JPH10245470A - Styrene-based copolymer resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-modified styrene-based resin composition excellent in balance between impact strength and appearance of molding product. SOLUTION: This rubber-modified styrene-based copolymer resin composition is obtained by dispersing rubber-like polymer particles into a copolymer obtained by copolymerizing a styrene-based monomer with a monomer which is copolymerizable with the styrene-based monomer. In the rubber-modified styrene- based copolymer, the rubber-like polymer is a copolymer composed of ethylene and >=6C unsaturated compound and >=6C unsaturated compound unit content is 20-60mol% and intrinsic viscosity [η] measured in tetralin solution at 135 deg.C is in the range of 0.1 to 10dl/g and glass transition temperature obtained in DSC is <=-30 deg.C and the content of a component, which flows at <=25 deg.C in temperature-raising and fractionating apparatus, is >=90wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a styrenic copolymer resin composition and a method for producing the same. More specifically, the present invention relates to a styrene-based copolymer resin composition containing a rubber having a specific structure and a method for producing the same.

[0002]

2. Description of the Related Art Styrene-based copolymers such as styrene-acrylonitrile copolymer and styrene-methyl methacrylate copolymer are excellent in molding processability, and when molded, the appearance of the molded product, mechanical properties, This resin is well-balanced in properties and dimensional stability.It is widely used in household electrical appliances and electronic equipment.However, to improve the impact strength of these styrenic copolymers, rubber is added and grafted. Thus, an impact-resistant styrene copolymer having improved impact resistance is used.

Recently, it has been used for molded products having a large and more complicated shape and a small thickness. Under such circumstances, a rubber-modified styrene-based copolymer resin having excellent moldability and high impact strength has been demanded.

The rubber-modified styrene-based copolymer resin is obtained by dispersing rubber particles in a styrene-based copolymer resin, and the properties of the rubbery polymer forming the dispersed rubber particles are important for product performance. Is known to have a significant effect.
As the rubber-like polymer forming the dispersed rubber particles, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, and the like conventionally produced by a polymerization method such as anionic polymerization are used.

It is generally known that the particle size and structure of rubber particles in a resin vary greatly depending on the type of rubber. For example, the shape of the rubber particles in the rubber-modified styrene copolymer resin usually has a so-called salami structure in many cases. See, for example, Angew. Makromol. Che
m. 58 / 59P175-198 (1977)).

[0006] According to these methods, the particle size and structure of the rubber particles in the resin change depending on the type of rubber, and the physical properties of the molded product change accordingly.

On the other hand, ethylene, propylene and diene have recently been copolymerized in the presence of a transition metal compound having a ligand consisting of cyclopentadienyl skeleton and methylaluminoxane as a promoter. It has been reported that a rubber having physical properties different from conventional ones can be obtained.

Further, copolymerizing ethylene with an olefin such as butene or hexene in the presence of a transition metal compound having a ligand composed of cyclopentadienyl skeleton and methylaluminoxane as a promoter. It is also reported that a rubber having different physical properties can be obtained.

For example, as a new propylene, ethylene, diene copolymer, a method for synthesizing a propylene, ethylene, diene copolymer using a catalyst comprising a metallocene compound having a crosslinked structure and an aluminoxane has recently been disclosed in Japanese Patent Application Laid-Open No. 2-64111. It is. In addition, DOW patent US
P5, 278, 272 also discloses a method for synthesizing a copolymer of ethylene and hexene.

[0010]

The method of combining a styrenic copolymer and a rubbery polymer for improving the impact strength is difficult because the physical properties of the composition are greatly changed by changing the type of rubber. Research and development
It has been disclosed in many patent publications and the like.

EPR and E which are rubbers containing no styrene
In PDM, a large amount of rubber must be added to improve the impact resistance, or a rubber copolymer containing a styrene component is added as a compatibilizer to uniformly disperse the rubber in the resin. Have been proposed in JP-A-1-146944 and JP-A-1-279944. However, these methods have a small effect as a compatibilizer and can reduce the amount of rubber to be used for improving impact resistance. There is a problem that it is impossible to improve the physical properties. At present, efforts are being made to improve new rubbers for the purpose of improving the physical properties, and development of a styrene-based copolymer resin having an excellent balance of physical properties is desired.

[0012]

Means for Solving the Problems The present inventors have intensively studied a method for synthesizing a styrenic copolymer resin using various rubbers in order to solve the above problems. The inventors have found that a styrene-based copolymer resin composition having an excellent balance of physical properties can be obtained by dispersing a polymer in a styrene-based copolymer resin, thereby completing the present invention. That is, the present invention includes the following inventions.

A rubber-modified styrene copolymer resin obtained by dispersing rubber-like polymer particles in a copolymer obtained by polymerizing a styrene monomer and a monomer copolymerizable with the styrene monomer. A rubbery polymer, which is a raw material for forming the rubbery polymer particles, comprises ethylene and carbon atoms
A copolymer comprising the above unsaturated compound, wherein the content of the unsaturated compound unit having 6 or more carbon atoms in the copolymer of ethylene and the unsaturated compound having 6 or more carbon atoms is 20 to 60 mol%. And the intrinsic viscosity [η] measured with a tetralin solution at 135 ° C. is 0.1 to 10 dl.
/ G, and the glass transition temperature determined by DSC is-
A rubber-modified styrene copolymer resin composition having a temperature of 30 ° C. or lower, and 90% or more of components flowing out at 25 ° C. or lower in a temperature-raising fractionator using dichlorobenzene as a mobile phase.

The rubbery polymer is (A) a compound represented by the following general formula (1, 2, 3)

[0015]

(A) M (R ¹ ) (R ² ) (R ³ ) General formula (1) (A) (B) M (R ¹ ) (R ² ) General formula (2) (A) (B ) (C) M (R ¹ ) General formula (3) (where A, B and C are a group consisting of an unsaturated compound bonded or coordinated to M, a cyclopentadienyl group or a derivative thereof, A ligand consisting of a group in which a heteroatom of Groups 13, 14, 15 and 16 of the periodic table is bonded or coordinated to M, A, B and C are each a single bond, A, B, and C may be bonded or coordinated to M, and include A, B, and C in which M is resonantly bonded.
R ¹ , R ² and R ³ each represent a hydrogen atom, a halogen atom, an organic metalloid group, an alkoxy group, an amino group, a hydrocarbon group or a hetero atom-containing hydrocarbon group, which may be the same or different from each other . R ¹ , R ² and R ³ may be crosslinked, or R ¹ , R ² and R ³ may be crosslinked with M. M is a metal of Group 3, 4 or 5 of the periodic table, a lanthanoid or an actinoid metal. (B) at least one compound selected from (B1) to (B3), which reacts with (A) to form a stable ionic complex; (B1) aluminoxane; (B2) reacts with (A) (B3) Lewis acid compound which forms a stable ionic complex by reacting with (A) to form a stable ionic complex (C) Accordingly, ethylene and an unsaturated compound having 6 or more carbon atoms are copolymerized using a catalyst comprising an organometallic compound of Group 1, 2 or 13 of the periodic table having at least one or more hydrocarbon residue. The rubber-modified styrenic copolymer resin composition according to claim 1, which is obtained.

A rubber-modified styrene according to or described above, wherein the styrene-based monomer and a copolymer of a monomer copolymerizable with the styrene-based monomer and the rubbery polymer are melt-mixed. A method for producing a system copolymer resin composition.

The rubbery polymer described in any of the above is dissolved in a solution containing a styrene monomer and a monomer copolymerizable with the styrene monomer, and the rubbery polymer obtained by polymerizing the solution is dissolved. A method for producing a rubber-modified styrene-based copolymer resin composition in which coalesced particles are dispersed.

In dispersing the rubber-like polymer particles,
Organic peroxide was added to 100 parts by weight of a solution in which the rubbery polymer was dissolved in a solution containing a styrene monomer or a styrene monomer and a monomer copolymerizable with the styrene monomer. A method for producing a rubber-modified styrene-based copolymer resin composition according to the above-mentioned, wherein 0.0005 to 0.05 part by weight is added and copolymerized.

A rubber-modified styrenic copolymer resin composition obtained by any one of the above production methods.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION A rubber-like polymer as a raw material for forming rubber-like polymer particles of the rubber-modified styrenic copolymer composition of the present invention is a copolymer comprising ethylene and an unsaturated compound having 6 or more carbon atoms. A copolymer of ethylene and an unsaturated compound having 6 or more carbon atoms, wherein the content of the unsaturated compound unit having 6 or more carbon atoms is in the range of 20 to 60 mol%, and The intrinsic viscosity [η] measured in the solution is in the range of 0.1 to 10 dl / g, and DS
The glass transition temperature determined by C is -30 ° C or lower, and the component which flows out at 25 ° C or lower by a temperature-raising fractionator using dichlorobenzene as a mobile phase is 90% or more is used.

Any of the above-defined rubbery polymers can be used without particular limitation, such as the production method. An example of a preferred polymerization method of the rubbery polymer is a copolymer of ethylene and an unsaturated compound having 6 or more carbon atoms in a catalyst system comprising the following general formula (1, 2, 3) (Chem. 3) and a cocatalyst. It is obtained.

[0022]

(A) M (R ¹ ) (R ² ) (R ³ ) General formula (1) (A) (B) M (R ¹ ) (R ² ) General formula (2) (A) (B) (C) M (R ¹ ) Formula (3) (A, B, C, M, R ¹ , R ² and R ³ are as defined above.) Used in the rubbery polymer of the present invention. Examples of unsaturated compounds having an unsaturated bond and having 6 or more carbon atoms include 3-metalpentene-1, 4-metalpentene-1, 2,3-dimethylbutadiene, 2-methyl-5-vinylpyridine,
Unsaturated compounds such as -hexene, 2-ethyl-1,2-ethyl-1-hexene, 1-octene, 1-decene, 1-nonene, 1-undecene, 1-dodecene, vinylcyclohexane, and styrene derivatives; Can be

The rubbery polymer of the present invention has an unsaturated compound unit having 6 or more carbon atoms having an unsaturated bond to ethylene in the range of 20 to 60 mol%, preferably 25 to 50 mol%. Has good physical properties.

Further, the intrinsic viscosity number [η] measured with a tetralin solution at 135 ° C. must be in the range of 0.1 to 20 dl / g, preferably 0.5 to 15, more preferably 1 to 10 dl / g. / G.

When [η] is 0.1 or less, physical properties deteriorate, which is not preferable. In addition, the dispersibility of the rubber particles in the resin having [η] of 20 or more and the moldability of the resin composition deteriorate, which is not preferable.

It is necessary that the glass transition temperature determined by a differential thermal analyzer (DSC) is -30 ° C. or less,
Preferably it is -40C or less. If the temperature exceeds -30 ° C, the impact strength decreases, which is not preferable.

Further, 90% or more, preferably 95% or more, of components flowing out at a temperature of 25 ° C. or less is obtained by a temperature raising and fractionating apparatus using dichlorobenzene as a mobile phase. A component which does not flow out at 25 ° C. or lower contains a large amount of ethylene chains and thus deteriorates the performance as a rubber.

As a temperature raising and fractionating apparatus used in the method of the present invention, a 1.07 cm diameter column was filled with Chromosolve-P, an infrared detector was attached, and 0-dichlorobenzene was used as a mobile phase at a rate of 2 ml / min. The measurement was performed while flowing.
A sample was prepared by injecting a sample solution in which 0.7 mg was dissolved in 2 ml of 0-dichlorobenzene into a 135 ° C. column, cooling the entire column to 0 ° C., and then raising the column temperature at a rate of 20 ° C./hour. The concentration of the polymer eluted at each temperature is determined by detecting with an infrared detector.

The styrene monomer referred to in the present invention includes styrene, side chain alkyl-substituted styrene such as α-methylstyrene and α-ethylstyrene, vinyl toluene, vinyl xylene, ot-butyl styrene, p- Examples thereof include nuclear alkyl-substituted styrenes such as t-butylstyrene and p-methylstyrene, halogenated styrenes such as monochlorostyrene, dichlorostyrene, triprostyrene, and tetrahydrostyrene, p-hydroxystyrene, and o-methoxystyrene.

Particularly preferred are styrene, α-methylstyrene and p-methylstyrene, and the styrene monomer can be used alone or in combination of two or more.

The monomers copolymerizable with the styrene monomer in the present invention include acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α-
Examples include acrylate monomers such as chloroacrylonitrile and methyl methacrylate, maleimide monomers such as maleimide and N-phenylmaleimide, and acrylates. One of these or a mixture of two or more thereof can be used.

The ratio of the styrene monomer and the monomer copolymerizable with the styrene monomer is 4%.
It is 0 to 90% by weight, preferably 50 to 85% by weight, and more preferably 60 to 85% by weight.

The rubber-like polymer particles are prepared by melt-mixing a predetermined amount of the rubber-like polymer with the styrene monomer and a copolymer of a monomer copolymerizable with the styrene monomer. The rubbery polymer particles are formed in a dispersed state in a system copolymer. Alternatively, by mixing a mixture of a styrene-based monomer to which a predetermined amount of a rubbery polymer is added and a monomer mixture of a monomer copolymerizable with the styrene-based monomer, The rubbery polymer particles are formed in a dispersed state.

Since the amount of the rubbery polymer used is different in the amount dispersed in the copolymer depending on the polymerization conditions and the like, a mixture of a styrene monomer and a monomer copolymerizable with the styrene monomer is used. In terms of the ratio of the rubbery polymer contained in the copolymerization of the monomer mixture, it is 3 to 50% by weight, preferably 5 to 40% by weight, more preferably 3 to 30% by weight based on the copolymer. It is.

The rubbery polymer of the present invention is a copolymer of ethylene and an unsaturated compound having 6 or more carbon atoms, and has a specific unsaturated compound content, intrinsic viscosity, glass transition temperature, and temperature rise as described above. The rubbery polymer can be used without limitation as long as it has a specific fractionation value in a fractionation apparatus, but the preferred production of the rubbery polymer is a catalyst system containing a transition metal compound shown below as a catalyst component. Can be performed.

The transition metal compound has at least one cyclopentadienyl group or a derivative group thereof, or a group containing a hetero atom belonging to Group 13, 14, 15, or 16 of the periodic table as a ligand. Periodic Table Group 3, Group 4, Group 5,
A metal complex containing a lanthanoid or actinoid metal.

These transition metal complexes are preferably used as carriers selected from organic compounds and inorganic compounds, preferably those supported on inorganic compounds. Examples of the organic compound carrier include crosslinked polystyrene, polyethylene, polypropylene, and carbon, and examples of the inorganic compound include inorganic oxides, metal carbonates, metal halides, and metal sulfates, such as silica gel, alumina, magnesium chloride, and magnesium carbonate. You.

The transition metal compound can be used in combination with a co-catalyst and, if necessary, other components.

As the transition metal compound, the compounds represented by the above-mentioned general formulas (1, 2, 3) can be used, which are specifically shown below.

The following are specific examples of the compound represented by the general formula (1). Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1,2 dimethylcyclopentadienyl) zirconium dichloride, bis (1,3 dimethylcyclopentadienyl) zirconium dichloride, Bis (1,2,3 trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,4 trimethylcyclopentadienyl) zirconium dichloride, bis (1,2,3,4 tetramethylcyclopentadienyl)
Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (1,2 diethylcyclopentadienyl) zirconium dichloride, bis (1,3 diethylcyclopentadienyl) ) Zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (phenylpropylcyclopentadienyl)
Zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4-methyl-1-indenyl) zirconium dichloride, bis (5-methyl-1-indenyl) zirconium dichloride, bis ( 6-methyl-1-indenyl) zirconium dichloride, bis (7-methyl-1-indenyl)
Zirconium dichloride, bis (5-methoxy-1-
Indenyl) zirconium dichloride, bis (2,3
-Dimethyl-1-indenyl) zirconium dichloride.

Bis (4-7-dimethyl-1-indenyl) zirconium dichloride, bis (4,7-dimethoxy-1-indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) ) Zirconium dichloride, (cyclopentadienyl)
(Dimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) ( (Pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (diethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (triethyl (Cyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride,
(Cyclopentadienyl) (pentaethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, (cyclopentadienyl) (2,7-di-tertbutylfluorenyl) zirconium dichloride, (Cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (t-butylcyclopentadienyl) zirconium Dichloride, (methylcyclopentadienyl) (fluorenyl) zirconium dichloride.

(Methylcyclopentadienyl) (2,7
-Di-t-butylfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (methylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (dimethylcyclopentane (Dienyl) (fluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (dimethyl (Cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (2, -Di-tert-butylfluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (diethylcyclopentane) Dienyl) (fluorenyl) zirconium dichloride, (diethylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (diethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, Ethylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (methylcyclopentadienyl) zirconium dichloride, ethylene bis (1,2 dimethylcyclopentadienyl) zirconium dichloride, ethylene bis (1,3 dimethylcyclopentadienyl) Zirconium dichloride, ethylene bis (1,2,3 trimethylcyclopentadienyl) zirconium dichloride, ethylene bis (1,2,4 trimethylcyclopentadienyl) zirconium dichloride Roraido, ethylenebis (1.
2,3,4 tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, ethylenebis (ethylcyclopentadienyl) zirconium dichloride, bis (1,2 diethylcyclopentadienyl) Zirconium dichloride, ethylenebis (1.3 diethylcyclopentadienyl) zirconium dichloride,
Ethylene bis (isopropylcyclopentadienyl) zirconium dichloride.

Ethylene bis (phenylpropylcyclopentadienyl) zirconium dichloride, ethylene bis (t-butylcyclopentadienyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4-methyl-1-indenyl) zirconium dichloride , Ethylene bis (5-
Methyl-1-indenyl) zirconium dichloride,
Bis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, bis (5-methoxy-
1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1)
-Indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl) zirconium dichloride, ethylenebis (fluorenyl) zirconium dichloride, ethylenebis (4.5,6,7tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (Fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (trimethylcyclo (Pentadienyl) zirconium dichloride, etherene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichlora De, ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl)
(Ethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (diethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride.

Ethylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (pentaethylcyclopentadienyl) zirconium dichloride,
Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl)
(2,7-dichlorofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (Methylcyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (methylcyclopentadienyl)
(2,7-di-tert-butylfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (methylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride , Ethylene (dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (octahydroble (Oenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (ethylcyclopentadienyl) (fluorenyl) zircon Dichloride, ethylene (ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (ethylcyclopentadiene) Enyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (2,
7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (Cyclopentadienyl) (4,5-methylenephenanthrene) zirconium dichloride, in addition to the above, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a methylphenylmethylene group, a diphenylmethylene group, 1,4-cyclopentane-di-ylidene group, 1,4-cyclohexane-di-ylidene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, dimethylgermylene group, dimethylstar Include those alkylene group is bonded. Further, a complex in which a zirconium atom is replaced by a titanium atom and a hafnium atom, and a complex in which bromide, iodide and fluoride are replaced by chloride are exemplified.

Specific examples of the compound for linking two cyclopentadienyl groups are given below. Dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-
Diethylcyclopentadienyl) zirgonium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-di-tertbutylcyclopentadienyl) zirconium dichloride, dimethyl Silylene bis (phenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2, 3,5-triethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-
Isopropylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-phenylpropylcyclopentadienyl) zirconium dichloride.

Dimethylsilylenebis (3-t-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (2,4
-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (2,4
-Dimethylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetrametercyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethyl Cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2.4-dimethylcyclopentadienyl) (2,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (2.3,
5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride And the like.

As compounds having no cyclopentadienyl group, bis [N, N-bis (trimethylsilyl) benzamidinato zirconium dichloride, bis [N, N-dimethylacetamidinate) zirconium dichloride, bis [(t -Butoxydimethylsilyl)
-T-butylaminozirconium dichloride, bis [(t-butoxydimethylsiloxy) bis (trimethylsilylzirconium, bis [N, N-dimethylacetamidinate] diethoxyzirconium, bis [N, N-
Dimethylacetamidinate) bis (diethylamino)
Zirconium, bis [(t-butoxydimethylsiloxy) bis (diethylamino) zirconium, bis [(t
-Butoxydimethylsilyl) -t-butylamino] dimethylzirconium, butylenebis [N. N-bis (trimethylsilyl) benzamidinato] zirconium dichloride, δ- (t-butylamino) valerule N-
[Bis (trimethylsilyl) amidinate] zirconium dichloride, diamidinato titanium dichloride, and the like, instead of zirconium atom, a complex in which titanium atom and hafnium atom are substituted, or a lanthanoid series or actinoid series metal complex may be used. Further, a complex in which bromide, iodide, or fluoride is used instead of chloride can be used. These compounds may be used alone or in combination of two or more.

Compound (B) capable of forming a stable ionic complex by reacting with the transition metal compound (A) as a co-catalyst
And at least one of the following (B-1) to (B-3) is used.

The component (B) includes (B-1)
An ionic compound formed from a bulky anion and a cation which reacts with the transition metal compound as the component (A) to form a stable ionic complex; (B-2) an aluminoxane;
-3) Lewis acid compounds which react with (A) to form a stable ionic complex.

As the component (B-1), any ionic compound capable of reacting with the transition metal compound of the component (A) to form a stable ionic complex can be used. The following general formula (4) (formula 4) and general formula (5)
(Formula 5)

[0051]

([L ¹ -R ⁴ ] ^{k +} ) _p ([Z] ⁻ ) _q General formula (4)

[0052]

Embedded image ^{([L 2] k +)} p ([Z] -) q formula (5) [However, L ² is ^{M 2, R 5 R 6 M} 3, R 7 3 C or R ⁸
M is ^3. In the formulas (4) and (5), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z
^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 A 1 A 2 ···} A n] - ( wherein, M ¹ is the periodic table 5-15 A group element, preferably an element belonging to groups 13 to 15 of the periodic table, wherein A ^{1 to An} are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, Carbon number 1
An alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and having 1 to 20 carbon atoms It represents a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. A ¹
Two or more of —A ⁿ may form a ring. n is an integer of [(valence of central metal M ¹⁾ +1]. ),
[Z ^{2] -} is the reciprocal of the acid dissociation constant logarithm (pKa) is -
A conjugate base of 10 or less Brönsted acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated.

[0053] Further, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, R ⁵ and R ⁶
Are each a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ⁷
Represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.

R ⁸ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is [L ¹ -R
⁴ ] and [L ² ] are ionic valences of 1 to 3, p is an integer of 1 or more, and q = (k × p). M ² contains an element of Groups 1 to 3, 11 to 13, and 17 of the periodic table;
³ represents an element in Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine; And phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ⁴ include hydrogen, a methyl group,
Examples of the group include an ethyl group, a benzyl group, and a trityl group. Specific examples of R ⁵ and R ⁶ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentane. And a dienyl group.

Specific examples of R ⁷ include a phenyl group, p-
Examples thereof include a tolyl group and a p-methoxyphenyl group, and specific examples of R ⁸ include tetraphenylporphine, phthalocyanine, allyl, and methallyl.

As specific examples of M ² , Li, N
a, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, N
i, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ¹ A ¹ A ^2]
... A ⁿ ], specific examples of M ¹ include B,
Al, Si, P, As, Sb, etc., preferably B and A
l.

[0060] Specific examples of A ^1, A ² ~A ⁿ is dimethylamino group as a dialkylamino group, a diethylamino group, a methoxy group as an alkoxy group or an aryloxy group, an ethoxy group, n- butoxy group,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, hydrocarbon groups such as phenoxy
Fluorine, chlorine, bromine, halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group and 3,5-dimethylphenyl group; Iodine, p-fluorophenyl group as a hetero atom-containing hydrocarbon group, 3,5
-Difluorophenyl group, pentachlorophenyl group,
Organic metalloid groups such as 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group, as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

Further, a non-coordinating anion, ie, pKa
-10 or less Brønsted acid alone or
Conjugated base [Z^Two ]^- Utensils
An example of the body is trifluoromethanesulfonic acid anion
(CF_Three SO_Three )^- , Bis (trifluoromethanesulfo
Nyl) methyl anion, bis (trifluoromethanesulfur)
Honyl) benzyl anion, bis (trifluoromethane)
Sulfonyl) amide, perchlorate anion (ClO_Four )
^- , Trifluoroacetate anion (CF_Three CO_Two ) ^- , F
Xafluoroantimony anion (SbF₆ )^- ,full
Orosulfonic acid anion (FSO_Three )^- , Chlorosulfo
Acid anion (ClSO_Three )^- , Fluorosulfonic acid
Nion / 5-antimony fluoride (FSO_Three / SbF_Five )
^- , Fluorosulfonic acid anion / 5-arsenic fluoride (F
SO_Three / AsF_Five )^- , Trifluoromethanesulfonic acid
/ 5-antimony fluoride (CF_Three SO_Three / SbF_Five )^- 
And the like.

Specific examples of the ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), that is, the compound of the component (B-1) include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
Boric acid (1,1'-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetrakis (pentafluorophenyl) borate porphyrin porphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned.

The component (B-1), an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), may be used alone or in combination of two or more. May be used.

On the other hand, the aluminoxane of the component (B-2) is represented by the general formula (6):

[0065]

Embedded image [In the formula, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, and s indicates a degree of polymerization.
It is an integer of 50, preferably 7 to 40. And the general formula (7)

[0066]

Embedded image Wherein R ⁹ and s are the same as above. ] And combinations thereof include the aluminoxane compounds shown.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the method is not particularly limited, and the reaction may be carried out according to a known method. . For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and water is added later, water of crystallization contained in a metal salt, etc., inorganic substances Reacting water adsorbed on organic substances with organic aluminum compounds,
There is a method in which a tetraalkyldialuminoxane is reacted with a trialkylaluminum and then with water. The aluminoxane may be toluene-insoluble. These aluminoxanes may be used alone or in a combination of two or more.

The Lewis acid which forms a stable ionic complex by reacting with the component (A) of the component (B-3) is not particularly limited, and may be an organic compound or a solid inorganic compound.

For example, a boron compound or an aluminum compound is preferably used as an organic compound, and a magnesium compound or an aluminum compound is preferably used as an inorganic compound.

Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy)
Aluminum methyl, (1,1-bi-2-naphthoxy)
Examples of aluminum compounds include aluminum methyl, magnesium compounds such as magnesium chloride and diethoxymagnesium, examples of aluminum compounds include aluminum oxide and aluminum chloride, and examples of boron compounds include triphenylboron and tris (pentafluorophenyl) boron. , Tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl)
Phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron,
Tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis (trifluoro) Methyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, Examples thereof include phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, and n-butyldifluoroboron. One of these Lewis acids may be used, or two or more thereof may be used in combination.

The ratio of the catalyst component (A) to the catalyst component (B) in the polymerization catalyst is preferably 10 to 10% by mole when the compound (B-1) is used as the catalyst component (B). : 1 to 1: 100, more preferably 2: 1 to 1:
In the case where the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 100,0.
00, more preferably 1:10 to 1: 10,000. The use ratio of the (A) catalyst component and the (B-3) catalyst component is preferably a molar ratio of 1: 0.1 to
1: 2,000, more preferably 1: 0.2 to 1: 1,
000, more preferably in the range of 1: 0.5 to 1: 500. As the catalyst component (B), (B-
1), (B-2) and (B-3) can be used alone or in combination of two or more.

The polymerization catalyst may contain the above components (A) and (B) as main components, or may contain at least components (A), (B) and (C) Those containing an organometallic compound belonging to Group 1, 2, or 13 of the Periodic Table having a bond of one or more metals and a hydrocarbon group can also be used.

As the component (C), an organoaluminum compound can be particularly preferably used. Here, the organoaluminum compound of the component (C) is represented by the general formula (8):

[0074]

Embedded image _R ¹⁰ _r AlQ _3-r general formula (8) [wherein, R ¹⁰ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, 6 carbon atoms 20
Represents an aryl group or a halogen atom, and r is an integer of 1 to 3. ] Is used.

Specific examples of the compound represented by the general formula (8) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1:10,
000, more preferably 1: 5 to 1: 2,000, and still more preferably 1:10 to 1: 1,000. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the copolymer, which is not preferable.

In the present invention, at least one of the catalyst components
One can be used by supporting it on a suitable carrier. The charge
There is no particular limitation on the type of body,
Body, any other inorganic and organic carriers
But especially inorganic oxide carriers or other
Are preferred. As the inorganic oxide carrier, specific
Typically, SiO_Two , Al_Two O_Three , MgO, ZrO_Two , T
10_Two , Fe_Two O_Three , B _Two O_Three , CaO, ZnO, Ba
O, ThO_Two And mixtures thereof, for example, silica aluminum
Na, zeolite, ferrite, glass fiber, etc.
No. Among them, especially SiO 2_Two , Al_Two O
_Three Is preferred. In addition, the inorganic oxide carrier is a small amount of carbon.
Acid salts, nitrates, sulfates and the like may be contained.

On the other hand, as a carrier other than the above, MgCl 2
A magnesium compound represented by the general formula MgR ¹¹ _x X ¹ _y represented by a magnesium compound such as ₂ , Mg (OC ₂ H ₅ ) ₂ or a complex salt thereof can also be used.

These co-catalysts can be used alone or in admixture of two or more.

The polymerization method of the rubbery polymer is not particularly limited, and can be used by a conventional method such as a solvent polymerization method, a bulk polymerization method in which substantially no solvent is present, or a gas phase polymerization method. There is no particular limitation, and the reaction is usually carried out at a normal temperature to 250 ° C. and at a normal pressure to 50 kg / cm ² .

The present invention also relates to a rubber-modified styrene-based resin composition in which a copolymer of a styrene-based monomer and a monomer copolymerizable with the styrene-based monomer is melt-mixed with the rubbery polymer. It is a method of manufacturing a product. There is no particular limitation on the method of melt mixing, and the melt mixing of these components may be performed at a temperature substantially higher than the melting point of the polymer having the highest melting point. If necessary, a known additive such as an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, or another nucleating agent is mixed with a Henschel mixer, a V-type blender or the like, and then, an extruder or a roll, a Banbury mixer, a kneader is used. It is preferable to melt-mix and then granulate once to form a pellet.

The present invention also relates to a rubber-modified styrene resin composition obtained by dissolving the above rubbery polymer in a mixture of a styrene monomer and a monomer copolymerizable with a styrene monomer, and polymerizing the solution. It is a manufacturing method of. That is, as a polymerization method, a solution obtained by dissolving a rubbery polymer in a mixture of a styrene monomer and a monomer copolymerizable with the styrene monomer is polymerized by bulk polymerization or bulk-suspension two-stage polymerization method. The polymerization method is not particularly limited, and is produced by thermal polymerization or catalytic polymerization.

The resin composition obtained by polymerization as described above is preferable because the impact strength is improved by a grafting effect on rubber as compared with a case where the resin composition is simply blended.

The rubber solution may contain a solvent such as benzene, toluene, xylene, ethylbenzene, acetone, isopropylbenzene, methyl ethyl ketone or methylene chloride.

In the present invention, a styrene-based monomer is grafted on a rubber-like polymer, and the rubber-like polymer is further made into particles and dispersed in a resin. These reactions are carried out by thermal polymerization or a polymerization initiator during the reaction. It is also preferred to use

Examples of the polymerization initiator which can be used in the present invention include, for example, benzoyl peroxide, lauroyl peroxide, t-butyl peroxypiparate, t-butyl peroxypentazoate, t-butyl peroxyisobutyrate. Rate, t-butyl peroxy octoate, cumyl peroxy octoate, 1,1-bis (t-butyl peroxy) 3,3,5-trimethylsiloxane, 2,2-bis (t-butyl peroxy) octane , N-butyl 4,4-bis (t-butylperoxy)
Valerate, 2,2-bis (t-butylperoxy) butane, t-butylperoxymaleic acid, t-butylperoxyisopropylcaponate, dicumylperoxide, t-butylhydroperoxide, cumenehadroperoxide, etc. Is mentioned. These may be used alone or in combination of two or more. For example, when an organic peroxide is used, 0.0005 to 0.05 parts by weight of the polymerization initiator is used with respect to 100 parts by weight of the solution in which the rubbery polymer is dissolved. Is preferred. If the amount is less than 0.05 part by weight, no giant particles are generated, and the surface condition of the molded article is favorable, and if it is 0.0005 parts by weight or more, an appropriate polymerization rate and a graft ratio to rubber are preferably maintained.

In the present invention, a chain transfer agent can be used for controlling the molecular weight of the styrene copolymer.
For example, α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan and the like can be used.

The polymerization of the present invention is a solution polymerization or a bulk polymerization, but the polymerization step is not limited to a specific reaction tank. For example, a complete mixing reaction tank, a tubular reaction tank, a tower reaction tank or the like is used. The type and number of the reaction vessels are not particularly limited.

The rubber-modified styrenic resin composition of the present invention may contain, if necessary, an antioxidant such as a hindered phenolic antioxidant, a phosphorus antioxidant, or a sulfur antioxidant;
A fluidity improver such as mineral oil and a release agent such as stearic acid, zinc stearate and organic polysiloxane may be added during the raw material solution or during or after the polymerization.

The resin composition of the present invention can be molded by a method commonly used for molding polystyrene such as injection molding or extrusion molding to produce a molded article having a good balance between rigidity and impact resistance. . The molding temperature at this time is not particularly limited and can be a normal molding temperature.
３００300 ° C.

[0090]

The present invention will be further described with reference to examples. Evaluation of physical properties (1) Izod impact strength: Measured according to JIS K-6871. (2) Flexural modulus: Measured according to JIS K-7203.

Example 1 [Synthesis of ethylene / octene-1 copolymer]
Toluene 5 in 0 liter stainless steel autoclave
Add 0 liter and keep 1-octene 5 at 20 ° C.
0 liter was introduced, 100 mmol of triisobutyl aluminum was further added, and ethylene gas was introduced at 20 ° C. to obtain 3 kg / cm ² -G and synthesized according to a conventional method (cyclopentadienyl) [N, N′-. A solution of 1 mmol of bis (trimethylsilin) penzamidinato] zirconium dichloride in toluene was added, and then 2 mmol of N, N'-dimethylanilinium and tetrakis (pentafluorophenyl) porate were added, and 3 kg of ethylene gas was added. The temperature was raised to 80 ° C. and the polymerization was carried out for 90 minutes while keeping the temperature constant at ² cm ² -G, whereby 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 4 dl
/ G, and the glass transition temperature determined by DSC is -42 ° C.
Using a dichlorobenzene as a mobile phase, an ethylene / octene-1 copolymer (octene-1 content: 26 mol%) was obtained in which a component flowing out at 25 ° C. or less was 99% or more in a temperature-raising fractionating apparatus.

[Production of Resin Composition] The above rubbery copolymer was added to Table 1 in 100 parts by weight of a polystyrene / acrylonitrile copolymer (manufactured by Mitsui Toatsu Chemicals, Inc., grade 120 PCR). At the indicated ratio, 0.1 part by weight of an antioxidant and 0.1 part by weight of calcium stearate were further added and mixed with a Henschel mixer, followed by heating and mixing at 230 ° C. with an extruder to obtain pellets. Using these pellets, an injection molding machine (FSM55, manufactured by Komatsu Seisakusho KK)
The test piece was molded in T) and the physical properties were measured. Table 1 shows the results.

Example 2 A rubber-modified styrene resin was produced by using a continuous mass polymerization apparatus in which a preheater was connected to the outlets of three serial reactors with a stirrer, and a vacuum tank was connected. In a first reactor equipped with a stirrer, 9 parts by weight of the rubbery polymer obtained in Example 1, 20 parts by weight of ethylbenzene, 60 parts by weight of styrene, 20 parts by weight of acrylonitrile, and 1,1-bis as an organic peroxide. (T
-Butyl peroxy) 3,3,5-trimethylcyclohexane 0.005 parts by weight of a raw material liquid was continuously supplied. The first reaction temperature is 142 ° C., the second reaction temperature is 145 ° C., the third reaction temperature is 145 ° C., the temperature of the preheater is kept at 210-250 ° C. The degree of vacuum was 40 Torr. Table 1 shows the measurement results of physical properties of the obtained polymer.

Example 3 In Example 2, styrene / acrylonitrile: 60 /
The procedure was performed under the same conditions as in Example 2 except that styrene and acrylonitrile were used in a ratio of 75/25 instead of 20 (weight ratio), and that 9 parts by weight of the rubbery polymer and 20 parts by weight of ethylbenzene were used. Table 1 shows the measurement results of physical properties of the obtained polymer.

Example 4 A rubbery polymer was polymerized in the same manner as in Example 1 except that the ethylene pressure was lowered, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 5 dl / g. , DSC
The ethylene / octene-1 copolymer (octene-1 content 34) having a glass transition temperature of -48 ° C. determined by the above and having 99% or more of components flowing out at 25 ° C. or less by a temperature-raising fractionator using dichlorobenzene as a mobile phase. Table 1 shows the results obtained in the same manner as in Example 2 except that 4.2 parts by weight (mol%) was used.

Comparative Example 1 Table 1 shows the results obtained in the same manner as in Example 1 except that polybutadiene (Asahi Kasei Diene 35AS) was used instead of the ethylene / octene copolymer.

Example 5 Copolymerization was conducted in the same manner as in Example 1 except that 1-decene was used in place of 1-octene, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 4.6 dl /. g, a component which flows out at 25 ° C. or less in a temperature-raising fractionating apparatus using dichlorobenzene as a mobile phase at a temperature of 25 ° C. or less to give a rubbery copolymer having a glass transition temperature of −50 ° C. determined by DSC. .
(1-decene content 28 mol%). The results of an experiment conducted in the same manner as in Example 1 except that 4.2 parts by weight were used are shown in Table 1.
Shown in

Example 6 Copolymerization was carried out in the same manner as in Example 1 except that 1-hexene was used in place of 1-octene, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 4.6 dl. / G, and using a dichlorobenzene as a mobile phase, 2
99% or more of components flowing out at 5 ° C. or less, and ethylene / 1- having a glass transition temperature of −38 ° C. determined by DSC.
The procedure was carried out under the same conditions as in Example 2 except that 4.2 parts by weight of the hexene copolymer (hexene content: 32 mol%) was used.

[Table 1]

[0099]

Industrial Applicability The rubber-modified styrenic resin composition of the present invention has an excellent balance between impact strength and appearance of a molded product, and can be used industrially in parts materials such as household electric appliances and electronic equipment. The value is great.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 51/04 C08L 51/04

Claims (6)

[Claims] 1. A rubber-modified styrene copolymer obtained by dispersing rubber-like polymer particles in a copolymer obtained by polymerizing a styrene monomer and a monomer copolymerizable with the styrene monomer. A coalescing resin composition, wherein the rubbery polymer as a raw material for forming the rubbery polymer particles is a copolymer of ethylene and an unsaturated compound having 6 or more carbon atoms, The content of the unsaturated compound unit having 6 or more carbon atoms in the copolymer with the above unsaturated compound is in the range of 20 to 60 mol%, and the intrinsic viscosity number [η] measured with a tetralin solution at 135 ° C. 0.1 to 10 dl
/ G, and the glass transition temperature determined by DSC is-
A rubber-modified styrene copolymer resin composition having a temperature of 30 ° C. or lower, and 90% or more of components flowing out at 25 ° C. or lower in a temperature-raising fractionator using dichlorobenzene as a mobile phase. 2. The rubbery polymer is represented by the following general formula (A): (A) M (R ¹ ) (R ² ) (R ³ ) 1) (A) (B) M (R ¹ ) (R ² ) General formula (2) (A) (B) (C) M (R ¹ ) General formula (3) (where A, B and C are , A group consisting of an unsaturated compound bonded or coordinated to M, a cyclopentadienyl group or a derivative thereof, or a hetero atom belonging to Group 13, 14, 15 or 16 of the periodic table is bonded to M or A ligand consisting of a coordinating group, wherein A, B and C may be bonded to each other by a single bond, a double bond or a combination thereof. Bonded or coordinated, and also includes A, B and C in which M is resonantly bonded.
R ¹ , R ² and R ³ each represent a hydrogen atom, a halogen atom, an organic metalloid group, an alkoxy group, an amino group, a hydrocarbon group or a hetero atom-containing hydrocarbon group, which may be the same or different from each other . R ¹ , R ² and R ³ may be crosslinked, or R ¹ , R ² and R ³ may be crosslinked with M. M is a metal of Group 3, 4 or 5 of the periodic table, a lanthanoid or an actinoid metal. (B) at least one compound selected from (B1) to (B3), which reacts with (A) to form a stable ionic complex; (B1) aluminoxane; (B2) reacts with (A) (B3) Lewis acid compound which forms a stable ionic complex by reacting with (A) to form a stable ionic complex An unsaturated compound having 6 or more carbon atoms having an unsaturated bond with ethylene by using a catalyst comprising an organometallic compound of Group 1, 2 or 13 of the Periodic Table having at least one or more hydrocarbon residue, The rubber-modified styrenic copolymer resin composition according to claim 1, which is obtained by copolymerizing 3. The rubbery polymer according to claim 1, wherein a copolymer of a styrene monomer and a monomer copolymerizable with the styrene monomer is melt-mixed with the rubber polymer. 2
A method for producing the rubber-modified styrenic copolymer resin composition according to the above. 4. The rubbery polymer according to claim 1 is dissolved in a solution containing a styrene monomer and a monomer copolymerizable with the styrene monomer, and the solution is polymerized. A method for producing a rubber-modified styrenic copolymer resin composition obtained by dispersing rubber-like polymer particles obtained by the above method. 5. The rubbery polymer contains a styrene monomer, or a styrene monomer and a monomer copolymerizable with the styrene monomer when dispersing the rubber polymer particles. 5. The rubber-modified styrenic copolymer resin composition according to claim 4, wherein 0.0005 to 0.05 part by weight of an organic peroxide is added to 100 parts by weight of the solution dissolved in the solution and copolymerized. Method of manufacturing a product. 6. A rubber-modified styrenic copolymer resin composition obtained by the production method according to claim 3.