JPH10237242A - Styrene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition useful as a material for a composite material or a heat-resistant elastomer being excellent in heat resistance, chemical resistance, etc., and having good toughness by mixing a syndiotactic styrene polymer with a styrene-derivative-terminated modified olefin polymer in a specified mixing ratio. SOLUTION: Highly syndiotactic styrene polymer of 99.9-0.1wt.% is mixed with 0.1-99.9wt.% styrene-derivative-terminated modified olefin polymer represented by formula (wherein R is H or a 1-20C alkyl, X is H, a halogen or a substituent containing at least one of C, tin and silicon; (n) is 1-4; (m) is 0 or a natural number; and Z is a bonding part derived from an olefinic monomer). The highly syndiotactic styrene polymer is a styrene polymer having a syndiotacticity corresponding to a racemic diad of 75% or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic resin composition, and more particularly, it has excellent heat resistance, chemical resistance and the like, has good toughness, and is used as a material for composite materials and a heat-resistant elastomer. The present invention relates to a styrene-based resin composition which is extremely useful in the fields of electrical equipment, electronic equipment and the like.

[0002]

2. Description of the Related Art The research group of the present inventors has previously succeeded in developing a styrenic polymer having a high syndiotacticity and further obtained a syndiotactic polymer obtained by copolymerizing this styrenic monomer with other components. Styrene-based copolymers have been developed (JP-A-62-104818, JP-A-63-104818).
2410009).

[0003] However, these styrenic polymers or copolymers having a syndiotactic structure are resins having a high glass transition point, so that they are excellent in heat resistance, chemical resistance and the like, but have insufficient toughness. Disadvantageously, it is brittle at room temperature. Was. In order to improve such toughness, a rubber component such as a hydrogenated styrene-butadiene-styrene block copolymer (SEBS) is blended, but the rubber component itself is expensive and a process of kneading the rubber component is required. There is a problem that it is indispensable and disadvantageous in the process, and a problem that the addition of an amorphous component inevitably lowers the original good characteristics (heat resistance and crystallization speed) of SPS. There has been a demand for the development of a technique that can sufficiently satisfy the requirements of the resin, toughness, and compatibility with other resins.

[0004]

Under such circumstances, the present invention has excellent heat resistance, chemical resistance, etc., and has good toughness.
An object of the present invention is to provide a styrene resin composition comprising a syndiotactic polystyrene and an olefin polymer modified with a terminal styrene derivative, which is extremely useful in the fields of home appliances, electric devices, and electronic devices.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the repeating units of a styrene-based polymer having a high degree of syndiotactic structure and an olefin-based monomer have a terminal. A styrene-based resin composition comprising a terminal styrene derivative-modified olefin polymer modified with a styrene derivative has excellent heat resistance, chemical resistance, etc. and good toughness, elongation and compatibility. Was found to have. The present invention has been completed based on such findings.

That is, the present invention relates to a styrenic polymer having a high syndiotactic structure (hereinafter, sometimes referred to as SPS) (A) (99.9 to 0.1% by weight) and the following general formula (1) The present invention provides a styrene resin composition comprising 0.1 to 99.9% by weight of an olefin polymer modified with a terminal styrene derivative (B).

[0007]

Embedded image

[Wherein, R is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
Wherein each R may be the same or different. X represents any of the following: Hydrogen atom,
A substituent containing at least one selected from a halogen atom, a carbon atom, a tin atom and a silicon atom;
n represents an integer of 1 to 4, and when n is 2 or more, each X
May be the same or different. Further, m is 0 or a natural number, and Z represents a chain portion derived from an olefin-based monomer. ]

[0009]

Embodiments of the present invention will be described below. 1. Styrene polymer having a high syndiotactic structure (SPS) (A) The tacticity of a styrene polymer having a syndiotactic structure (SPS) is determined by a nuclear magnetic resonance method using isotope carbon ( ¹³ C-NMR method).
The styrenic polymer having a syndiotactic structure is usually determined by a racemic diad
A styrene polymer having a syndiotacticity of 5% or more, preferably 85% or more, or 30% or more, preferably 50% or more in racemic pentad. The monomer used for the polymerization is a compound represented by the general formula (2).

[0010]

Embedded image

Wherein X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; n shows the integer of 1-5. When n is 2 or more, each X may be the same or different. ]
The compound represented by is used. Specifically, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene
Alkyl styrene such as dimethyl styrene, p-ethyl styrene, m-ethyl styrene, p-tert-butyl styrene; vinyl benzene such as p-divinyl benzene, m-divinyl benzene, tridivinyl benzene; p-chloro styrene, m-chloro Halogenated styrenes such as styrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene , Methoxystyrene, ethoxystyrene, t-butoxystyrene, and other alkoxystyrenes, vinyl biphenyls, vinyl phenyl naphthalenes, vinyl phenyl anthracenes, halogenated vinyl biphenyls, trialkylsilyl vinyl biphenyls, halo Down-substituted alkyl styrene, alkyl silyl styrenes, phenyl group-containing silyl styrenes,
Examples include halogen-containing silyl styrenes, silyl group-containing silyl styrenes, or a mixture of two or more thereof. A styrene-based polymer is a homopolymer obtained by homopolymerization of the monomer, a copolymer obtained by copolymerization of two or more monomers, a hydrogenated polymer thereof, a mixture thereof, or a copolymer containing these as a main component. Refers to coalescence. Particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), and poly (m-styrene).
-Chlorostyrene), poly (p-fluorostyrene),
Examples include hydrogenated polystyrene and copolymers containing these structural units.

The styrenic polymer may be used alone or in combination of two or more. Although the molecular weight of the styrene polymer is not particularly limited, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. Furthermore, the molecular weight distribution is not limited in its width, and various types can be applied.

The styrenic polymer having such a syndiotactic structure can be produced by a known method (for example, Japanese Patent Application Laid-Open No. 62-187708,
JP-A-1-46912, JP-A-1-178505
No.). 2. Terminal styrene derivative-modified olefin polymer (B) (i) Examples of the olefin monomer include ethylene;
Propylene; butene-1; pentene-1; hexene-
1; heptene-1; octene-1; nonene-1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-
1; 3-methylpentene-1; 3-methylhexene-
1; 4-methylhexene-1; 5-methylhexene-
1, 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; α-olefin such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; 1,3-difluoroethylene; 3-fluoropropene; trifluoroethylene;
Halogen-substituted α-olefins such as 3,4-dichlorobutene-1, cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; One or more olefinic monomers such as cyclic olefins such as -methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; and 5-benzylnorbornene are used. As the polymer having an olefin-based monomer as a repeating unit, a polymer having one of the above-mentioned olefin-based monomers as a repeating unit or a polymer in which two or more kinds are randomly or block-copolymerized and chained are also preferably mentioned. . (ii) Terminal styrene derivative-modified olefin polymer (B)
Is represented by the following general formula (1), and the terminal of the repeating unit of the olefin-based monomer must be modified with a styrene derivative.

[0014]

Embedded image

In the formula, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably hydrogen. Each R may be the same or different. X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; Specifically, hydrogen, chlorine,
Halogen atoms such as bromine and fluorine, methyl groups, ethyl groups,
Alkyl group such as tertiary butyl group, alkoxy group such as methoxy group, ethoxy group, t-butoxy group, vinyl group, vinylphenyl group, halogen-substituted alkyl group, alkylsilyl group, phenyl group-containing silyl group, halogen-containing silyl group And a silyl group-containing silyl group. n
Represents an integer of 1 to 4, but when n is 2 or more, that is, when X is plural, each X may be the same or different. Further, m is 0 or a natural number, and Z represents a chain portion derived from the olefin-based monomer. In the styrene derivative portion present at the terminal of the structure represented by the general formula (1), the position where a vinyl group (when R is a hydrogen atom) or an alkyl-substituted vinyl group (when R is an alkyl group) is attached: Any of the ortho, meta and para positions may be used, but the para position is preferably used. (iii) The method for producing the olefin macromer (b) modified with a terminal styrene derivative represented by the general formula (1) is not particularly limited, and is, for example, a known method disclosed in JP-A-06-122711. Specifically, it can be obtained by performing living polymerization of olefins using a catalyst comprising a specific vanadium compound and an organoaluminum compound, and reacting with a styrene derivative at the end of the polymerization. 3. The styrenic resin composition according to the present invention includes thermoplastic resins other than SPS and various additional components such as inorganic fillers, antioxidants, nucleating agents, plasticizers, as long as the object of the present invention is not impaired. Additives such as an agent, a release agent, a flame retardant, a flame retardant auxiliary, and an antistatic agent can be blended. Thermoplastic resins other than SPS can be arbitrarily selected from known resins, and specifically, for example, linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic Polyolefin resins including tic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, cyclic polyolefin, poly-4-methylpentene, polystyrene, HIPS, ABS, AS
And polystyrene resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polyamide 6, polyamide 6, and 6, polyphenylene ether, and polyphenylene sulfide. In addition, a rubber-like elastic body can also be mentioned as a kind of thermoplastic resin.

For example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated Styrene-butadiene block copolymer (SEB),
Styrene-butadiene-styrene block copolymer (S
BS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer Copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEP)
S), ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (AB
S), methyl methacrylate-butadiene-styrene-
Core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MA
S), octyl acrylate-butadiene-styrene-
Core shell rubber (MABS), alkyl acrylate-
Core-shell type particle-like elastic materials such as butadiene-acrylonitrile-styrene core-shell rubber (ABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane; Rubber and the like.

Of these, SBR, SEB, S
BS, SEBS, SIR, SEP, SIS, SEPS,
Core-shell rubber, EPM, EPDM, or rubber modified from these are preferably used. In addition, these rubber-like elastic bodies can be used alone or in combination of two or more. Various inorganic fillers such as fibrous, granular, and powdery materials are used. For example, examples of the fibrous inorganic filler include glass fiber, carbon fiber, and whisker. Examples of the shape of the fibrous inorganic filler include a whisker itself, in addition to a cross-like shape, a mat-like shape, a cut bundle shape, a short fiber shape, and the like. Examples of the granular or powdery inorganic filler include talc, carbon black, graphite,
Titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, glass beads, etc. Is mentioned. Among such inorganic fillers, glass fillers such as glass powder, glass flake, glass beads, glass filament, glass fiber, glass lobing, and glass mat are particularly preferable.

The inorganic filler preferably has been subjected to a surface treatment with a coupling agent such as a silane coupling agent or a titanium coupling agent in order to improve the adhesion to the resin. Used. Such an inorganic filler may be used alone, but may be used in combination of two or more if necessary. Other nucleating agents include metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate) and metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate. ,
Any known compounds such as talc and phthalocyanine derivatives can be arbitrarily used.

As the plasticizer, any known plasticizer such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalate ester, polystyrene oligomer, polyethylene wax, mineral oil and silicone oil can be used. . Release agents include polyethylene wax, silicone oil, long-chain carboxylic acid, long-chain carboxylate, etc.
Any known one can be used.

The antioxidant can be arbitrarily selected from known ones such as phosphorous, phenol and sulfur. As flame retardants, brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether;
Any known brominated aromatic compounds such as brominated diphenylalkane and brominated diphenyl ether can be used. In addition, as the flame retardant auxiliary, antimony compounds such as antimony trioxide, and others can be arbitrarily selected and used, respectively, one type alone may be used alone, or two or more types may be used in combination. Can also be used. 4. The styrenic resin composition according to the present invention is a styrenic polymer (SP) having a high syndiotactic structure.
S) (A) and an olefin polymer modified with a terminal styrene derivative (B).
PS (A) 99.9-0.1% by weight, preferably 90-
10% by weight, more preferably 80 to 50% by weight, and the terminal styrene derivative-modified olefin polymer (B) 0.1 to 0.1% by weight.
99.9% by weight, preferably 10-90% by weight, more preferably 20-50% by weight. (6) The method for producing the styrenic resin composition according to the present invention is not particularly limited, and conditions such as the order of addition and the mixing method can be arbitrarily set. The composition also includes those obtained by mixing and then kneading the components. The method of melt-kneading is not particularly limited, and a conventionally known method can be used.

[0021]

Next, the present invention will be described in more detail by way of examples. [Production Example 1] Synthesis of terminal styrene-modified ethylene-propylene copolymer (B) 500 ml of toluene was placed in a 1-liter separable flask equipped with a stirrer and a thermometer.
After cooling to 0 ° C., a solution of 25 mmol of diethylaluminum chloride in n-heptane and 1.5 mmol of a solution of 1.5 mmol of tris (2-methyl-1,3-butanedionato) vanadium in toluene were added at that temperature. Next, 700 mmH
g, and a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied for 2 hours to copolymerize ethylene and propylene. Next, after adding a toluene solution of 100 mmol of divinylbenzene cooled to -60 ° C, the temperature of the reaction system was raised to -40 ° C over 1 hour, and the mixture was further stirred for 0.5 hour. The obtained reaction product was added to 5 liters of a methanol mixture containing a trace amount of hydrochloric acid to precipitate a polymer, and then filtration and washing with 3 liters of methanol for 0.5 hours were repeated twice. The obtained polymer was dried under reduced pressure at 30 ° C. for 12 hours, and 8.5 g was obtained.
Was obtained. Analysis of this polymer gave the following results. According to GPC measurement, the weight average molecular weight was 320.
00, and Mw / Mn = 1.21. H-
From NMR, the ratio of secondary H to tertiary H was used to determine C ₂ / C ₃
= 49/51 (mol / mol), and from the molecular weight of the ethylene-propylene copolymer and the proton intensity of the methylene portion of the terminal vinyl group of divinylbenzene, the number of styrene structural units at the end of the ethylene-propylene copolymer was about 2 It turned out to be. Further, FT-IR confirmed absorption of a terminal vinyl group at 1630 cm ^-1 . [Production Example 2] Synthesis of Terminal Styrene-Modified Propylene Polymer (B) In Production Example 1, except that 200 ml of propylene was added and polymerization was performed for 2 hours instead of using a mixed gas of ethylene and propylene. In the same manner as described above, 1.8 g of a dry polymer was obtained. Analysis of this polymer gave the following results. According to GPC measurement, the weight average molecular weight was 122000 and Mw / Mn = 1.35. Further, FT-IR confirmed absorption of a terminal vinyl group at 1630 cm ^-1 . [Production Example 3] Syndiotactic polystyrene (SP
S) Production of (A) A well-dried 1-liter separable flask was charged with 200 ml of fully dehydrated toluene and styrene monomer, respectively. Subsequently, 9.9 × 10 ^-5 mol of triisobutylaluminum (TI
BA) and 9.9 × 10 ⁻⁵ mol of triethylaluminum (TEA) were added, and the temperature was raised to 70 ° C.

Next, a previously prepared catalyst mixture (methylaluminoxane / triisobutylaluminum / pentamethylcyclopentadienyltitanium trimethoxide = 75)
1.7 ml of a toluene solution of / 25/1 (molar ratio, Ti = 3 mmol / l) was added, and polymerization was carried out for 2 hours. Add the polymerization contents to 5 liters of methanol,
The polymer component was precipitated. After washing once more, the mixture was filtered, dried under reduced pressure at 200 ° C. for 3 hours, and dried at 27.1.
g of polymer were obtained.

The polymer was analyzed and the following results were obtained. According to GPC measurement, the weight average molecular weight was 250,000.
And Mw / Mn = 3.0. Example 1 25 parts by weight of the terminal styrene-modified ethylene-propylene copolymer (B) obtained in Production Example 1 (ie, the component (A) was added to 100 parts by weight of the SPS (A) obtained in Production Example 3 above 80% by weight, the component (B) is 20% by weight), and then a small injection molding machine (injection molding machine manufactured by Niigata Iron and Steel Works:
MIN-7, cylinder temperature 290 ° C, mold temperature 150
C) to produce a dumbbell for tensile test (ASTM4). The tensile elongation at break was measured according to JIS K7113 and found to be 15%. Example 2 The procedure of Example 1 was repeated, except that the amount of component (B) was changed to 100 parts by weight.
That is, the component (A) is 50% by weight and the component (B) is 50% by weight. The measured tensile elongation at break was 28%. [Example 3] In Example 1, instead of the terminal styrene-modified ethylene-propylene copolymer obtained in Production Example 1,
Terminal styrene-modified propylene polymer 25 obtained in Production Example 2
The procedure was performed in the same manner as in Example 1 except that the amount was changed to parts by weight. That is,
The component (A) is 80% by weight and the component (B) is 20% by weight. The measured tensile elongation at break was 11%. [Comparative Example 1] In Example 1, without using the component (B),
Only the SPS obtained in Production Example 3 as the component (A) was used. The measured tensile elongation at break was 1%.

[0024]

The styrenic resin composition of the present invention has excellent heat resistance, chemical resistance and the like, has good toughness and compatibilizing ability, and is useful as a material for a composite material or a heat-resistant elastomer.

Claims (1)

[Claims] 1. A styrene polymer having a high syndiotactic structure (A) in an amount of 99.9 to 0.1% by weight, and an olefin polymer modified with a terminal styrene derivative represented by the following general formula (1) (B): A styrenic resin composition comprising 0.1 to 99.9% by weight. Embedded image [Wherein, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and each R may be the same or different. X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; n represents an integer of 1 to 4, and when n is 2 or more, each X may be the same or different. Further, m is 0 or a natural number,
Z represents a chain portion derived from the olefin-based monomer. ]