used. Further, a catalyst other than the above phase transfer catalyst can also be used, and as such a catalyst, crown ethers,
Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.

The caustic alkali is preferably used in an equimolar amount with respect to the compound represented by the general formula (9). More preferably, 1.1 to 1.5 times the molar amount is used. The reaction temperature and reaction time are 20 to 90 ° C.
10 minutes to 3 hours, more preferably 40 to 70 ° C. for 30 minutes to 20 hours.

The modification (graft polymerization) of the olefinic elastomer (or the olefinic elastomer composition) with such a glycidyl compound can be carried out by either a solution method or a melt-kneading method. In the case of the melt-kneading method, the olefinic elastomer, the above-mentioned glycidyl compound for modification, and the catalyst as required are charged into an extruder, a twin-screw kneader, or the like, and heated to a temperature of 180 to 300 ° C. to melt. While kneading for 0.1 to 20 minutes. In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene and stirred at a temperature of 90 to 200 ° C for 0.1 to 100 hours. In any case, a usual radical polymerization catalyst can be used as the catalyst, and specific examples thereof include benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid. , Peroxides such as dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tert-butylperoxypivalate, 2,5-dimethyl-2,5-ditert-butylperoxyhexyne,
Examples thereof include diazo compounds such as azobisisobutyronitrile. The amount of catalyst added is modified glycidyl compound 1
It is about 0.1 to 10 parts by weight with respect to 00 parts by weight. A phenolic antioxidant can be added during the graft reaction. However, when the radical polymerization catalyst is not added, it is preferable not to add it.

The mixing ratio of the (ii) glycidyl compound is 100 parts by weight of the (i) olefin elastomer (or olefin elastomer composition).
It is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight. When the blending amount of the glycidyl compound is less than 0.01 parts by weight, it is difficult to achieve a high graft ratio, and when it exceeds 30 parts by weight, the molecular weight of the modified olefin elastomer obtained is lowered.

The compounding ratio of the above-mentioned (a) modified olefin elastomer and (b) PAS is 2 to 70% by weight, preferably 10 to 10% by weight of the (a) modified olefin elastomer, based on the total weight of both. 40% by weight,
(B) PAS is 98 to 30% by weight, preferably 90 to 6
It is 0% by weight. If the amount of (a) the modified olefin elastomer is less than 2% by weight (that is, if the amount of (b) PAS exceeds 98% by weight), the effect of improving the physical properties such as impact resistance of PAS by the blending is not sufficient, and If the amount of (a) the modified olefin elastomer exceeds 70% by weight (that is, if the amount of (b) PAS is less than 30% by weight), the PAS properties are impaired.

The PAS resin composition of the present invention contains a filler such as an inorganic filler or carbon black, and other additives such as a heat stabilizer, a light stabilizer, a flame retardant and a plasticizer for the purpose of modifying the filler. Agents, antistatic agents, foaming agents, nucleating agents and the like can be added. Further, a small amount of undeionized PAS may be added as long as the excellent impact resistance aimed at by the present invention can be obtained.

The composition of the present invention comprising such (a) modified olefin elastomer and (b) deionized PAS comprises (a) modified olefin elastomer, (b) deionized PAS and, if necessary, 220-300 ° C., preferably 240-, by using a kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, or a Brabender Plastograph (registered trademark). It can be obtained by kneading in a molten state at 280 ° C.

[0038]

[Butene content 80%, melt flow rate (230
℃, 2.16kg load) 1.5g / 10 minutes]

(B) Ethylene-propylene copolymer rubber (EPR) [Propylene content 70%, melt flow rate (23
0 ° C, 2.16 kg load) 1.7 g / 10 minutes]

[2] Modification monomer AXE: Glycidyl compound represented by the chemical formula (8) [manufactured by Kanegafuchi Chemical Industry Co., Ltd.] [3] Radical generator POX: Perhexin 2-5B [manufactured by NOF Corporation] [4] Polyarylene sulfide (ii) Poly (p-phenylene) sulfide (PPS manufactured by Topren Co., Na content about 2000 ppm) (b) Poly (p-phenylene) sulfide (PPS manufactured by Topren Co., was added to an aqueous acetic acid solution having a pH of 4). Soaking and stirring for 30 minutes reduced the Na content to 120 ppm)

Examples 1 to 10 and Comparative Examples 1 to 18 Olefin-based elastomers, modifying monomers shown in Tables 1 to 3, and radical generators in the amounts shown in the same table were dry blended with a Henschel mixer. , Then in a single-screw extruder with 30 mmφ and L / D = 25, 200
The mixture was melt-kneaded at 30 ° C. at 30 ° C. for graft polymerization. The melt flow rate (MFR) of the modified olefin elastomer thus obtained and the graft ratio of the modifying monomer were measured. The results are shown in Tables 1 to 3.

Next, the above-mentioned modified olefin elastomer and the various PPSs shown in Tables 1 to 3 were mixed in the ratio shown in the same table, and the mixture was mixed with a 20 mmφ twin-screw extruder at 300 ° C.
The resin composition was obtained by kneading at 400 rpm. The DuPont impact strength, Izod impact strength, flexural modulus, flexural strength, tensile yield strength, and tensile elongation at break of the thermoplastic resin composition thus obtained at 23 ° C. were measured based on the following criteria. The results are shown in Tables 1 to 3.

(1) Melt flow rate (MFR): J
Measured according to IS K7210. (Temperature 190 ° C., load 1.05 kg) (2) Grafting ratio of modifying monomer: The modified olefin elastomer is dissolved in boiling xylene, the insoluble matter is removed, and then the dissolved component is precipitated with methanol.
After pressing to a thickness of about 0 μm and measuring the IR spectrum, the peak of stretching of the C═O bond of AXE (1648 cm
⁻¹ ) and one of the peaks (840 cm ⁻¹ ) peculiar to isotactic PP were calculated. (3) DuPont impact test: Measured according to JIS K7211. (4) Izod impact strength: Measured according to JIS K7110. (5) Flexural modulus and flexural strength: JIS K7203
Measured by. (6) Tensile yield strength: Measured according to JIS K7113. (7) Tensile elongation at break: Measured according to JIS K7113.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

As is clear from Tables 1 to 3, a resin composition comprising PPS purified by a conventional method and a modified olefin-based elastomer maintains good mechanical properties originally possessed by PPS resin. In addition, it shows good impact resistance (Comparative Examples 1, 4, 5, 8, 10, 13, 14, 1).
7). However, the resin composition of the present invention comprising the deionized PAS and the modified olefin-based elastomer exhibits remarkably high impact resistance while maintaining the good mechanical properties originally possessed by the PPS resin (Examples 1 to 1). 1
0). On the other hand, a resin composition comprising PPS and an unmodified olefinic elastomer by a conventional method (Comparative Example 3,
7, 12, 16) and a resin composition comprising deionized PPS and an unmodified olefin-based elastomer (Comparative Examples 2, 6, 9, 11, 15) are both impact resistance and tensile rupture. The growth was pretty bad. It is considered that this is because the unmodified olefin elastomer is inferior in compatibility with PPS as compared with the modified olefin elastomer.

A composition comprising PPS and an unmodified olefinic elastomer prepared by a conventional method, and a deionized P
Comparing the composition consisting of PS and the unmodified olefin elastomer, the impact resistance of both is almost the same or the latter is rather inferior. In contrast, it is surprising to compare a conventional composition of PPS and a modified olefinic elastomer with a composition of the invention of deionized PPS and a modified olefinic elastomer. In addition, the latter is far superior in impact resistance.

As described in detail above, the PAS resin composition of the present invention has a significantly improved impact resistance without impairing the properties such as heat resistance and mechanical strength originally possessed by PAS. . The PAS resin composition of the present invention having such characteristics is used as various engineering plastics.
In particular, it is suitable as a forming raw material for automobile parts, home electric appliance parts, industrial material parts, packaging materials and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Ikeda 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. An olefin elastomer having the following general formula (1): (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and m is 1 to 4
A modified olefin elastomer grafted with a glycidyl compound represented by the formula (1) and a polyarylene sulfide resin having an alkali metal content reduced to 900 ppm or less by deionization treatment. Composition.