JPH01182344A - Styrene based polymer resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition, containing a styrene based polymer with a syndiotactic structure, thermoplastic resin and/or rubber and inorganic filler and having excellent heat resistance and further mechanical physical properties, such as tensile modulus of elasticity or tensile strength. CONSTITUTION:A composition containing (A) 1-98wt.%, preferably 5-95wt.% styrene based polymer, obtained by polymerizing a styrene based monomer in the presence of a condensation product of a titanium compound with water and a trialkylaluminum as a catalyst in, e.g., an inert hydrocarbon solvent, and mainly having a syndiotactic structure, (B) 1-98wt.%, preferably 5-95wt.% thermoplastic resin and/or rubber, preferably polystyrene having an atactic structure, rubber-like polymer containing a styrene based compound as one component thereof, etc., and (C) 1-60wt.%, preferably 5-50wt.% inorganic filler, preferably glass fibers, carbon fibers or titanium dioxide.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a styrene polymer resin composition, and more particularly to a styrenic polymer resin composition having excellent heat resistance and mechanical properties. Polymer resin compositions are used in various industrial materials that require heat resistance, including heat-resistant structural materials.

It is widely and effectively used as a material for machine parts.

[Prior art and problems to be solved by the invention] Generally, in order to improve the mechanical properties and thermal properties of crystalline polyolefin, inorganic fillers are added to the blend with other resins. ing.

Among them, thermal properties were improved by blending a styrene polymer with a syndiotactic structure with a high melting point (Japanese Patent Application Laid-open No. 1048111/1982), which was previously developed by the applicant, into a thermoplastic resin. Attempts have been made to improve this (Japanese Unexamined Patent Publication No. 62-257950).

However, in the above-mentioned conventional technology, the mechanical strength did not exceed that of each of the resins to be blended, and was insufficient.

It is an object of the present invention to overcome the above-mentioned conventional drawbacks and to provide a styrene polymer resin composition that has excellent heat resistance, flexibility, and mechanical properties.

[Means for Solving the Problems] That is, the present invention provides (a) 1 to 98% by weight of a styrenic polymer mainly having a syndiotactic structure; (b)
The present invention provides a styrenic polymer resin composition containing 1 to 98% by weight of a thermoplastic resin and/or rubber and (c) 1 to 60% by weight of an inorganic filler.

In the composition of the present invention, a styrenic polymer mainly having a syndiotactic structure is used as component (a).

The mainly syndiotactic structure of this styrenic polymer means that the stereochemical structure is mainly syndiotactic, that is, the main chain formed from carbon-carbon bonds has alternating phenyl groups or substituted phenyl groups as side chains. It has a three-dimensional structure located in the opposite direction, and its toughness can be determined by nuclear magnetic resonance method using carbon isotope ("C-NM").
R method). Toughness measured by the C-NMR method is expressed by the proportion of consecutive constituent units, e.g. 2 in the case of diats, 3 in the case of triats, and 5 in the case of pentads. However, the styrenic polymer mainly having a syndiotactic structure as used in the present invention usually has a diad content of 75% or more, preferably 85% or more, or a pentad (racemic pentad) content of 30% or more, preferably Polystyrene, poly(alkyl styrene), poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoic acid ester) and mixtures thereof, or mixtures thereof, having a syndiotacticity of 50% or more, or containing these as the main component. Here, poly(alkylstyrene) includes poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), etc. Examples of (halogenated styrene) include poly(chlorostyrene), poly(bromostyrene), poly(
fluorostyrene), etc. Furthermore, examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(
p-chlorostyrene), poly(m-chlorostyrene),
Poly(p-fluorostyrene), and even styrene and P-
Examples include copolymers with methylstyrene.

The styrenic polymer used in the present invention is not limited in molecular weight, but preferably has a weight average molecular weight of 10,000 or more, most preferably 50,000 or more. Here, when the weight average molecular weight is 10 and the ungrooved one has insufficient heat resistance and mechanical strength of 9, no sufficient improvement is observed even after blending. Furthermore, there are no restrictions on the molecular weight distribution, and various types of styrenic polymers can be used. It has much better heat resistance than polymers.

Such styrenic polymers having a mainly syndiotactic structure can be produced by using a titanium compound and a condensation product of water and trialkylaluminum as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene polymers) (Japanese Patent Application Laid-Open No. 1983-1999).
187708).

The above component (a) is present in the composition in an amount of 1 to 98% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight.
It is contained in a proportion of . If the content of component (a) is less than 1% by weight, no improvement in heat resistance is observed. On the other hand, if it exceeds 98% by weight, there is no significant difference in the properties of the polymer itself, and there is no point in blending this styrenic polymer having a syndiotactic structure as a modifier.

Next, in the composition of the present invention, a thermoplastic resin and/or rubber other than the above-mentioned styrenic polymer mainly having a syndiotactic structure is used as component (b).

Various thermoplastic resins can be selected depending on the intended use of the composition, and there are no particular limitations. For example, polystyrene with atactic structure, polystyrene with isotactic structure, and AS resin.

In addition to styrene polymers such as ABS resin, polyesters such as polyethylene terephthalate, polycarbonate, polyphenylene oxide, condensation polymers such as polyester, acrylic polymers such as polyacrylic acid, polyacrylic acid ester, polymethyl methacrylate, and polyethylene. , polypropylene, polybutene, polyolefins such as poly4-methylpentene-1° ethylene-propylene copolymer, and halogen-containing vinyl compound polymers such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride.

Among these, polystyrene with an atactic structure, specifically, those having a weight average molecular weight of 50,000 to 500. Goo,
General-purpose polystyrene with a density of 1.04 to 1.065 g/cm': ABS resin; polyester, specifically, an intrinsic viscosity [η] of 0.4 to 1.5 dj/g, preferably 0.5 to
1.4dj/g, density 1.3:4-1.40g/cm
', polyethylene terephthalate with a melting point of 255 to 260°C; polycarbonate, specifically viscosity average molecular weight 2
0,000-40,000. Density 1.19-122g/
ca+' polycarbonate: polyether, specifically weight average molecular weight 5,000 N10,000° density 1
．． 05 to 1.07 g/ls'' of polyphenylene oxide is suitable.

On the other hand, various rubbers can be used, but the most suitable one is a rubbery copolymer containing a styrene compound as one of its components.For example, the butadiene moiety of a styrene-butadiene block copolymer is partially or fully hydrogenated rubber (SEBS), styrene-butadiene copolymer rubber (SBR), methyl acrylate-butadiene-styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber (ABS rubber), Acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber (AABS), methyl methacrylate-alkyl acrylate-styrene copolymer rubber (
MAS), methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber (MABS), and the like. Rubber-like copolymers containing these styrene compounds as one of their components have styrene units, so they have good dispersibility in component (a), a styrenic polymer that mainly has a syndiotactic structure. , the effect of improving physical properties is remarkable. Other examples of rubbers that can be used include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber, polysulfide rubber, thiol rubber, acrylic rubber, urethane rubber,
Examples include silicone rubber, epichlorohydrin rubber, polyether/ester rubber, and polyester/ester rubber.

The above component (b) is present in the composition in an amount of 1 to 98% by weight, preferably 5 to 95% by weight, more preferably 20 to 80% by weight.
It is contained in a proportion of . Here, when the content of the four components (b) is less than 1% by weight, there is no significant difference in properties from the styrenic polymer having a syndiotactic structure alone. On the other hand, if it exceeds 98% by weight, no improvement in mechanical or thermal properties can be expected due to the styrenic polymer having a syndiotactic structure.

Furthermore, in the composition of the present invention, an inorganic filler is used as component (C). The inorganic filler may be fibrous, granular, or powdery. Examples of the fibrous inorganic filler include glass fiber, carbon fiber, and alumina fiber, with glass fiber and carbon fiber being particularly preferred. Here, the shape of the glass fibers includes cross-like, mat-like, focused-cut shape, short fiber, and filament-like shapes, but it is preferably focused-cut shape, and has a length of 0.05+a.
m~13mm% fiber diameter is 5~15μ-,
In particular, carbon fibers treated with silane are preferred, and carbon fibers based on polyacrylonitrile (PAN') are preferred, and chopped fiber types are more preferred, with a length of about 31 mm and a diameter of 7 mm. ~15μm
On the other hand, talc and carbon black can be used as granular or powdery inorganic fillers.

Graphite, titanium dioxide, silica, mica.

Examples include calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, etc., and titanium dioxide is particularly preferred. Here, the crystal form of titanium dioxide includes rutile type, brutzite type, and anatase type, but rutile type and anatase type are preferable, and the average particle size is 0.15.
~0.40μ layer, and further contains Zn, Aj,
It may also be one treated with Si or the like.

The above-mentioned component (C) is present in the composition in an amount of 1 to 80% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight.
It is contained in a proportion of . If the content of component (C) is less than 1% by weight, sufficient effect as a filler will not be recognized, while if it exceeds 60% by weight, it will not be able to be uniformly dispersed and the mechanical strength will be poor. becomes.

The composition of the invention is basically as described above (a).

It consists of components (b) and (C), and various additives such as nucleating agents, antioxidants, plasticizers, compatibilizers, lubricants, colorants, antistatic agents, etc. are added as necessary. In particular, it is desirable to add a nucleating agent, an antioxidant, and a plasticizer. Talc is preferably used as the nucleating agent here, and is added in an amount of 0.1 parts by weight per 100 parts by weight of the composition of the present invention.
It is blended in a proportion of ~10 parts by weight.

Although there are various antioxidants, phosphorus antioxidants and phenolic antioxidants are particularly preferred.

The composition of the present invention may be uniformly prepared by kneading the above-mentioned components using a kneader, mixing roll, extruder, etc., or by solution blending, etc.

[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto as long as the scope of the present invention is not exceeded.

Reference Example 1 (Production of polystyrene mainly having a syndiotactic structure) 2 ft of toluene as a solvent, 1 mmol of cyclopentadienyl titanium trichloride as a catalyst component, and 0.8 mol of methylaluminoxane as an aluminum atom were added to a reaction vessel. , Styrene 3 at 20°C
．． After the completion of the 0 reaction in which 8j2 was added and the polymerization reaction was carried out for 1 hour, the product was washed with a hydrochloric acid-methanol mixture to decompose and remove the catalyst component. It was then dried to obtain 330 g of a polymer. Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 95% by weight. This polymer had a weight average molecular weight of 290,000, a number average molecular weight of tsa, ooo, and a melting point of 270°C. In addition, this polymer can be used for isotopic carbon nuclear magnetic resonance ("
Analysis by C-NMR) showed absorption at 145.35 pp.2 due to the syndiotactic structure, and the syndiotacticity in pentad calculated from the peak area was 96%.

Example 1 35 parts by weight of polystyrene having a syndiotactic structure obtained in Reference Example 1 above, polycarbonate (trade name: Idemitsu Polycarbonate A) as a thermoplastic resin
3000. Viscosity average molecular weight 28,500-30,500
．． Density 1.20g/c+*3. Idemitsu Petrochemical Trout) 35
Parts by weight are glass fibers with an average fiber length of 3mm (9wA manufactured by Asahi Fiberglass), fiber diameter 10-15μm.

30 parts by weight of chopped strands) were triblended, 1 part by weight of talc (trade name: Talc-FFR, manufactured by Asada Seifun ■) was added as a crystal nucleating agent, mixed in a Henschel mixer, and then extruded using an extruder. The pellets were kneaded, extruded, and pelletized. Then, test pieces were formed from the pellets and the mechanical strength and heat distortion temperature were measured. The results are shown in Table 1.

Example 2 In Example 1, instead of polycarbonate, 255°C,
A test piece was obtained by carrying out the same operation as in Example 1, except that a material having a density of 1.34 g/cm' (manufactured by Mitsubishi Rayon Co., Ltd.) was used. The test results are shown in Table 1.

Example 3 The same procedure was carried out except that 45 parts by weight of polystyrene having a syndiotactic structure obtained in Reference Example 1, 45 parts by weight of polyethylene terephthalate (same as that used in Example 2), and 10 parts by weight of glass fiber were blended. A test piece was obtained by performing the same operation as in Example 2. The test results are shown in Table 1.
Example 4 In Example 1, atactic polystyrene (trade name: Idemitsu Steel 11530) was used instead of polycarbonate.
0. Weight average molecular weight 370. Goo, Melt Index 2. Density 1.05g/c+a', Idemitsu Petrochemical ■
A test piece was obtained in the same manner as in Example 1, except that the same method was used as in Example 1.

The results are shown in Table 1.

Example 5 In Example 1, polyphenylene oxide (Catalog No.) was used instead of polycarbonate.

V-100, weight average molecular weight 7,200, density 1.0
6g/cm".

5CIENTIFIC POLYMER PRODUCTS
A test piece was obtained in the same manner as in Example 1, except that a test piece (manufactured by INC.) was used. The results are shown in Table 1.

Example 6 A test piece was obtained in the same manner as in Example 1, except that ABS resin (trade name: JSRABS 15. manufactured by Japan Synthetic Rubber ■) was used instead of polycarbonate.

The results are shown in Table 1.

Example 1 The procedure was the same as in Example 1, except that methyl methacrylate-n-butyl acrylate-styrene copolymer (manufactured by Rohm & Haas, trade name: M330) was used instead of polycarbonate. A test piece was obtained. The results are shown in Table 1.

Example 8 45 parts by weight of the syndiotactic polystyrene obtained in Reference Example 1 above, 45 parts by weight of atactic polystyrene (same as that used in Example 4) as the thermoplastic resin
Weight part and carbon fiber (product name: trading card,
PAN type chopped fiber, made by Toshi ■, average length 3
A test piece was obtained in the same manner as in Example 1, except that 10 parts by weight (am, diameter 7 to 10 μm) was blended. The results are shown in Table 1.

Example 9 In Example 8, titanium dioxide (trade name: Titania 16809 manufactured by Ishihara Sangyo ■) 1 was used instead of carbon fiber.
A test piece was obtained in the same manner as in Example 8 except that 0 parts by weight was added. The results are shown in Table 1.

-□Example 10 35 parts by weight of polystyrene having a syndiotactic structure obtained in Reference Example 1 above, 20 parts by weight of the same atactic polystyrene used in Example 4 as thermoplastic resin, Example 7 as rubber Example 1 except that 15 parts by weight of the same methyl methacrylate-n-butyl acrylate-styrene copolymer used in Example 1 and 30 parts by weight of the same glass fiber as used in Example 1 were used. I did the same thing. The results are shown in Table 1.

Comparative Example 1 In Example 1, polystyrene 5 having a syndiotactic structure obtained in Reference Example 1 without adding glass fiber was used.
A test piece was obtained in the same manner as in Example 1, except that 0 parts by weight and 50 parts by weight of polycarbonate (the same as used in Example 1) were used. The results are shown in Table 1.

Comparative Example 2 In Comparative Example 1, polyethylene terephthalate (used in Example 2) was used instead of polycarbonate to obtain a test piece. The results are shown in Table 1.

Comparative Example 3 A test piece was obtained in the same manner as in Comparative Example 1, except that 50 parts by weight of atactic polystyrene (same as that used in Example 4) was used instead of polycarbonate.

The results are shown in Table 1.

Comparative Example 4 A test piece was obtained in the same manner as in Comparative Example 1, except that 50 parts by weight of polyphenylene oxide (the same as that used in Example 5) was used instead of polycarbonate.

The results are shown in Table 1.

Comparative Example 5 A test piece was obtained in the same manner as in Comparative Example 1, except that 50 parts by weight of ABS resin (the same as that used in Example 6) was used instead of polycarbonate. The results are shown in Table 1.

Comparative Example 6 Same as Comparative Example 1 except that 50 parts by weight of methyl methacrylate-n-butyl acrylate-styrene copolymer (same as that used in Example 7) was used instead of polycarbonate. A test piece was obtained in the same manner. The results are shown in Table 1.

Comparative Example: 15 parts by weight of polystyrene having a syndiotactic structure obtained in Example 1, 15 parts by weight of atactic polystyrene used in Example 4 as a thermoplastic resin, and 70 parts by weight of glass fiber used in Example 1. Although an attempt was made to obtain a test piece in the same manner as in Example 1 except for using the following materials, it was not uniformly dispersed and no test piece was obtained.

Re-SPS; syndiotactic polystyrene PC:
Polycarbonate PUT, polyethylene terephthalate aPs; atactic polystyrene ppo, polyphenylene oxide ABS; acrylonitrile'-butadiene-styrene copolymer MAS; methyl methacrylate-n-butyl acrylate-styrene copolymer GF; glass fiber CF, carbon fiber umbrella 2 7MA (THERMAL MECHANICA
L ANALYSIS).

[Effects of the Invention] The styrenic polymer composition of the present invention has excellent heat resistance. Moreover, it has excellent mechanical properties such as tensile modulus and tensile strength.

Therefore, the styrenic polymer composition of the present invention can be effectively used as a heat-resistant structural material.

Claims (1)

[Claims] (1) (a) 1-98% by weight of a styrenic polymer mainly having a syndiotactic structure, (b) 1-98% by weight of a thermoplastic resin and/or rubber, and (c) 1-60% by weight of an inorganic filler. A styrenic polymer resin composition comprising: