JP4335092B2 - Propylene elastomer - Google Patents

Description

  The present invention relates to a novel propylene-based elastomer that is excellent in transparency, rigidity, and heat sealability and particularly excellent in impact absorption, and is suitable as a compounding agent for resins.

  Propylene-based elastomers obtained by copolymerizing propylene, 1-butene and ethylene are used for films, sheets and the like because they are excellent in transparency, impact absorption, heat sealability and the like.

  Such propylene-based elastomers are generally manufactured using a solid titanium-based catalyst, but conventional propylene-based elastomers have further improved impact absorption and transparency in applications such as resin modifiers. Was desired.

  The present inventors have studied propylene-based elastomers in view of such conventional techniques, and include units derived from propylene, 1-butene and ethylene at a specific ratio, and have a small molecular weight distribution (Mw / Mn). It has been found that the propylene / 1-butene / ethylene elastomer is excellent in transparency, rigidity, heat sealability and the like, and has an excellent impact absorption compared to a conventionally known propylene elastomer. And it discovered that this propylene-type elastomer can be manufactured using a specific metallocene compound catalyst component, and came to complete this invention.

  An object of the present invention is to provide a novel propylene / 1-butene / ethylene copolymer elastomer that is excellent in transparency, rigidity, and heat sealability and particularly excellent in shock absorption and is suitable as a compounding agent for resins. It is said.

The propylene-based elastomer according to the present invention is
(1) (a) a unit derived from propylene in an amount of 50 to 85 mol%, (b) a unit derived from 1-butene in an amount of 5 to 40 mol%, and (c) a unit derived from ethylene. The amount of units contained from 10 to 40 mol% and derived from 1-butene is greater than the amount of units derived from ethylene;
(2) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3 or less.

  The propylene-based elastomer according to the present invention as described above is [A] a transition metal compound represented by the following general formula [I];

[Wherein, M is a transition metal atom of Group IVB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon A halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of the groups adjacent to each other is bonded to bond these groups A ring may be formed together with carbon atoms to be formed, and X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or divalent. Silicon-containing group, divalent germanium-containing group, divalent tin-containing group,- O—, —CO—, —S—, —SO—, —SO ₂ —, —NR ⁵ —, —P (R ⁵ ) —, —P (O) (R ⁵ ) —, —BR ⁵ — or — AlR ⁵ —. (Wherein R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms)];
[B] a compound capable of activating the transition metal compound [A], and
(B-1) an organoaluminum compound,
(B-2) an organoaluminum oxy compound, and
(B-3) Propylene, 1-butene and ethylene in the presence of an olefin polymerization catalyst containing at least one compound selected from compounds which react with the transition metal compound [A] to form ion pairs. Can be obtained by copolymerization.

  The transition metal compound [A] is preferably represented by the following formula [II].

(In the formula, M, R ¹ , R ³ , X ¹ , X ² and Y are as defined in the formula [I], and R ^{21 to} R ²⁴ and R ^{41 to} R ⁴⁴ are a hydrogen atom, a halogen atom, An alkyl group or an aryl group, and the alkyl group or aryl group may be substituted with a halogen or an organic silyl group, and adjacent substituents may form a ring).

  The propylene-based elastomer as described above may be graft-modified with a polar monomer. The propylene elastomer according to the present invention can be suitably used as a compounding agent for resins.

  The propylene-based elastomer according to the present invention is excellent in transparency, rigidity, heat resistance, and heat sealability, and particularly excellent in shock absorption. Furthermore, this modified product of propylene-based elastomer is excellent in adhesion to metals or polar resins.

  Such a propylene-based elastomer according to the present invention can be used for a wide range of applications such as films and sheets, but is particularly suitable as a compounding agent for resins.

Hereinafter, the propylene-based elastomer according to the present invention will be specifically described.
(1) Composition The propylene-based elastomer according to the present invention is a random copolymer of propylene, 1-butene and ethylene,
(a) a unit derived from propylene in an amount of 50 to 85 mol%,
(b) a unit derived from 1-butene in an amount of 5-40 mol%, preferably 7-40 mol%, more preferably 10-35 mol%,
(c) containing 10 to 40 mol% of units derived from ethylene;
And contains more units (b) derived from 1-butene than units (c) derived from ethylene.

This propylene elastomer may contain a small amount of units derived from olefins other than propylene, 1-butene and ethylene, for example, in an amount of 10 mol% or less.
(2) Intrinsic viscosity [η]
The intrinsic viscosity [η] (measured at 135 ° C. in decalin) of the propylene elastomer according to the present invention is 0.1-12 dl / g, preferably 0.5-12 dl / g, more preferably 1-12 dl / g. It is.

(3) Molecular weight distribution The molecular weight distribution (Mw / Mn) of the propylene elastomer according to the present invention is 3 or less, preferably 2.0 to 3.0, more preferably 2.0 to 2.5. This molecular weight distribution can be determined by gel permeation chromatography GPC.

(4) Melting point The melting point Tm of the propylene elastomer according to the present invention is preferably 25 to 85 ° C. This melting point can be measured by a differential scanning calorimeter.

(5) Crystallinity The crystallinity of the propylene elastomer according to the present invention is preferably 15% to 45%. This crystallinity can be measured by an X-ray diffraction method.

The propylene-based elastomer according to the present invention as described above is
[A] a specific transition metal compound as described below;
[B] a compound capable of activating the transition metal compound [A], and
(B-1) an organoaluminum compound,
(B-2) an organoaluminum oxy compound, and
(B-3) Propylene, 1-butene and ethylene in the presence of an olefin polymerization catalyst containing at least one compound selected from compounds which react with the transition metal compound [A] to form ion pairs. Can be obtained by copolymerization.

  The olefin polymerization catalyst used in the present invention will be described below. The transition metal compound [A] used in the present invention is represented by the following general formula [I].

  In the formula, M is a transition metal of groups IV to VIB of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, zirconium, Hafnium, particularly preferably zirconium.

Substituents R ^{1 to} R ⁴
R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, a silicon-containing group, It may be an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of groups adjacent to each other may be bonded to form a ring together with the carbon atom to which these groups are bonded. Each of R ^{1 to} R ^{4, which} is represented by 2 each, indicates that it is preferable to combine them by a combination of the same symbols when they are combined to form a ring. For example, R ¹ and R ¹ It is shown that it is preferable to combine with each other to form a ring.

Specifically, examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl and octyl. Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl, adamantyl,
Alkenyl groups such as vinyl, propenyl, cyclohexenyl,
Arylalkyl groups such as benzyl, phenylethyl, phenylpropyl,
Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, And aryl groups such as biphenylyl.

  Rings formed by combining these hydrocarbon groups include condensed rings such as benzene, naphthalene, acenaphthene and indene, and hydrogen on condensed rings such as benzene, naphthalene, acenaphthene and indene. Examples include groups in which an atom is substituted with an alkyl group such as methyl, ethyl, propyl, or butyl.

These hydrocarbon groups may be substituted with halogen.
Silicon-containing groups include monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenyl Trihydrocarbon-substituted silyl such as silyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether, silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylphenyl Etc.

  Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

  The sulfur-containing group includes a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Phosphonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate and other sulfonate groups, methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate And sulfinate groups such as trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

  Nitrogen-containing groups include amino groups, alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino, and aryls such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. An amino group or an alkylarylamino group is exemplified.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.
X ¹ and X ²
X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, an oxygen-containing group or a sulfur-containing group. Specific examples of these atoms or groups include the same atoms and groups as those represented by R ^{1 to} R ⁴ .

Y
Y is a C1-C20 divalent hydrocarbon group optionally substituted with halogen, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-,- CO -, - S -, - SO -, - SO 2 -, - NR 5 -, - P (R 5) -, - P (O) (R 5) -, - BR 5 - or -AlR ⁵ - with is there. (Wherein, R ⁵ is a hydrogen atom, a hydrocarbon group similar to the above halogen atoms, having 1 to 20 carbon atoms which may be substituted with a halogen.)
Specifically, the divalent hydrocarbon group having 1 to 20 carbon atoms includes methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene. Examples include alkylene groups such as methylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. Moreover, the halogenated hydrocarbon group etc. which halogenated said C1-C20 bivalent hydrocarbon group, such as chloromethylene, are mentioned.

Divalent silicon-containing groups include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p -Tolyl) silylene, alkylsilylene such as di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene groups, tetramethyl-1,2-disilyl, alkyldisilyl such as tetraphenyl-1,2-disilyl, alkylaryl Examples thereof include disilyl and aryldisilyl groups.

  Examples of the divalent germanium-containing group and the divalent tin-containing group include compounds in which silicon of the divalent silicon-containing group is replaced with germanium or tin. Specific examples of such a compound represented by the formula [I] are shown below.

Bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, Bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (neopentylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (1-cyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis {1- ( 3-methylcyclopentadienyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,4-dimethylcyclopentadienyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3, Five -Trimethylcyclopentadienyl)}
Zirconium dichloride etc.

  In the present invention, among the transition metal compounds represented by the formula [I], a compound represented by the following formula [II] is preferably used.

(In the formula, M, R ¹ , R ³ , X ¹ , X ² and Y are as defined in the formula [I], and R ^{21 to} R ²⁴ and R ^{41 to} R ⁴⁴ are a hydrogen atom, a halogen atom, An alkyl group or an aryl group, and the alkyl group or aryl group may be substituted with a halogen or an organic silyl group, and adjacent substituents may form a ring).

Specific examples of such a compound represented by the formula [II] are shown below.
rac-ethylene-bis (1-indenyl) zirconium dichloride,
rac-ethylene-bis (1-indenyl) zirconium dibromide,
rac-ethylene-bis (1-indenyl) dimethylzirconium,
rac-ethylene-bis (1-indenyl) diphenylzirconium,
rac-ethylene-bis (1-indenyl) methylzirconium monochloride,
rac-ethylene-bis (1-indenyl) zirconium bis (methanesulfonate),
rac-ethylene-bis (1-indenyl) zirconium bis (p-toluenesulfonate),
rac-ethylene-bis (1-indenyl) zirconium bis (trifluoromethanesulfonate),
rac-ethylene-bis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis (1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (i-propyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (n-butyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-Di (cyclohexyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)
} Zirconium dichloride,
rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylenebis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-Dimethylsilylenebis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium- (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-α-acenaphthoindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl)
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis (2-phenyl-4-phenylindenyl)) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (p-toluenesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (methylsulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfinate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoroacetate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (n-butoxide),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (n-butoxide),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (phenoxide),
rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (8-methyl-9-naphthyl) indenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biferinyl) indenyl)} zirconium dichloride,
rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-ethylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylgermylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-n-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride and the like.

  In the present invention, transition metal compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten in the compounds as described above can also be exemplified.

  The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but R-type or S-type can also be used. In the present invention, the above transition metal compounds may be used in combination.

  In the present invention, (B-1) an organoaluminum compound, (B-2) an organoaluminum oxy compound as a compound [B] (hereinafter also referred to as component [B]) that can activate the transition metal compound [A]. And (B-3) at least one compound selected from compounds that react with the transition metal compound [A] to form an ion pair is used.

The organoaluminum compound (B-1) used in the present invention is represented by, for example, the following general formula [IV].
R ¹ _n AlX _3-n ... [IV]
(In Formula [IV], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3).
In the above general formula [IV], R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically includes a methyl group, an ethyl group, and n-propyl group. Group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As such an organoaluminum compound (B-1), specifically,
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum,
Alkenyl aluminum such as isoprenyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide,
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide,
Examples thereof include alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound (B-1), a compound represented by the following general formula [V] can also be used.
R ¹ _n AlY _3-n ... [V]
(In the formula [V], R ¹ is the same as above, and Y is —OR ² group, —OSiR ³ ₃ group, —OAlR ⁴ ₂ group, —NR ⁵ ₂ group, —SiR ⁶ ₃ group or —N ( R ⁷ ) AlR ⁸ ₂ group, n is 1 to ² , R ² , R ³ , R ⁴ and R ⁸ are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ⁶ and R ⁷ are a methyl group, an ethyl group, etc.)
Specific examples include the following compounds.
(1) Compounds represented by R ¹ _n Al (OR ² ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide,
(2) Compounds represented by R ¹ _n Al (OSiR ³ ₃ ) _3-n , such as Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc.
(3) Compounds represented by R ¹ _n Al (OAlR ⁴ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂ ,
(4) Compounds represented by R ¹ _n Al (NR ⁵ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlN
HMe, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ , (5) a compound represented by R ¹ _n Al (SiR ⁶ ₃ ) _3-n , For example, (iso-Bu) ₂ AlSi Me ₃
(6) R ¹ _n Al (N (R ⁷ ) AlR ⁸ ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso -Bu) ₂ etc.

Of these, compounds represented by the general formulas R ¹ ₃ Al, R ¹ _n Al (OR ² ) _{3 -n} , R ¹ _n Al (OA ¹ R ⁴ ₂ ) _{3 -n} are preferred, and R is particularly an isoalkyl group. , N = 2 is preferred.

  These can also be used in combination. The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known benzene-soluble aluminoxane, or a benzene-insoluble organoaluminum oxy compound as disclosed in JP-A-2-276807. It may be a compound.

The aluminoxane as described above can be produced, for example, by the following method.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with the suspension of the hydrocarbon medium.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound by distillation from the recovered solution of the above aluminoxane, it may be redissolved in the solvent.

Specific examples of the organoaluminum compound used for producing the aluminoxane include the same compounds as those described above as the organoaluminum compound (B-1).
Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferred. The organoaluminum compound (B-2) can also be used in combination.

  Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, petroleum fractions such as gasoline, kerosene, light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, among others , Hydrocarbon solvents such as chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligrams of Al in 100 ml of benzene, mixing at 60 ° C. for 6 hours with stirring, and then attaching a jacket. Using a G-5 glass filter, hot filtration was performed at 60 ° C., and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the Al atoms present in the total filtrate were removed. It is determined by measuring the abundance (x mmol) (x%).

  The compound (B-3) (hereinafter also referred to as component (B-3)) that reacts with the transition metal compound [A] used in the present invention to form an ion pair is disclosed in JP-A-1-501950. Lewis described in Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-547718, etc. Mention may be made of acids, ionic compounds and carborane compounds.

Lewis acids include triphenylboron, tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, tris (pentafluorophenyl) ) boron, and the like _{MgCl 2, Al 2 O 3,} SiO 2 -Al 2 O 3.

  Examples of ionic compounds include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra And (pentafluorophenyl) borate.

The carborane compounds include dodecaborane, 1-carbaundecaborane, bis n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundaca) borate, tri-n-butylammonium (trideca Hydride-7-carbaoundeca) borate and the like.

  These can also be used in combination of two or more. In the present invention, the compound (B-1), (B-2) or (B-3) as described above may be used in combination as the compound [B] capable of activating the transition metal compound [A]. it can.

  The olefin polymerization catalyst used in the present invention can be prepared by mixing the transition metal compound [A] and the component [B] as described above in an inert hydrocarbon solvent or an olefin solvent.

  Examples of the inert hydrocarbon solvent used for the preparation of the olefin polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and hexadecane, cyclopentane, cyclohexane, and methylcyclopentane. , Alicyclic hydrocarbons such as cyclooctane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, petroleum fractions such as gasoline, kerosene and light oil, or these A mixture or the like can be used.

In preparing the catalyst from each of these components, the transition metal compound [A] is used at a concentration of about 10 ⁻⁸ to 10 ⁻¹ mol / liter (polymerization volume), preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter. It is desirable to use it.

When (B-1) and / or (B-2) is used as component [B], the atomic ratio of aluminum in component [B] to the transition metal of transition metal compound [A] (Al / transition metal) ) And is usually used in an amount of 10 to 10000, preferably 20 to 5000. When this organoaluminum compound (B-1) and organoaluminum oxy compound (B-2) are used in combination, the aluminum atom (Al-1) in (B-1) and the aluminum atom in (B-2) It is desirable that the atomic ratio (Al-1 / Al-2) of (Al-2) is 0.02 to 3 and further 0.05 to 1.5.

  When (B-3) is used as component [B], the molar ratio of transition metal compound [A] to component (B-3) ([A] / (B-3)) is usually 0. 0.01 to 10 is preferably used in an amount of 0.1 to 5.

Each of the above catalyst components may be mixed in a polymerization vessel, or those previously mixed may be added to the polymerization vessel.
When these components are mixed in advance, they can be contacted at a temperature of usually −50 to 150 ° C., preferably −20 to 120 ° C. for 1 minute to 50 hours, preferably 5 minutes to 25 hours. Further, the mixing temperature may be changed during the mixing contact.

  The olefin polymerization catalyst used in the present invention may be a solid olefin polymerization catalyst in which at least one of the above components [A] and [B] is supported on a granular or fine particle solid (carrier).

This carrier may be an inorganic carrier or an organic carrier. As the inorganic carrier, for example, porous oxides such as SiO ₂ and Al ₂ O ₃ are preferably used. Examples of the organic carrier include those having 2 to 1 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene.
A (co) polymer produced mainly from an α-olefin of 4 or a polymer or copolymer produced mainly from vinylcyclohexane or styrene can be used.

  The olefin polymerization catalyst used in the present invention can also be used after forming a prepolymerized catalyst by prepolymerizing each catalyst component with an olefin. As the olefin used for the prepolymerization, olefins such as propylene, ethylene and 1-butene are used, but these and other olefins may be used in combination.

  In the present invention, when forming the olefin polymerization catalyst, in addition to the above components, other components useful for olefin polymerization, such as water as a catalyst component, can be used.

  The propylene-based elastomer of the present invention can be produced by copolymerizing propylene, 1-butene and ethylene in the presence of the olefin polymerization catalyst as described above so that the final composition ratio is obtained. it can.

  The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or solution polymerization, or a gas phase polymerization method. In the liquid phase polymerization method, the same inert hydrocarbon solvent used in the catalyst preparation described above can be used, and propylene can also be used as a solvent.

When the polymerization is carried out by the suspension polymerization method, the temperature is from -50 to 100 ° C, preferably from 0 to 90 ° C. When the polymerization is carried out by the solution polymerization method, from 0 to 250 ° C, preferably from 20 to 200 ° C. It is desirable to carry out at temperature. When the polymerization is carried out by gas phase polymerization method, at a temperature of 0 to 120 ° C. Preferably 20 to 100 ° C., atmospheric pressure to 100 kg / cm ² preferably conducted under a pressure of normal pressure to 50 kg / cm ² desirable.

  The polymerization can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting propylene-based elastomer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature and the polymerization pressure.

Modified Propylene Elastomer In the present invention, the above propylene elastomer may be graft-modified with a polar monomer.

  Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, chlorides. Vinyl etc. are mentioned.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (
(Meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, (Meth) acrylic acid esters such as butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate,
10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, Examples include glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

  Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.

(Wherein R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, preferably 6 to 12 carbon atoms, preferably And a cycloalkyl group having 6 to 8. The above alkyl group and cycloalkyl group may further have a substituent.
Examples of such amino group-containing ethylenically unsaturated compounds include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenylamino methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as ethyl and cyclohexylaminoethyl methacrylate
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine Allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N -Acrylamide derivatives such as methylacrylamide
Aminostyrenes such as p-aminostyrene
Examples include 6-aminohexyl succinimide and 2-aminoethyl succinimide.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one unsaturated bond polymerizable in one molecule and at least one epoxy group is used. As such an epoxy group-containing ethylenically unsaturated compound, for example,
Glycidyl acrylate, glycidyl methacrylate, etc.
Mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, mono- and diglycidyl esters of tetrahydrophthalic acid, mono- and glycidyl esters of itaconic acid, mono-butenetricarboxylic acid And diglycidyl esters, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid ^TM
) Mono- and diglycidyl esters, endo-cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ) mono- and diglycidyl esters, allyl succinic acid Mono- and glycidyl esters of dicarboxylic acids such as mono- and glycidyl esters (C1-C12 of alkyl groups in the case of mono-glycidyl esters), alkyl glycidyl esters of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether , Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3- Examples include methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide.

  The aromatic vinyl compound is represented by the following formula.

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. R ³ is an alkyl group having 1 to ³ carbon atoms. A hydrocarbon group or a halogen atom, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, and a chlorine atom, a bromine atom, or an iodine atom, where n is usually 0 to 5, preferably 1 to 5. (It is an integer.)
Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4 -Vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N- Examples include vinyl pyrrolidone.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept- Examples thereof include unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).

Examples of this derivative include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Product, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Examples thereof include dimethyl acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.

Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferable.
Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, pt- Examples include vinyl butyl benzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate.

Preparation of Modified Propylene Elastomer The modified propylene elastomer according to the present invention is obtained by graft polymerization of a polar monomer on the propylene elastomer as described above.

  When the above polar monomer is graft-polymerized to the propylene elastomer, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the propylene elastomer. used.

This graft polymerization is usually carried out in the presence of a radical initiator. As the radical initiator, an organic peroxide or an azo compound can be used.
Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5 -Bis (t-
(Butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, acetylperoxy Oxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide, etc. It is done.

  Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile. The radical initiator is desirably used in an amount of about 0.001 to 10 parts by weight with respect to 100 parts by weight of the propylene-based elastomer.

The radical initiator can be used as it is mixed with a propylene-based elastomer and a polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. As this organic solvent, any organic solvent capable of dissolving the radical initiator can be used without particular limitation. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, octane. , Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and Chlorinated hydrocarbons such as tetrachloroethylene, alcohol solvents such as methanol, ethanol, n-propinol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone solvents such as down, ester solvents, dimethyl ether, diethyl ether, such as ethyl acetate and dimethyl phthalate, di -n- amyl ether, can be used ether solvents such as tetrahydrofuran and dioxy anisole.

  In addition, when a polar monomer is graft-polymerized to the propylene-based elastomer, a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.

Reducing substances include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine, hydrazine, and further —SH, SO ₃ H, —NHNH ₂ , —COCH (OH) And compounds containing a group such as-.

  Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride, cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, and ethyl mercaptan. Benzenesulfonic acid, p-toluenesulfonic acid, and the like.

In the present invention, the reducing substance can be used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the propylene-based elastomer.
Graft modification of the propylene-based elastomer with a polar monomer can be performed by a conventionally known method. For example, the propylene-based elastomer is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. The reaction can be carried out preferably by reacting at a temperature of 80 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours.

  The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the propylene-based elastomer. For example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, and heptane. A solvent or the like can be used.

Further, a modified propylene elastomer can be produced by reacting a propylene elastomer and a polar monomer in the absence of a solvent using an extruder or the like. This reaction is usually at or above the melting point of the propylene elastomer, specifically at a temperature of 120 to 250 ° C., usually 0.5.
It is desirable to be performed for 10 minutes.

  The modified amount of the modified propylene elastomer thus obtained (polar monomer graft amount) is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight, more preferably 0.2 to 10% by weight. % Is desirable.

〔Example〕
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

In the following examples, the physical properties of the elastomer were measured as follows.
(1) Composition
^It calculated | required using < ¹³ > C-NMR.

(2) Intrinsic viscosity [η]
Measured in 135 ° C decalin.
(3) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Millipore.

The separation column is TSK GNH HT, the column size is 27 mm in diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and BHT ( (Takeda Pharmaceutical Co., Ltd.) was used at 0.025 wt%, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, the sample injection amount was 500 microliters, and a differential refractometer was used as the detector. Standard polystyrenes were manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and pressure chemicals were used for 1000 <Mw <4 × 10 ⁶ .

(4) Melting point (Tm)
About 5 mg of elastomer sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, and then heated at 10 ° C./minute. It was obtained from the endothermic curve. For the measurement, a DSC-7 type apparatus manufactured by Perkin Elmer was used.

(5) Crystallinity Immediately after the elastomer was hot pressed at 200 ° C. using a spacer of 200 mm × 200 mm (thickness 1 mm), it was cooled for 5 minutes under a load of 100 kg / cm ² with a cooling press at 20 ° C. After a week, X-ray diffraction was measured.

(6) Young's modulus ASTM D638 TYPE IV dumbbells were punched from the 200 mm x 200 mm (1 mm thick) elastomer sheet prepared in (5) above, and the chuck distance was 64 mm using an Instron universal testing machine. The initial elastic modulus (kgf / cm ² ) obtained as a Young's modulus was obtained from the obtained load-elongation curve using a tangential auxiliary line.

E = (F ₁ / A) × (L ₀ / L ₁ )
E ... Initial elastic modulus (= Young's modulus)
F ₁ ... Load at an arbitrary point on the auxiliary line (kgf)
L ₁ ... growth for the F _i of the auxiliary line (cm)
L ₀ ... Chuck distance (cm)
A: Original minimum cross-sectional area of the test piece (cm ² )
(7) Izod impact strength (IZ)
Measured according to ASTM D256.

A 2 liter autoclave thoroughly purged with nitrogen is charged with 950 ml of hexane and 50 g of 1-butene, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene and ethylene are supplied, and the total pressure is 7 kg / cm ² G, 0.330 mmol of methylaluminoxane, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride in terms of Zr atom, 0.001 Polymerization was carried out for 30 minutes while maintaining a total pressure of 7 kg / cm ² G by continuously supplying a molar ratio of 95: 5 with propylene and ethylene. After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

The obtained polymer (propylene-based elastomer) was 28.0 g, and the polymerization activity was 56.
kg · polymer / mmol Zr · hr. This polymer contained 15.3 mol% units derived from 1-butene and 15.1 mol% units derived from ethylene. The intrinsic viscosity [η] was 2.4 dl / g.

  Table 1 shows the measured physical properties of the obtained polymer.

In Example 1, propylene, ethylene and 1-butene were copolymerized in the same manner as in Example 1 except that 60 g of 1-butene was charged.
The obtained polymer (propylene elastomer) was 24.1 g, and the polymerization activity was 48.
kg · polymer / mmol Zr · hr. This polymer contained 20.0 mol% of units derived from 1-butene and 15.0 mol% of units derived from ethylene. The intrinsic viscosity [η] was 2.3 dl / g.

  Table 1 shows the measured physical properties of the obtained polymer.

In Example 1, propylene, ethylene and 1-butene were copolymerized in the same manner as in Example 1 except that 65 g of 1-butene was charged.
The obtained polymer (propylene elastomer) was 22.1 g, and the polymerization activity was 44.
kg · polymer / mmol Zr · hr. The polymer contained 24.9 mole percent units derived from 1-butene and 15.2 mole percent units derived from ethylene. The intrinsic viscosity [η] was 2.2 dl / g.

  Table 1 shows the measured physical properties of the obtained polymer.

In Example 1, propylene, ethylene and 1-butene were copolymerized in the same manner as in Example 1 except that 70 g of 1-butene was charged.
The obtained polymer (propylene elastomer) was 20.0 g, and the polymerization activity was 40
kg · polymer / mmol Zr · hr. This polymer contained 30.0 mol% units derived from 1-butene and 15.0 mol% units derived from ethylene. The intrinsic viscosity [η] was 2.2 dl / g.

  Table 1 shows the measured physical properties of the obtained polymer.

[Preparation of modified propylene-based elastomer]
Using toluene as the reaction solvent, 825 g of the propylene-based elastomer obtained in Example 1 per 5.7 liter of toluene was dissolved at 160 ° C.

To this solution was then slowly fed maleic anhydride in toluene (4.13 g / 250 ml) and dicumyl peroxide in toluene (0.33 g / 50 ml) from separate conduits over 4 hours.

  After completion of the supply, the reaction was further continued at 160 ° C. for 30 minutes, and then cooled to room temperature to precipitate a polymer. The precipitated polymer was filtered, repeatedly washed with acetone, and dried under reduced pressure at 80 ° C. overnight to obtain the desired modified propylene elastomer.

Elemental analysis was performed on this modified propylene-based elastomer, and the amount of maleic anhydride grafted was measured. As a result, it was found that 0.2 g of maleic anhydride was graft-polymerized per 100 g of the modified propylene-based elastomer.

The properties such as melt properties of the obtained modified propylene elastomer were measured. The results are shown in Table 2.
[Create film]
0.1mm thick aluminum sheet on the press plate, polyethylene terephthalate (PET)
A sheet and an aluminum sheet having a thickness of 100 μm with the center cut into a 15 cm × 15 cm square were laid in this order, and a 3.3 g sample was placed in the center (the cut out portion). Then PE
A T sheet, an aluminum plate, and a press plate are further stacked in this order.

The sample sandwiched between the above press plates is placed in a 200 ° C hot press, preheated for about 7 minutes, and then pressurized (50 kg / cm ² G) depressurization operation is performed to remove bubbles in the sample. Repeat several times. Then, finally, the pressure is increased to 100 kg / cm ² G and heated under pressure for 2 minutes. After depressurization, the press plate is taken out from the press machine, transferred to another press machine in which the crimping part is maintained at 0 ° C., subjected to pressure cooling at 100 kg / cm ² G for 4 minutes, then depressurized, and a sample is taken out. In this way, a film having a uniform thickness of about 150 to 170 μm was obtained.

[Measurement of adhesive strength to aluminum]
The film obtained above was sandwiched between two 15 cm × 15 cm aluminum sheets (thickness 50 μm), and the aluminum sheet and the modified propylene elastomer were bonded together under the same pressing conditions as described above. A 15 mm width strip was cut out from the obtained laminate, and the peel strength at the adhesive interface between the aluminum sheet and the modified propylene elastomer was measured. The results are shown in Table 2.

  In Example 5, a modified propylene elastomer was obtained in the same manner as in Example 5 except that the polar monomer was replaced with 2-hydroxypropyl acrylate. The results are shown in Table 2.

  In Example 5, a modified propylene elastomer was obtained in the same manner as in Example 5 except that the propylene elastomer to be modified was replaced with the propylene elastomer of Example 2. The results are shown in Table 2.

Claims (5)

(1) (a) a unit derived from propylene in an amount of 50 to 85 mol%,
(b) a unit derived from 1-butene in an amount of 5 to 40 mol%,
(c) containing 10 to 40 mol% of units derived from ethylene;
And the amount of units derived from 1-butene is greater than the amount of units derived from ethylene,
(2) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(3) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less,
(4) A resin compounding agent comprising a propylene-based elastomer having a melting point measured by a differential scanning calorimeter in a range of 25 to 85 ° C. [A] a transition metal compound represented by the following general formula [I];
[Wherein, M is a transition metal atom of Group IVB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon A halogenated hydrocarbon group of 1 to 20, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and a part of the groups adjacent to each other is bonded to bond these groups A ring may be formed together with carbon atoms to be formed, and X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or divalent. Silicon-containing group, divalent germanium-containing group, divalent tin-containing group,- O—, —CO—, —S—, —SO—, —SO ₂ —, —NR ⁵ —, —P (R ⁵ ) —, —P (O) (R ⁵ ) —, —BR ⁵ — or — AlR ⁵ —. (Wherein R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms)];
[B] a compound capable of activating the transition metal compound [A], and
(B-1) an organoaluminum compound,
(B-2) an organoaluminum oxy compound, and
(B-3) in the presence of an olefin polymerization catalyst comprising at least one compound selected from compounds that react with the transition metal compound [A] to form ion pairs,
The resin compounding agent comprising a propylene-based elastomer according to claim 1, which is obtained by copolymerizing propylene, 1-butene and ethylene. The [A] transition metal compound according to claim 2 is represented by the following formula [II]: a resin compounding agent comprising a propylene-based elastomer according to claim 1;
(In the formula, M, R ¹ , R ³ , X ¹ , X ² and Y are as defined in the formula [I], and R ^{21 to} R ²⁴ and R ^{41 to} R ⁴⁴ are a hydrogen atom, a halogen atom, An alkyl group or an aryl group, and the alkyl group or aryl group may be substituted with a halogen or an organic silyl group, and adjacent substituents may form a ring). The resin compounding agent comprising a propylene-based elastomer according to any one of claims 1 to 3, wherein the crystallinity of the elastomer measured by an X-ray diffraction method is in the range of 15 to 45%. (1) (a) a unit derived from propylene in an amount of 50 to 85 mol%,
(b) a unit derived from 1-butene in an amount of 5 to 40 mol%,
(c) containing 10 to 40 mol% of units derived from ethylene;
And the amount of units derived from 1-butene is greater than the amount of units derived from ethylene,
(2) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3 or less. The modification characterized in that the propylene elastomer according to claim 1 is graft-modified with a polar monomer. A resin compounding agent composed of a propylene-based elastomer.