JPH04159364A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To improve impact characteristics and toughness by compounding a specific polyphenylene sulfide with an olefinic copolymer consisting of an alpha-olefin and a glycidyl ester of an alpha,beta-unsatd. acid. CONSTITUTION:An alkali metal sulfide, a dihalobenzene, and a hydroxylated arom. halogen compd. are allowed to react in an org. amide solvent at 200-300 deg.C for 0.5-30hr, and if necessary, thermally treated to give a polyphenylene sulfide having a melt viscosity of 200P or higher and a hydroxyl group content of 0.1-5mol% based on phenylene sulfide units. Separately, an alpha-olefin is copolymerized with 1-30wt.% glycidyl ester of an alpha,beta-unsatd. acid to give an olefinic copolymer. 60-99.5wt.% the polyphenylene sulfide is compounded with 40-0.5wt.% the copolymer.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention consists of an olefinic copolymer consisting of a specific polyphenylene sulfide containing a hydroxyl group and a-olefin/glycidyl ester of an α,β-unsaturated acid. The present invention relates to a resin composition that is characterized by the following, and particularly to a resin composition that exhibits excellent properties in heat resistance, solvent resistance, and toughness.

[Prior art and problems to be solved by the invention] Polyphenylene sulfide is known as a high-performance resin that exhibits excellent properties such as heat resistance, flame retardance, chemical resistance, moldability, and electrical properties. It is widely used in applications such as electrical/electronic parts and automobile parts.

By blending polyphenylene sulfide with fibrous reinforcing materials such as glass fiber and carbon fiber, and inorganic fillers such as talc, clay, and mica, performance such as strength, rigidity, heat resistance, toughness, and dimensional stability can be greatly improved. be able to. However, polyphenylene sulfide has serious drawbacks such as poor ductility and brittleness compared to engineering plastics such as nylon, polycarbonate, polybutylene terephthalate, and polyacetal. Therefore, its application to many uses is restricted.

Conventionally, blending a flexible polymer with polyphenylene sulfide has been a common technique for improving the toughness and impact resistance properties of polyphenylene sulfide. For example, a method of mixing polyphenylene sulfide with an olefin copolymer of α-olefin/α, β-unsaturated acid (Japanese Patent Application Laid-Open No. 2-1231
60, etc.) and a method of mixing an olefin copolymer consisting of α-olefin/glycidyl ester of α, β-unsaturated acid (JP-A-58-154757, JP-A-59-152953, etc.) ) are disclosed. However, the molecular chains of ordinary polyphenylene sulfide have poor reactivity, so even if a highly reactive olefin copolymer containing epoxy groups is added, the adhesion at the interface with polyphenylene sulfide is insufficient. However, there is a problem in that a sufficient effect of improving impact properties is not obtained, and the heat resistance and solvent resistance of the obtained blend material are reduced.

On the other hand, compositions using polyphenylene sulfide treated with various methods to improve the adhesion of the interface between polyphenylene sulfide and a flexible polymer have been disclosed. For example, graph unsaturated carboxylic acid or its anhydride on polyphenylene sulfide that has been acid-treated and washed!・Copolymerized α-olefin copolymer (JP-A-62-169854, etc.) and α-olefin/α
.

A composition containing an olefin copolymer consisting of glycidyl ester of β-unsaturated acid (JP-A-62-1
53343, etc.), and compositions in which a thermoplastic elastomer is blended with amino group-containing and/or amide group-containing polyphenylene sulfide (Japanese Patent Laid-Open No. 61-207462, etc.) have been disclosed. However, even in these compositions, the effect of improving impact properties is insufficient.

Therefore, the present inventor conducted extensive studies with the aim of improving the adhesion at the interface between polyphenylene sulfide and an olefin copolymer, and obtaining a resin composition that has a remarkable effect of improving impact properties and toughness. By blending a specific olefin copolymer with polyphenylene sulfide resin, it was possible to improve the adhesion at the interface, and the present invention was completed based on the discovery that a blend material that solved the problems of the above-mentioned conventional technology could be provided. I ended up doing it.

[Means for Solving the Problems] The present invention provides (a) polyphenylene sulfide 60 to 99.5% having a melt viscosity of 200 voids or more and containing 0.1 to 5 mol% of hydroxyl groups (per phenyl sulfide unit).
5% by weight and (b) 40 to 0.5% by weight of an olefin copolymer consisting of α-olefin/glycidyl ester of α,β-unsaturated acid. .

The content of hydroxyl groups in the hydroxyl group-containing polyphenylene sulfide used in the present invention is preferably 0.1 to 5 mol% (per phenyl sulfide unit).

Particularly preferred is 0.5 to 3 mol%. When the hydroxyl group content of polyphenylene sulfide is less than 0.1 mol%,
The desired improvement effect is not observed, and if it exceeds 5 mol %, a decrease in mechanical strength is observed, which is not preferable.

Furthermore, the hydroxyl group-containing polyphenylene sulfide used in the present invention has ÷-(D-8÷7) as its structural unit.
Those containing 0 mol% or more, especially 90 mol% or more are preferable. In addition, if the structural unit is less than 30 mol%, preferably less than 10 mol%, m-phenylene sulfide unit m-[]-”'T, o-phenylene sulfide unit phytoketone unit →-(D←s 4 c o+
, diphenylene sulfide unit key X giant Σ-()-5+
, phenylene sulfide ether units, 1,000-<El)-S + O, and the like may be contained.

The hydroxyl group-containing polyphenylene sulfide used in the present invention can be produced by, for example, JP-A-64-4
It can be produced according to Japanese Patent No. 8828, that is, by a method of polymerizing an alkali metal sulfide and dino-10 benzene in an organic amide solvent in the presence of a hydroxyl group-containing aromatic halide.

Alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof, which may also be used in the form of hydrates.

These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base, and may be prepared in situ or outside the system prior to adding dichlorunzene into the polymerization system. It is okay to use something like this.

Hydroxyl group-containing aromatic compounds include 2,3-dichlorophenol, 2,4-dichlorophenol, 2,5
-dichlorophenol, 2,6-dichlorophenol,
3,4-dichlorophenol, 3.5-dichlorophenol, 2,4-dibromophenol, 2,3.5-1-dichlorophenol, 2.3.6-trichlorophenol, 2,4.5-trichlorphenol Phenol, 2,4.6-trichlorophenol, 3,4.5-trichlorophenol, 2,4.6-tribromophenol, 1,3-dihydroxy-4,6-dichlorobenzene, 2゜4-dichloro- Examples include 1-naphthol, 2,4-dichloro-6-methylphenol, and mixtures thereof.

The amounts of the alkali metal sulfide and hydroxyl group-containing aromatic halide to be charged are (alkali metal sulfide):(hydroxyl group-containing aromatic halide) -1°00:0.10 to 3.
A range of 0.0 is preferred.

Examples of dihalobenzene include p-dichlorobenzene, p-dibromobenzene, p-shortbenzene, m-dichlorobenzene, m-dibromobenzene, m-shortbenzene, and 1-chloro-4-bromobenzene. The amounts of the alkali metal sulfide and dihalobenzene to be charged are preferably in a molar ratio of (alkali metal sulfide)=(dihalobenzene)-1, oo:o, in the range of 90 to 1.10.

As the polymerization solvent, polar solvents are preferred, and particularly preferred are aprotic organic amides that are stable at high temperatures and against alkalis. Some examples of organic amides include N,
N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-
Examples include caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea, and mixtures thereof.

The amount of organic amide used as a solvent is 3 to 60% by weight, preferably 7 to 60% by weight of the polymer produced by polymerization.
It can be used within a range of 40% by weight. Polymerization is carried out at 200-300°C, preferably 220-280°C.
．． It is carried out under stirring for 5 to 30 hours, preferably 1 to 15 hours.

Further, the polymer obtained by the above method can be cured by heat treatment in an oxygen atmosphere or by heat treatment with addition of peroxide or the like to increase the degree of polymerization. This curing is carried out, for example, by treatment in an air atmosphere at a temperature range of 200 to 280°C for 1 to 12 hours.

In particular, in order to obtain a composition with excellent impact properties and toughness, a hydroxyl group-containing borephenylene sulfide polymer is cured in a non-oxidizing inert gas at a temperature ranging from about 200°C to about 280°C for 1 to 24 hours. It is preferable to do so.

Non-oxidizing inert gases that can be used in the present invention include helium, argon, nitrogen, carbon dioxide, water vapor, etc., or mixtures thereof, with nitrogen being preferred from an economic standpoint.

The hydroxyl group-containing polyphenylene sulfide used in the present invention needs to have a melt viscosity of 200 voids or more, particularly preferably 400 voids or more before curing,
The melt viscosity after heat curing is preferably 800 to 30,000 poise.

Particularly preferably, the melt viscosity after heat curing is 1000 to 20
000 Boise. If the melt viscosity before heat curing is less than 200 poise or the melt viscosity after heat curing is less than 800 poise, a polyphenylene sulfide composite acid with excellent toughness cannot be obtained, probably because the molecular weight is too low. Furthermore, if the melt viscosity after heating and curing exceeds 30,000 voids, the viscosity is too high and molding may not be possible. The melt viscosity of the hydroxyl group-containing polyphenylene sulfide was measured using a Koka type flow tester (dice; diameter 0.5 mm, length 2 mm).
The test was carried out at 300° C. and under a load of 10 kg.

The specific olefin copolymer used in the present invention is α
- It is a copolymer consisting of an olefin and a glycidyl ester of an α,β-unsaturated acid. Examples of the α-olefin here include ethylene, propylene, and butene-1, but ethylene is preferably used. Also α, β−
Glycidyl esters of unsaturated acids are compounds represented by the general formula (R represents a hydrogen atom or a lower alkyl group), and specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. , Glycidyl methacrylate is long 19
Preferred and often used. The content of glycidyl ester of α, β-unsaturated acid in the olefin copolymer is 1 to
30 weight 9o, especially 3 to 20 weight % is preferable (4,<,1
If it is less than 1.30% by weight, the desired improvement effect cannot be obtained.
If it exceeds 8% by weight, a gel will be formed during melt mixing with polyphenylene sulfide, resulting in decreased extrusion stability and molding processability, which is not preferable. Furthermore, the olefin copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ethers, vinyl acetate, vinyl propionate, etc., in an amount of 40 mol% or less and within a range that does not impede the purpose of the present invention. One or more types of vinyl esters, esters of acrylic acid and methacrylic acid such as methyl, ethyl, and propyl, acrylonitrile, and esters may be copolymerized.

The blending ratio of the constituent components of the resin composition of the present invention is 60 to 99.5M of the hydroxyl group-containing polyphenylene 1 nonsulfide resin.
% by weight, preferably 80-97% by weight and 40-0.5% by weight, preferably 20% by weight of an A-refine copolymer consisting of α-olefin/glycidyl ester of α,β-unsaturated acid.
~3% by weight.

If the amount of the olefin copolymer is less than 0.5% by weight, the desired improvement effect cannot be obtained, and if it exceeds 40% by weight, not only will the excellent heat resistance and solvent resistance of the polyphenylene sulfide itself deteriorate, This is not preferable because gel is formed during melt mixing, resulting in decreased extrusion stability and molding processability.

The resin composition of the present invention can be produced by various known methods. The resin used as a raw material is either mixed in a dry powder state in a mixer such as a tumbler, Henschel mixer, ball mill, or ribbon blender, or is further hardened by heat treatment. A resin composition is produced by mixing the dry powder or pellets thus prepared in a blender or the like, and then melt-mixing them. Alternatively, the raw material resins may be separately supplied to a melt mixer and melt-mixed to produce a resin composition. Melt mixing is performed using a kneader, Panbury mixer, pusher, etc.
A method such as melt-kneading at a temperature of ~350°C is used. There are no particular restrictions on the melt-mixing method, but in consideration of operability, it is preferable to use an extruder.

In addition, conventionally known fibrous and inorganic powder fillers, such as glass fibers, bicomponent fibers, silica fibers, alumina fibers, carbonized Fillers such as silicon fiber, zirconia fiber, calcium titanate fiber, wollastonite, calcium sulfate fiber, aramid fiber, wholly aromatic polyester fiber, calcium carbonate, magnesium carbonate, talc,
Fillers such as mica, clay, silica, alumina, kaolin, zeolite, gypsum, calcium silicate, magnesium silicate, calcium sulfate, titanium oxide, magnesium oxide, carbon black, graphite, iron oxide, zinc oxide, copper oxide, and Inorganic fillers such as glass beads, glass powder, glass balloons, quartz, and quartz glass can also be blended. Further, two or more of these fillers can be used in combination, and if necessary, they can be pretreated with a coupling agent such as a silane type or a titanium type before use.

Furthermore, the resin composition of the present invention may be used with conventionally known mold release agents, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, crystal nucleating agents, foaming agents, rust preventive agents, etc., to the extent that the objects of the present invention are not impaired. One or more of additives such as additives, ion trapping agents, flame retardants, flame retardant aids, colorants such as dyes and pigments, antistatic agents, waxes, and small amounts of other types of polymers may be used in combination.

The additive may be added by any method. For example, it can be added to individual resins before or during the formation of the composition, or it can be added after the composition is formed or even when the composition is melted.

[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited only to these Examples.

Reference Example 1 (Synthesis of hydroxyl group-containing polyphenylene sulfide) Internal volume 530 equipped with stirrer, dehydration tower and jacket
N-methyl-2-pyrrolidone (hereinafter NMP
) 1101 and sodium sulfide (purity: Na28
60.2% by weight) 61゜1kg was charged and heated with a jacket while stirring until the internal temperature reached approximately 200℃.
Dehydration was performed through a dehydration tower. At this time, a distillate of 13.51+ mainly consisting of water was distilled off. Next, 68.0 kg of p-dichlorobenzene (hereinafter abbreviated as p-DCB)
and 0.76 kg of 2,4-dichlorophenol (p-DC
(approximately 1 mol% addition to B) was added together with NMP48I, and the temperature was raised to 225°C over 2 hours.
After reacting for an hour, the temperature was raised to 250°C over 30 minutes, and the reaction was further continued at 250°C for 3 hours. At this time, the pressure is 10
．． It rose to 2 kg/cm2.

After the reaction was completed, the reaction mixture was transferred to a solvent recovery vessel equipped with a stirrer, a jacket, and a vacuum line.

At this time, NMP was added (301). Subsequently, the mixture was heated under reduced pressure to distill off 2 Ill of a distillate mainly consisting of NMP. Subsequently, water 200II was added and the mixture was heated and stirred with the water slurry at 80° C. for 15 minutes, followed by centrifugation to recover the polymer. When unreacted 2,4-dichlorophenol remaining in the filtrate was measured by gas chromatography (GC-12A manufactured by Shimadzu Corporation), the conversion rate of 2,4-dichlorophenol was 89%.

Furthermore, the polymer was returned to the solvent recovery vessel, 200 I of water was added, heated and stirred at 100°C for 30 minutes, and after cooling, the polymer powder was recovered using a centrifuge. Note that this operation was repeated twice.

The obtained polymer was transferred to a jacketed ribbon blender and dried. The hydroxyl group-containing polyphenylene sulfide thus obtained is designated as PP5-I. Melt viscosity of the obtained PP5-I (diameter 0.5 mm at 300°C,
The value measured with a Koka type flow tester using a die with a length of 2 mm and a load of 10 kg was 680 voids.

This PP5-I was transferred to a jacketed ribbon blender and cured in air at 235°C for 2 hours to achieve a melt viscosity of 800°C.
A polymer with zero voids was obtained. The hydroxyl group-containing polyphenylene sulfide thus obtained is referred to as pps-n.

Reference Example 2 (Curing with non-oxidizing inert gas) PPS-
Transfer 1 to a jacketed ribbon blender and blend with 4004! The temperature was raised to 230° C. and curing was performed for 10 hours while flowing nitrogen at a flow rate of /hr. The melt viscosity after curing was 1800 voids. The hydroxyl group-containing polyphenylene sulfide thus obtained is referred to as pps-m.

Reference Example 3 Synthesis of hydroxyl group-containing polyphenylene sulfide using p-DC
B64.6kg, 2.4-dichlorophenol 4.57
kg (approximately 6 mol % added to p-DCH), but the same operation as in Reference Example 1 was performed. The viscosity of the obtained polymer was 380 voids. When unreacted 2,4-dichlorophenol remaining in the filtrate was measured by gas chromatography, the conversion rate of 2,4-dichlorophenol was 89%. This polymer was transferred to a jacketed ribbon blender and cured in air at 235° C. for 2 hours to obtain a polymer with a melt viscosity of 8000 voids. The hydroxyl group-containing polyphenylene sulfide thus obtained is treated with P P 5-IV.

Reference Example 4 (Synthesis of polyphenylene sulfide) Polyphenylene sulfide was synthesized in the same manner as in Reference Example 1 except that the hydroxyl group-containing aromatic halide was not added.

The viscosity of the obtained polymer was 610 voids. This polymer was transferred to a jacketed ribbon blender and cured in air at 235° C. for 2 hours to obtain a polymer with a melt viscosity of 8000 poise. The polymer thus obtained is referred to as pps-v.

Example 1.2 pps-n or PP5-I [190% by weight and ethylene/
Glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical,
10 wt.

A test piece was prepared by injection molding the obtained pellet at 290°C, and the test piece was tested for Izod impact strength (ASTM D~2).
Measured in accordance with 56, notched), tensile elongation (AST
Measured according to M D-638, tensile speed 5 mm/m1n), heat distortion temperature (ASTM D-648
The load was 18.6 kg/cm2). In addition, the change in weight was measured after a 1/8 inch thick test piece for heat distortion temperature section J was immersed in gasohol at 125°C (gasoline/methanol weight ratio 80/20) for 8 hours. This was evaluated for solvent resistance. The results are shown in Table 1. As shown in Table 1, the composition of the present invention has the same heat deformation temperature and solvent resistance as a composition without the olefin copolymer, and also has extremely high tensile elongation and impact strength.

Comparative Example 1.2 pps-■ or p instead of pps-n or PP5-m
The same operation as in Example 1 was performed except that ps-v was used. The results are shown in Table 1.

Examples 3 to 5, Comparative Examples 3 to 5 pps-m, ethylene/glycidyl methacrylate copolymer, and glass fiber were kneaded in the composition shown in Table 1, and the same operations as in Example 1 were performed. The results are shown in Table 1.

[Effects of the Invention] As described above, the resin composition of the present invention is a polymeric material that has the excellent solvent resistance and heat resistance of polyphenylene sulfide, and also has excellent mechanical strength. It is useful for automobiles, electrical/electronic applications, etc.

Claims (1)

[Claims] (1) (a) 60 to 99.5% by weight of polyphenylene sulfide having a melt viscosity of 200 poise or more and containing 0.1 to 5 mol% of hydroxyl groups (per phenyl sulfide unit); and (b) α-olefin/ Olefin copolymer 40 consisting of glycidyl ester of α,β-unsaturated acid
-0.5% by weight of a polyphenylene sulfide resin composition.