JPH10306182A - Rubber-modified styrene resin composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-modified styrene resin compsn. excellent in moldability and impact strength by dispersing particles of a rubberlike ethylene/α-olefin/diene random copolymer having specified ratios of constituting units in a styrene (co)polymer. SOLUTION: This compsn. is prepd. by dispersing particles of a rubberlike ethylene/α-olefin/diene random copolymer in a styrene homo- or copolymer. The rubberlike copolymer comprises ethylene units, α-olefin (e.g. propylene) units, and diene (e.g. 1,4-hexadiene) units, and in the copolymer, the content of diene unit is 0.1-50 wt.%; the molar ratio of ethylene unit to α-olefin unit is (90/10)-(50/50); and the ratio of the number of moles of the total unsatd. bonds (M) to the number of moles of diene unit (Mo) satisfies the relation: 0.1<M/Mo<0.9. The rubberlike copolymer is prepd. pref. by the copolymn. in the presence of a catalyst prepd. by using a transition metal compd. having a ligand having a cyclopentadienyl backbone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-modified styrenic resin composition and a method for producing the same. More specifically, the present invention relates to a rubber-modified styrenic resin composition using a specific rubber component and a method for producing the same.

[0002]

2. Description of the Related Art Polystyrene is excellent in molding processability. When molded, the appearance of the molded product, mechanical properties, electrical properties,
It is a resin with a good balance of dimensional stability and other properties.It is widely used in household electrical appliances and electronic equipment.However, styrene is used to improve the brittleness, chemical resistance, and abrasion resistance of polystyrene. Impact-resistant polystyrene is used, in which rubber is added to a copolymer of acrylonitrile and acrylonitrile and grafted to improve the impact resistance. Recently, it has come to be used for moldings having a large and more complicated shape and a small thickness. Under such circumstances, a rubber-modified styrene-based resin having excellent moldability and high impact strength has been demanded.

[0003] The rubber-modified styrene resin is obtained by dispersing rubber particles in a styrene resin. The properties of the rubbery polymer forming the dispersed rubber particles may have an important effect on product performance. Are known. As the rubbery polymer forming the dispersed rubber particles, polybutadiene rubber, styrene / butadiene rubber, and the like conventionally produced by a polymerization method such as anionic polymerization have been 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. The physical properties of a molded product have been improved by these methods, but they are not yet sufficient.

On the other hand, it has recently been proposed to copolymerize ethylene, propylene and diene in the presence of a transition metal compound having a ligand comprising a cyclopentadienyl skeleton and methylaluminoxane as a cocatalyst. It has been reported that a rubber having physical properties different from that of the above 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.

[0006]

The conventional method of improving the impact resistance by adding rubber to improve the physical properties of a rubber-modified styrenic resin is not always satisfactory as a method of improving the balance of physical properties. Was. There is a demand for the development of a rubber-modified styrenic polymer having improved physical property balance. An object of the present invention is to provide a rubber-modified styrenic resin having an improved balance of impact resistance.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on resins using various rubber-like polymers, and as a result, have found that a rubber-modified styrene resin composition has a specific property. When a rubber-modified styrene-based resin composition obtained by dispersing a rubber-like polymer in a homopolymer or a copolymer of a styrene-based monomer in the form of particles is used as a molded product, the performance of the molded product is excellent. And found that the present invention was completed.

That is, according to the present invention, rubber-like polymer particles are dispersed in a styrene monomer or a copolymer obtained by polymerizing a styrene monomer and a monomer copolymerizable with the styrene monomer. A rubber-modified styrenic resin composition, wherein the rubber-like polymer as a raw material for forming the rubber-like polymer particles is a random copolymer composed of ethylene, α-olefin, and diene,
In the copolymer of ethylene, α-olefin and diene, the content of the diene unit is in the range of 0.1 to 50% by weight, and α to the α-olefin and ethylene content.
The olefin content is 10 to 50 mol%, the ethylene content is 90 to 50 mol%, and the number of moles of unsaturated bonds (M) and the number of moles of diene units (M ₀ ) contained in the copolymer are as follows: A rubber-modified styrenic resin composition having a relationship represented by the following formula (Formula 2).

[0009]

(Equation 2) In the presence of a catalyst comprising a transition metal compound having a ligand consisting of a cyclopentadienyl skeleton and, if necessary, a cocatalyst, the rubbery polymer according to
-A rubber-modified styrene resin composition obtained by copolymerizing an olefin and a diene.

Is dissolved in a styrene monomer or a styrene monomer and a monomer copolymerizable with the styrene monomer, and the solution is polymerized to obtain a rubber polymer. A method for producing a rubber-modified styrenic resin composition, characterized in that the composition is obtained by granulating styrene.

The rubber-modified styrene-based polymer according to the above, wherein when the rubber-like polymer is formed into particles, 0.0005 to 0.05 parts by weight of an organic peroxide is added to 100 parts by weight of the solution in which the rubber-like polymer is dissolved. A method for producing a resin composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Styrene monomers used in the present invention include side chain alkyl-substituted styrenes such as styrene, α-methylstyrene and α-ethylstyrene: vinyltoluene, vinylxylene, and ot-butyl. Styrene, pt
-Alkyl-substituted styrenes such as -butylstyrene and p-methylstyrene: halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene: and p-hydroxystyrene, o
-Methoxystyrene and the like. Particularly preferably,
Styrene, α-methylstyrene, and p-methylstyrene. The styrene monomers may be used alone or in combination of two or more. Preferably, styrene, α-methylstyrene, p-methylstyrene or a mixture thereof is used.

In the present invention, the monomer copolymerizable with the styrene monomer used together with the styrene monomer is not particularly limited. For example, acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α
-Vinyl cyanide compound monomers such as chloroacrylonitrile: methyl methacrylate, ethyl methacrylate,
Methacrylate monomers such as propyl methacrylate and butyl methacrylate: acrylate monomers such as methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate: array amides such as maleimide, N-methylmaleimide and N-phenylmaleimide Monomers: Other monomers having an unsaturated group such as maleic anhydride, acrylamide, allylamine, acrylic acid and the like are mentioned, and acrylonitrile and methyl methacrylate are particularly preferable.

The proportion of the monomer which can be copolymerized with the styrene monomer which is a component of the copolymer of the present invention is not particularly limited, and may not be used. They can be selected so as to obtain desired physical properties in combination. Normally, when a monomer copolymerizable with a styrene monomer is used, its amount is preferably in the range of 5% to 95% of the monomer used. Also, a tertiary or quaternary copolymer in which a part is replaced with one or more other monomers in a proportion of 30% by weight or less based on the total amount of the monomers may be used.

The rubber-like polymer particles are formed by polymerizing the above-mentioned styrene-based monomer or a mixture of the above-mentioned monomers to which a predetermined amount of the rubber-like polymer described below has been added, so that a rubber-like polymer It can also be obtained by forming coalesced particles in a dispersed state.

[0016] The ethylene, α-
The copolymer of an olefin and a diene is obtained by copolymerizing ethylene, an α-olefin and a diene, and the α-olefin may have a linear or branched structure or a cyclic structure. 1, pentene-1,
Hexene-1, heptene-1, octene-1, decene-
Examples thereof include linear olefins such as 1, branched olefins such as methylpentene and methylhexene, and α-olefins having a cyclic structure such as cyclopentene, cyclohexene, norbornene, and vinylcyclohexane. The diene may be linear or branched, and may contain a hetero atom or atomic group such as oxygen, sulfur, and boron. For example, 1,3
-Butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 4-methyl-1,5-
Hexadiene, 1,6-heptadiene, 7-methyl-
1,6-octadiene, 1,7-octadiene, 1,8
-Nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,13-tetradecadiene, norbornadiene, vinylidene norbornene, ethylidene norbornene, divinylbenzene, divinylcyclohexane, cyclopentadiene, dicyclopentadiene, etc. Is exemplified.

The copolymer of propylene, ethylene and the above-mentioned diene can be conventionally synthesized using a catalyst comprising a transition metal compound and an organometallic compound, and titanium halide and an organometallic compound are used as the transition metal compound. Can be polymerized using a solid catalyst comprising an organoaluminum compound or a catalyst comprising an aluminoxane and a transition metal catalyst soluble in a hydrocarbon solvent, but a copolymer of an α-olefin and a diene other than ethylene and propylene is Polymerization is extremely difficult with a conventional catalyst system comprising a transition metal compound and an organometallic compound, and the copolymerization of propylene with ethylene and the above-described diene also has poor randomness of ethylene and propylene and poor copolymerizability with diene. ,
It was very difficult to control the structure of the copolymer according to the purpose.

On the other hand, the catalyst used in the polymerization in the present invention is a group 3 of the periodic table having a cyclopentadienyl compound represented by a combination of dicyclopentadienyl zirconium dichloride and aluminoxane as a ligand,
An activator comprising an aluminoxane compound which is a Group 4 or 5 transition metal compound, and which is obtained by reacting an organic aluminum with water or water of crystallization, if necessary, or a cyclopentadienyl compound Group 3, 4 and 5 of the Periodic Table
A catalyst in which an activator composed of a compound forming a stable anion with a metal cation complex of group III can be used.

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

As the transition metal compound, a compound represented by the above general formula (1, 2, 3) (formula 1) can be used.
This is specifically shown below. (A) The following general formula (1, 2, 3)

[0023]

(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 ) a group consisting of an unsaturated compound of the general formula (3) wherein A, B and C are bonded or coordinated to M, a cyclopentadienyl group or Its derivative groups, groups 13 and 14 of the periodic table,
A ligand consisting of a group in which a group 15 and group 16 heteroatom is bonded or coordinated to M, wherein A, B and C are bonded to each other by a single bond, a double bond or a combination thereof; May be. A, B and C are bonded or coordinated to M, and include A, B and C in which M is resonance-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 the third group of the periodic table, the fourth
Group 5, Group 5, lanthanoid or actinoid metals. Here, specific examples of the compound represented by the general formula (1) include the following. 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) (tetra (Methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl)
(Diethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentane Ethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, (cyclopentadienyl) (2,7-di-tertbutylfluorenyl) zirconium dichloride, (cyclopentadienyl) (octa (Hydrofluorenyl) zirconium dichloride, (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (t-butylcyclyl) Pentadienyl) zirconium dichloride, (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methylcyclopentadienyl) (2,7-di t-butyl fluorenyl)
Zirconium dichloride.

(Methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (methylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride , (Dimethylcyclopentadienyl) (2,7-di-t
(Butylfluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (ethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (ethylcyclopentadiyl) Enil) (4
-Methoxyfluorenyl) zirconium dichloride,
(Diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (diethylcyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (diethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (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, ethylenebis (1.2,3,4 tetramethylcyclopentadienyl)
Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, ethylene bis (ethylcyclopentadienyl) zirconium dichloride, bis (1,2 diethylcyclopentadienyl) zirconium dichloride, ethylene bis (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, ethylenebis (4-
Methyl-1-indenyl) zirconium dichloride,
Ethylene bis (5-methyl-1-indenyl) zirconium dichloride, bis (6-methyl-1-indenyl) zirconium dichloride, ethylene bis (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, ethylene bis (fluorenyl) zirconium dichloride, ethylene bis (4.5,6,7 tetrahydro-1-indenyl)
Zirconium dichloride, ethylene bis (fluorenyl) zirconium dichloride.

Ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride,
Ethylene (cyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, etherene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium Dichloride, ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadienyl) (diethylcyclopentadienyl) ) Zirconium dichloride, ethylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, ethylene (cyclopentadiene) 1) (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 Ride.

Ethylene (methylcyclopentadienyl)
(4-methoxyfluorenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (2,7-di-tbutylfluorenyl) zirconium dichloride, ethylene ( Dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (dimethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (Ethylcyclopentadienyl) (2,7
-Di-t-butylfluorenyl) zirconium dichloride, ethylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, ethylene (ethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene ( Diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (2,7-di-tertbutylfluorenyl) zirconium dichloride, ethylene (diethylcyclopentadienyl) (octahydrofluorenyl) Zirconium dichloride, ethylene (diethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (4,5-
Methylenephenanthrene) zirconium dichloride,
In addition, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a methylphenylmethylene group, a diphenylmethylene group, a 1,4-cyclopentane-di-ylidene group, a 1,4
-Cyclohexane-di-ylidene group, dimethylsilylene group, methylphenylsilylene group, diphenylsilylene group, dimethylgermylene group, dimethylstannylene group and the like are exemplified. A complex in which a zirconium atom is replaced with a titanium atom and a hafnium atom,
In addition, bromide, iodide,
Complexes changed to fluoride are mentioned.

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-dimethylcyclopentadienyl)
(3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2.4-dimethylcyclopentadienyl) (2,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (2 3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl)
(T-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, and the like.

Compounds having no cyclopentadienyl group include 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 2) and general formula (5)
(Formula 3)

[0034]

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

[0035]

Embedded image ^{([L 2] k +)} p ([Z] -) q ··· (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.

R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and 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 and 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.

[0043] 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.

As the component (B-1), an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex 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):

[0048]

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)

[0049]

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. 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.

When the catalyst component (A) and the catalyst component (B) are used in the polymerization catalyst, the molar ratio is preferably 10 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 the 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 as the component (C) is represented by the general formula (8):

[0057]

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 above 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: 10,0.
00, more preferably 1: 5 to 1: 2,000, further preferably 1:10 to 1: 1,000. By using the catalyst component (C), the polymerization activity per transition metal can be improved.
A large amount remains in the copolymer, which is not preferred.

In the present invention, at least the catalyst component
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
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.

As the co-catalyst, one or more of them can be used as a mixture.

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 200 ° C. and at a normal pressure to 50 kg / cm ² .

Usually, the molar ratio of ethylene to α-olefin in the rubbery polymer ethylene, α-olefin or diene copolymer obtained by such a method is 50/50 to 50/50.
Preferably it is in the range of 90/50 mol. α-olefin content of α-olefin and ethylene content is 1
If the amount is less than 0 mol%, the effect of improving the balance between the moldability and physical properties of the styrene-based resin is reduced. 50 mol%
Exceeding the range is not preferred because the properties and effects of the rubber are reduced.

The diene content is 0.1 to 50% by weight, preferably 1 to 30% by weight.

In the present invention, the bonding mode of the rubber-like polymer is important, and the number of moles of unsaturated bonds (M) and the number of moles of diene units (M ₀ ) contained in the rubber-like copolymer are represented by the following formula (M ₀ ). The feature is that the relationship is represented by Expression 3).

[0067]

(Equation 3) The mole number (M) of the unsaturated bond contained in the rubbery copolymer can be determined by calculating from the infrared absorption spectrum or NMR spectrum of the copolymer from the absorption spectrum of the unsaturated group. The diene content (M ₀ ) can be similarly calculated from the infrared absorption spectrum or NMR spectrum of the copolymer. However, based on the number of moles of the diene monomer supplied at the time of polymerization, the amount of unreacted monomer at the end of polymerization is determined. It can also be calculated from the difference in the number of moles.

When the relational expression (Equation 3) between the number of moles of unsaturated bonds (M) contained in the rubbery copolymer and the number of moles of diene units (M ₀ ) is less than 0.9, it means that Both double bonds react and both α-olefin and ethylene copolymers are bonded by diene, diene is bonded to each other, or diene is introduced in a cyclic structure. 0.1% of the diene
This is included, and the remaining unsaturated bonds of the diene do not undergo the above reaction.

The fact that the relational expression (Equation 3) between the number of moles of unsaturated bonds (M) contained in the rubbery copolymer and the number of moles of diene units (M ₀ ) exceeds 0.1 means that the diene When the two double bonds of both react with each other, a structure in which the α-olefin / ethylene copolymer is bonded by a diene, a structure in which diene is bonded to each other, or a diene introduced in a cyclic structure of diene is 0.9%. It is included below.

According to the present invention, a molded article having a good balance between rigidity and impact resistance can be produced by molding by a method generally used for molding polystyrene such as injection molding. The molding temperature is not particularly limited and can be a normal molding temperature, and is usually 160 to 300 ° C. There is no particular limitation on the method of mixing the above components, or a method of mixing with known additives such as an antioxidant, an ultraviolet absorber, a lubricant, an antistatic agent, or another nucleating agent, if necessary. It is preferable that the components are mixed with a Henschel mixer, a V-type blender or the like, then melt-mixed with an extruder or a roll, a Banbury mixer, a kneader or the like, and granulated once to form pellets.

In the present invention, the rubbery polymer is dissolved in a styrene monomer or a mixture of a styrene monomer and a monomer copolymerizable with the styrene monomer, and the solution is polymerized. It is also possible to produce a rubber-modified styrenic resin composition. As a polymerization method, a solution prepared by dissolving a rubber-like polymer in a styrene-based monomer or a mixture of a styrene-based monomer and a monomer copolymerizable with a styrene-based monomer is subjected to bulk polymerization or bulk suspension in two steps. It is obtained by polymerization by a polymerization method or the like, but the polymerization method is not particularly limited, and is produced by thermal polymerization or catalytic polymerization.

The rubber solution may contain a solvent such as ethylbenzene, methylene chloride and methyl ethyl ketone so that the rubber can be easily dissolved.

In the present invention, it is not necessary to use a polymerization initiator when granulating the rubber-like polymer, but it is more preferable to use it. When an organic peroxide is used as the polymerization initiator, it is preferable to use 0.0005 to 0.05 parts by weight of the organic peroxide with respect to 100 parts by weight of the solution in which the rubbery polymer is dissolved. Use of more than 0.05 parts by weight is not preferable because some giant particles are generated and the surface condition of the molded product may be deteriorated.

The rubber-modified styrenic resin composition of the present invention may optionally contain an antioxidant such as a hindered phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, etc.
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.

[0075]

The present invention will be specifically described below with reference to examples.

Evaluation of physical properties Izod impact strength: Measured according to JIS K-6871.

Example 1 [Synthesis of α-olefin / ethylene / diene copolymer]
50 liters of toluene was placed in a 200 liter stainless steel autoclave, 1,4-hexadiene and propylene were introduced while maintaining the temperature at 20 ° C., 100 mmol of triisobutylaluminum was further introduced, and ethylene gas was further introduced at 20 ° C. 3kg / cm ² −
A solution prepared by dissolving 1 mmol of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride in toluene synthesized according to a conventional method was added as G, and N, N'-dimethylanilinium, tetrakis Mooney viscosity ML 1 _{+ 4 was} obtained by adding 2 mmol of (pentafluorophenyl) borate, introducing ethylene gas, and keeping the pressure constant at 3 kg / cm ² -G, heating to 80 ° C. and polymerizing for 90 minutes.
(100 ° C.) is 28, the content of diene units in the copolymer is 4.5% by weight, the propylene content relative to the total of propylene and ethylene is 35 mol%, and the ethylene content is 65 mol%
A rubbery polymer was obtained in which the molar number of unsaturated bonds (M) contained in the copolymer / the molar number of diene units (M ₀ ) was 0.85.

[Synthesis of Rubber-Modified Styrenic Resin Composition]
A rubber-modified styrenic resin was produced using a continuous bulk polymerization apparatus comprising three reactors with a stirrer connected in series. In a first reactor equipped with a stirrer, 4.2 parts by weight of the rubbery polymer obtained above, 15 parts by weight of ethylbenzene, 79 parts by weight of styrene, and 1,1-bis (t-butyl) as an organic peroxide. A raw material liquid containing 0.005 parts by weight of (peroxy) 3,3,5-trimethylcyclohexane was continuously supplied and polymerized to obtain a rubber-modified styrene resin composition. Table 1 shows the measurement results of physical properties of the obtained polymer.

Example 2 A rubbery polymer was synthesized in the same manner as in Example 1 except that ethylidene norbornene was used instead of 1,4-hexadiene. The rubbery polymer obtained had a Mooney viscosity ML _{1 + 4} (100 ° C.) of 22, a diene unit content of the copolymer of 4.0% by weight, a propylene content of 40 mol% based on the total of propylene and ethylene, and The content was 60 mol%, and the number of moles of unsaturated bonds (M) / the number of moles of diene units (M ₀ ) contained in the copolymer was 0.80.

Using the obtained rubber-like polymer, a rubber-modified styrene resin was synthesized in the same manner as in Example 1 using a bulk polymerization apparatus. Table 1 shows the measurement results of the physical properties of the obtained polymer.
Shown in

Example 3 In Example 1, butene-1 was used instead of propylene.
A rubbery polymer was synthesized in the same manner as in Example 1 except for
Was. The resulting rubbery polymer has Mooney viscosity ML _{1 + 4}(1
(00 ° C.) is 20 and the content of diene units in the copolymer is 4.2.
Wt%, butene-based on the sum of butene-1 and ethylene
1 content was 12 mol%, and ethylene content was 88 mol%.
The number of moles of unsaturated bonds (M) contained in the copolymer /
Number of moles of diene unit (M₀) Was 0.82.

Using the obtained rubber-like polymer, a rubber-modified styrene resin was synthesized in the same manner as in Example 1 using a bulk polymerization apparatus. Table 1 shows the measurement results of the physical properties of the obtained polymer.
Shown in

Example 4 Using 9.5 parts by weight of the rubbery polymer obtained in Example 2, 15 parts by weight of ethylbenzene and a mixed solution of styrene and acrylonitrile (acrylonitrile 2
A rubber-modified styrene resin was produced in the same manner as in Example 1 except that 75 parts by weight (containing 5% by weight) was used. Table 1 shows the measurement results of physical properties of the obtained polymer.

Comparative Example 1 Polystyrene containing no propylene / ethylene / diene copolymer (525-5 manufactured by Mitsui Toatsu Chemicals, Inc.)
Table 1 shows the physical property measurement results of 1).

[0085]

[Table 1]

[0086]

Industrial Applicability The rubber-modified styrene resin composition of the present invention has an excellent balance between impact strength and appearance, and has a great industrial value in applications of component materials such as home electric appliances and electronic equipment. Things.

Claims (4)

[Claims] A rubber-like polymer particle is dispersed in a copolymer obtained by polymerizing a styrene-based monomer or a styrene-based monomer and a monomer copolymerizable with a styrene-based monomer. A rubber-modified styrenic resin composition, wherein the rubbery polymer as a raw material for forming the rubbery polymer particles is a random copolymer comprising ethylene, an α-olefin, and a diene, wherein the ethylene and the α- In the copolymer of olefin and diene, the content of the diene unit is 0.1 to 5;
0 to 10% by weight based on the α-olefin and ethylene content.
The ethylene content is 90 to 50 mol%, and the number of moles of unsaturated bonds (M) and the number of moles of diene units (M ₀ ) contained in the copolymer are represented by the following formula (Formula 1). A rubber-modified styrenic resin composition characterized in that: (Equation 1) 2. The rubber-like polymer according to claim 1, wherein the transition metal compound having a ligand comprising a cyclopentadienyl skeleton and, if necessary, ethylene and a catalyst comprising a promoter. A rubber-modified styrene resin composition obtained by copolymerizing an α-olefin and a diene. 3. The rubbery polymer according to claim 1 is dissolved in a styrene monomer or a styrene monomer and a monomer copolymerizable with the styrene monomer, and the solution is polymerized. A method for producing a rubber-modified styrenic resin composition, characterized in that the rubbery polymer is obtained by granulating a rubber-like polymer. 4. The method according to claim 3, wherein when the rubbery polymer is formed into particles, 0.0005 to 0.05 parts by weight of an organic peroxide is added to 100 parts by weight of the solution in which the rubbery polymer is dissolved. A method for producing a rubber-modified styrenic resin composition of the above.