JPH0967478A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having high elastic modulus and high impact strength. SOLUTION: This resin composition is produced from (A) a thermoplastic resin, (B) an olefin polymer having an intrinsic viscosity [η] of 0.5-10dl/g and the maximum peak temperature (Tm) of >=100 deg.C in the endothermic curve measured by a differential scanning calorimeter (DSC), (C) a propylene homopolymer having an intrinsic viscosity [η] of 0.5-10dli/g and an mr/(mm+rr) value of 0.8-1.2 in a diad distribution measured by NMR, (D) an elastomer and (E) a modified olefinic polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having a high elastic modulus and impact strength.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Thermoplastic resins such as polyolefins, polyamides, polystyrenes, etc. are excellent in rigidity, heat resistance, impact strength and the like, and are therefore used in various fields such as various molded articles.

As a method for further improving the impact strength of such a thermoplastic resin such as polypropylene, there is known a method of producing a block copolymer by homopolymerizing propylene and then copolymerizing propylene and ethylene. Has been.

Further, JP-A-5-202152 discloses that (1) 20 to 99% by weight of a crystalline polymer having a propylene unit content of 95% by weight or more, and (2) an ethylene unit content of 20 to 90%. When a polypropylene molding material comprising 1 to 80% by weight of an amorphous ethylene-propylene copolymer is produced in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound, an amorphous ethylene-propylene copolymer is used. Disclosed is a method for producing a polypropylene molding material, which comprises carrying out the above polymerization using a specific crosslinked metallocene compound and an aluminoxane. It is described that the polypropylene molding material obtained by this method is particularly excellent in low-temperature impact strength.

Further, as a method of further improving the impact resistance of the thermoplastic resin, it is known to blend the thermoplastic resin with an elastomer. In recent years, the demand for physical properties of thermoplastic resins has become more and more strict, and the emergence of thermoplastic resin compositions having more excellent properties has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and an object thereof is to provide a thermoplastic resin composition having a high elastic modulus and impact strength.

[0007]

SUMMARY OF THE INVENTION A thermoplastic resin composition according to the present invention comprises (P) a thermoplastic resin; 10 to 90% by weight, and (Q) (q-1) an intrinsic viscosity [η] of 0.5 to 10 dl / (q-2) the temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 1
Olefin polymer having a temperature of 00 ° C or higher; 5 to 80% by weight
And (R) (r-1) intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, and (r-2) in the diad distribution measured by NMR, the value of mr / (mm + rr) is 0. Propylene homopolymer in the range of 0.7 to 1.3; 5 to 80% by weight; (S) elastomer; 0 to 50% by weight; (T) modified olefin polymer; the (P) thermoplastic resin , (Q) olefin polymer, (R) propylene homopolymer, and (S) elastomer in an amount of 0.5 to 20% by weight based on 100 parts by weight in total.

In the present invention, the olefin polymer (Q)
Where (a-1) the intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, and (a-2) the temperature at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) ( Tm) is 10
It is 0 ° C or higher, (a-3) contains propylene-derived constitutional units in a proportion of 100 to 80 mol%, contains ethylene-derived constitutional units in a proportion of 0 to 10 mol%, and contains carbon. It is preferably a propylene polymer containing a constituent unit derived from an α-olefin having 4 to 12 atoms in a proportion of 0 to 15 mol%.

The thermoplastic resin composition of the present invention has a high elastic modulus and impact strength.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic resin composition according to the present invention will be specifically described below. In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization.
The term is sometimes used to include not only a homopolymer but also a copolymer.

The thermoplastic resin composition according to the present invention comprises (P) a thermoplastic resin, (Q) (q-1) and an intrinsic viscosity [η] in the range of 0.5 to 10 dl / g. -2) The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 1
The olefin polymer having a temperature of 00 ° C. or higher and (R) (r-1) intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, and (r-2) in the diad distribution measured by NMR, It is formed from a propylene homopolymer having a value of / (mm + rr) in the range of 0.7 to 1.3, an (S) elastomer, and a (T) modified olefin polymer.

First, the thermoplastic resin (P), olefin polymer (Q), propylene homopolymer (R), elastomer (S) and modified olefin polymer (T) will be described.

Thermoplastic resin (P) As the thermoplastic resin (P), the following olefin polymer (Q), propylene homopolymer (R), α-olefin homopolymer other than elastomer (S), α-olefin Copolymer, olefin polymer such as copolymer of α-olefin and vinyl monomer, polyamide, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene, polyvinyl chloride, polyphenylene oxide, petroleum resin, etc. Is mentioned.

Olefin Polymer (Q) The olefin polymer (Q) is a homopolymer of olefins or a copolymer of two or more olefins.

Specific examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 3-. Methyl-1-butene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-
Α-Olefins having 2 to 20 carbon atoms such as eicosene; cyclopentene, cycloheptene, norbornene,
5-ethyl-2-norbornene, tetracyclododecene, 2-
Examples thereof include cyclic olefins having 3 to 20 carbon atoms such as ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be mentioned.

The olefin polymer (Q) is preferably a polymer having an olefin having 3 to 6 carbon atoms as a main constituent unit, and particularly a polymer having a propylene unit as a main constituent unit (propylene weight). (Combined) is preferable.

When the olefin polymer (Q) is a propylene polymer, the constituent unit derived from propylene is 80 to 100 mol%, preferably 90 to 100 mol%, more preferably 92 to 100 mol%. The content of the constituent unit derived from ethylene is 0 to 10 mol%, preferably 0 to 8 mol%, more preferably 0 to 6 mol%. 0 to 15 constitutional units derived from the selected olefin
Mol%, preferably 0-10 mol%, more preferably 0
It is desirable that the polymer is contained at a ratio of ˜5 mol%.

The olefin polymer (Q) contains 3-methyl-1 in addition to the constituent units derived from the above olefins.
-Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-
Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluene , Allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane and other structural units derived from olefins having a branched structure; 1,3-butadiene, 1,3-
Pentadiene, 1,4-pentadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-
1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl- 1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl- Carbon number of 4 to 2 such as 1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene
The constituent unit derived from the diene compound of 0 may be contained in a proportion of 5 mol% or less.

The olefin polymer (Q) has an intrinsic viscosity [η] of 0.5 to 10 dl / g, preferably 1.
It is in the range of 5 to 3.5 dl / g, and the temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 100 ° C or higher, preferably 125 to 16
It is preferably in the range of 7 ° C.

The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is
Approximately 5mg of sample is packed in aluminum pan and 200 ℃ at 10 ℃ / min
It is determined from an endothermic curve when the temperature is raised to 200 ° C., the temperature is held at 200 ° C. for 5 minutes, the temperature is lowered to room temperature at 10 ° C./min, and then the temperature is raised at 10 ° C./min. Measured by Perkin Elmer
A DSC-7 type device was used.

Olefin polymer (Q) as described above
Are, for example, (A-1) a racemate of a transition metal compound represented by the following formula (I), (B) an organoaluminum oxy compound (B-1), or (B-2) the transition metal compound ( A-1) to polymerize an olefin in the presence of a compound which reacts with A-1) to form an ion pair and, if necessary, an olefin polymerization catalyst (1) comprising an organoaluminum compound or two or more olefins. Or (Ia)
A solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components;
(II) an organometallic catalyst component (b), and (III) a silicon compound (c) represented by the following formula (i) or a compound (d) having two or more ether bonds existing through a plurality of atoms. Olefin polymerization catalyst formed from (2)
It can be produced by polymerizing an olefin in the presence of or copolymerizing two or more kinds of olefins.

Next, the olefin polymerization catalyst (1) and the olefin polymerization catalyst (2) will be specifically described. The olefin polymerization catalyst (1) includes (A-1) a racemic transition metal compound represented by the following formula (I), (B) (B-1) an organoaluminum oxy compound, and / or (B- 2) A compound that reacts with the transition metal compound (A-1) to form an ion pair, and, if necessary, (C) an organoaluminum compound.

The transition metal compound (A-1) has the following formula (I):
Is a racemate of the transition metal compound.

[0024]

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In the formula, M ¹ represents a transition metal atom of groups IV to VIB of the periodic table, specifically, zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, Preferred is zirconium, titanium or hafnium.

R ¹ , R ² , R ³ and R ^{4, which} may be the same or different, are hydrocarbon groups having 1 to 20 carbon atoms and halogenated hydrocarbon groups having 1 to 20 carbon atoms. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom. Of the groups represented by R ¹ , R ² , R ³ and R ⁴ ,
Part of the groups adjacent to each other may be bonded to each other to form a ring with the carbon atom to which the groups are bonded. Note that R
¹ , R ² , R ³ and R ⁴ are each indicated at two places. For example, R ¹ and R ¹ may be the same or different groups. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrocarbon groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl,
Alkyl groups such as nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl And aryl groups such as dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, and phenanthryl.

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

Examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups in which the above hydrocarbon group is substituted with halogen. Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl,
Trihydrocarbon-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted trimethylphenyl and the like And an aryl group.

Further, as the silicon-containing group, other than the above
Examples include groups represented by SiR ₃ [wherein R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

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

Further, as the oxygen-containing group, -OSiR
₃ [where R is a halogen atom, having 1 to 1 carbon atoms.
0 alkyl group or aryl group having 6 to 10 carbon atoms].

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur. Further, as the sulfur-containing group, other than the above-mentioned -SR [where R
Is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms].

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Further, as the nitrogen-containing group, -N other than the above is used.
R ₂ [where R represents a halogen atom and a carbon atom number of 1 to
Alkyl group of 10 or aryl group having 6 to 10 carbon atoms].

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Further, as the phosphorus-containing group,
PR ₂ [where R is a halogen atom and has 1 carbon atom
To 10 alkyl groups or aryl groups having 6 to 10 carbon atoms].

Examples of the halogen include fluorine, chlorine, bromine and iodine. Among them, a hydrocarbon group is preferable, and in particular, a hydrocarbon group having 1 to 4 carbon atoms of methyl, ethyl, propyl, and butyl, a benzene ring formed by combining hydrocarbon groups, and a hydrocarbon group are preferable. The hydrogen atom on the benzene ring formed by bonding is methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, iso-butyl, tert
It is preferably a group substituted with an alkyl group such as -butyl.

X ¹ and X ^{2, which} may be the same or different, each represents a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

The hydrocarbon group has 1 to 20 carbon atoms.
Are preferred, and specifically, R ¹ , R ² , R
The same groups as ³ and R ⁴ can be mentioned. As the halogenated hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms is preferable. Specifically, R ¹ , R ² ,
The same groups as R ³ and R ⁴ can be mentioned.

As the oxygen-containing group and the halogen atom,
The same groups or atoms as those of R ¹ , R ² , R ³ and R ⁴ can be exemplified. Examples of the sulfur-containing group include groups similar to R ¹ , R ² , R ³ and R ⁴ , and methylsulfonate,
Trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate Sulfonate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include the same silicon-substituted alkyl group and silicon-substituted aryl group as described above. Of these, halogen atoms and C1-20
Is preferably a hydrocarbon group or a sulfonate group.

Y ¹ is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, --O--, --CO. -,-
S -, - SO -, - SO 2 -, - Ge -, - Sn -, -
NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )-,-
BR ⁵ — or —AlR ⁵ — [wherein R ⁵ may be the same or different from each other and is a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group or an alkoxy group].

The hydrocarbon group has 1 to 2 carbon atoms.
A divalent hydrocarbon group of 0 is preferable, and specific examples thereof include methylene, dimethylmethylene, 1,2-ethylene and dimethyl-1,2-.
Ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,
Examples thereof include alkylene groups such as 2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

The halogenated hydrocarbon group is preferably a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and specifically, the above divalent halogenated hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. And a group obtained by halogenating the hydrocarbon group.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; tetramethyl-1,2-disilyl, tetraphenyl-
Alkyldisilyl groups such as 1,2-disilyl; alkylaryldisilyl groups; and aryldisilyl groups.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Further, the divalent silicon-containing group, the divalent germanium-containing group, and the divalent tin-containing group include any one of silicon, germanium and tin among the groups represented by the following [Chemical Formula 5]. Groups.

Of these, substituted silylene groups such as dimethylsilylene group, diphenylsilylene group and methylphenylsilylene group are particularly preferable. Specific examples of the racemate of the transition metal compound represented by the above formula (I) include racemates of the following compounds.

Dimethylsilylene-bis (1-cyclopentadienyl) zirconium dichloride, dimethylsilylene
-Bis {1- (3-methylcyclopentadienyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,4-
Dimethylcyclopentadienyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,5-trimethylcyclopentadienyl)} zirconium dichloride and the like.

Furthermore, transition metal compounds in which zirconium metal, titanium metal and hafnium metal in the above compounds are replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal and tungsten metal can be mentioned.

In the present invention, among the transition metal compounds represented by the above formula (I), a racemic transition metal compound represented by the following formula (III), (IV) or (V) is used. Is preferred.

[0051]

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[0052] In the formula, M ¹ is, M ¹ in the formula (I)
The transition metals of Groups IV to VIB of the Periodic Table similar to the above are preferable, zirconium, titanium or hafnium are preferable, and zirconium is particularly preferable.

R ¹¹ , R ¹² and R ^{14 to} R ^{16, which} may be the same or different, are each a hydrogen atom, a halogen atom,
Hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
A halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group,
It represents a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and some of the groups adjacent to each other may be bonded to each other to form a ring with the carbon atom to which those groups are bonded.

Specifically, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, which is similar to the above formula (I), Mention may be made of oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups.

R ¹³ represents an aryl group having 6 to 16 carbon atoms, specifically, phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl and the like. . Of these, phenyl, naphthyl and phenanthryl are preferred. These aryl groups may be substituted with the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above.

[0056] X ¹ and X ² may be the same or different from each other, are the same as X ¹ and X ² in the formula (I), the halogen atom, a hydrocarbon group or a sulfonate having 1 to 20 carbon atoms It is preferably a group.

[0057] Y ¹ is the same as Y ¹ in the formula (I), the dimethylsilylene group, diphenylsilylene group,
A substituted silylene group such as a methylphenylsilylene group is preferred.

Specific examples of the racemate of the transition metal compound represented by the above formula (III) include racemates of the following compounds. Dimethylsilylene-bis {1- (4
-Phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-
Bis {1- (2-methyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, dimethylsilylene-bis {1-
(2-Methyl-4- (β-naphthyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-
4- (2-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-)
(9-Anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (9-
Phenanthryl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (penta Fluorophenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (m -Chlorophenyl) indenyl)} zirconium dichloride,
Dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenylindenyl) } Zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,
Dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl)
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl) Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-
Methyl-4- (o, o'-dimethylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2
-Methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-
Methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-
Methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-
4- (m-biphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl -Four-
(M-Trimethylsilylphenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-ethyl-4- (α -Naphthyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl)
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-ethyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene
-Bis {1- (2-ethyl-4- (2-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene -Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, diphenylsilylene-
Bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2 -n-Propyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- ( 2-n-propyl-4- (β-naphthyl)
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-n-propyl-4- (1-anthracenyl))
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-n-propyl-4- (2-anthracenyl))
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl)
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, dimethylsilylene-bis {1-
(2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-
Butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-butyl-
4- (1-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-butyl-4-
(2-anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-butyl-4-
(9-Anthracenyl) indenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-i-butyl-4-
(9-Phenanthryl) indenyl)} zirconium dichloride, diethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, di- (i-
Propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride , Dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, diphenylsilylene-bis {1- (2-Methyl-4-phenylindenyl)} zirconium dichloride, di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, di (p-
Chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, methylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, ethylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, dimethylgermylene-bis {1- ( 2-Methyl-4-phenylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, dimethylsilylene-bis {1- (2-methyl-4) -Phenylindenyl)} zirconium dimethyl,
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, dimethylsilylene -Bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, dimethylsilylene-bis {1-
(2-methyl-4-phenylindenyl)} titanium dichloride, dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} hafnium dichloride and the like.

Furthermore, transition metal compounds in which zirconium metal, titanium metal and hafnium metal in the above compounds are replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal and tungsten metal can be mentioned.

Next, the transition metal compound represented by the general formula (IV) will be described.

[0061]

Embedded image

[0062] In the formula, M ¹ is, M ¹ in the formula (I)
The same transition metals as those in Groups IV to VIB of the Periodic Table, which are preferably titanium, zirconium or hafnium, and particularly preferably zirconium.

R ²¹ and R ²² may be the same or different and each 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. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Specifically, similar to the above formula (I), a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, Mention may be made of oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups.

Of these, R ²¹ is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. R ²²
Is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ²³ and R ^{24, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, and specifically are the same as those exemplified in the above general formula (I). .

Of these, R ²³ is preferably a secondary or tertiary alkyl group. R ²⁴ may contain a double bond or a triple bond. X ¹ and X ^2, X ¹ in may be the same or different from each other, the formula (I)
And is the same as X ^2.

[0068] Y ¹ is the same as Y ¹ in the formula (I). Specific examples of the racemate of the transition metal compound represented by the above formula (IV) include racemates of the following compounds.

Dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
Dimethylsilylene-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7
-Dimethyl-4-sec-butylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-
4-t-Butylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7- Dimethyl-4-n-hexylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7- Dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, dimethylsilylene-
Bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, dimethyl Silylene
-Bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, dimethylsilylene
-Bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, Di (i-propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, di (n-butyl) silylene-bis {1- (2,7-dimethyl- 4-i-propylindenyl)} zirconium dichloride, di (cyclohexyl)
Silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride, methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)}
Zirconium dichloride, diphenylsilylene-bis {1
-(2,7-Dimethyl-4-t-butylindenyl)} zirconium dichloride, diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, diphenylsilylene-bis {1- (2,7-dimethyl-
4-Ethylindenyl)} zirconium dichloride, di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, di (p-
Chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-
i-Propylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-
Ethylindenyl)} zirconium dibromide, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride, dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl) } Zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)}
Zirconium dichloride, dimethylsilylene-bis {1-
(2,3,7-Trimethyl-4-sec-butylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-t-butylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-Trimethyl-4-n-hexylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-
4-Cyclohexylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Methylcyclohexylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2 , 3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, di (i-propyl) silylene-bis {1- (2,3,7-trimethyl-4-i -Propylindenyl)} zirconium dichloride, di (n-butyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, di (cyclohexyl) silylene-bis { 1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium Dichloride, methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, diphenylsilylene-bis {1- (2,3,7-trimethyl-4-t -Butylindenyl)} zirconium dichloride, diphenylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, diphenylsilylene-
Bis {1- (2,3,7-trimethyl-4-ethylindenyl)}
Zirconium dichloride, di (p-tolyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, di (p-chlorophenyl) silylene-bis {1- (2 , 3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, dimethylsilylene- Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl) } Zirconium-bis (methanesulfonato), dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (p
-Phenylsulfinato), dimethylsilylene-bis {1-
(2-Methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, dimethylsilylene-
Bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} Zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} titanium dichloride, dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7) -Methylindenyl)} hafnium dichloride and the like.

Among these, those having a branched alkyl group such as i-propyl, sec-butyl, tert-butyl group at the 4-position are particularly preferable. In the present invention, the general formula (I
A racemic transition metal compound represented by V) is used as a catalyst component for propylene polymerization, but R type or S type can also be used.

The transition metal compound represented by the general formula (IV) as described above can be synthesized from an indene derivative by a known method, for example, the method described in JP-A-4-268307.

Next, the transition metal compound represented by the general formula (V) will be described. The transition metal compound represented by the general formula (V) includes EP-549900 and Canada-20.
The compound described in No. 84017.

[0073]

Embedded image

In the formula, M ³ is a transition metal of Group IVB of the periodic table, preferably titanium, zirconium or hafnium, particularly preferably zirconium. R ³¹ may be the same or different, and each represents a hydrogen atom, a halogen atom, preferably a chlorine atom or a bromine atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and 1 carbon atom. 10 halogenated alkyl group having carbon atoms 6 to 10, preferably 6 to 8 aryl _{group, -NR 2, -SR, -OSiR 3} , -SiR 3 or -PR ₂ groups [wherein, R is A halogen atom, preferably a chlorine atom, having 1 to 10 carbon atoms, preferably 1 to 3
Or an aryl group having 6 to 10, preferably 6 to 8 carbon atoms].

R ^{32 to} R ^{38, which} may be the same or different from each other, represent the same atom or group as those of R ^21, and at least two adjacent groups of the groups represented by R ^{32 to} R ³⁸ are adjacent to each other. The groups, together with the atoms to which they are attached, may form an aromatic or aliphatic ring.

X ⁴ and X ⁵ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 1 to 10 carbon atoms, preferably 1 carbon atoms. ~ 3 alkoxy groups, 6 to 1 carbon atoms
0, preferably 6 to 8 aryl groups, 6 to 6 carbon atoms
10, preferably 6 to 8 aryloxy groups, 2 to 10 carbon atoms, preferably 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferably 7 to 10 arylalkyl groups, carbon atoms Represents an alkylaryl group having 7 to 40, preferably 7 to 12, an arylalkenyl group having 8 to 40, preferably 8 to 12 carbon atoms, an OH group or a halogen atom. Z ² is

[0077]

Embedded image

--O--, --CO--, --S--, --SO--,-
SO₂-, -Ge-, -Sn-, -NR³⁹-, -P (R
³⁹)-, -P (O) (R³⁹)-, -BR³⁹-Or-A
lR ³⁹-.

However, R ³⁹ and R ⁴⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methyl group, a carbon atom. Fluoroalkyl group having 1 to 10 carbon atoms, preferably CF ₃ group, aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, preferably pentafluorophenyl A group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methoxy group, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, 7 to 40 carbon atoms,
It is preferably an arylalkyl group having 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an alkylaryl group having 7 to 40 carbon atoms and 7 to 12 carbon atoms.

R ³⁹ and R ⁴⁰ may form a ring together with the atom to which they are bonded. M ³ represents silicon, germanium or tin, preferably silicon or germanium.

Here, the above-mentioned alkyl group is a linear or branched alkyl group, and halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly a fluorine atom or a chlorine atom. Is.

Among the compounds represented by the general formula (V), M ³ is zirconium or hafnium,
R ³¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, and R ^{32 to} R ³⁸ may be the same or different from each other, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A group, X ⁴ and X ^{5, which} may be the same or different from each other, are an alkyl group having 1 to 3 carbon atoms or a halogen atom, and Z ² is

[0083]

[Chemical 6]

(In the formula, M^ThreeIs silicon and R³⁹and
R⁴⁰Are carbon atoms which may be the same or different from each other.
An alkyl group having 1 to 4 carbon atoms or 6 to 10 carbon atoms
A compound which is an aryl group) is preferred, and the substituent R is
³²And R³⁸Is a hydrogen atom, R³³~ R ³⁷Is carbon
Compounds having 1 to 4 alkyl groups or hydrogen atoms
The thing is more preferable.

Further, among the compounds represented by the general formula (IV), M ³ is zirconium and R ³¹ is
Alkyl groups having 1 to 4 carbon atoms which are the same as each other,
R ³² and R ³⁸ are hydrogen atoms, R ^{33 to} R ³⁷ may be the same or different, are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X ⁴ and X ⁵ are Both are chlorine atoms, and Z ² is

[0086]

[Chemical 7]

(In the formula, M ³ is silicon, R ³⁹ and R ⁴⁰ may be the same or different from each other, and are an alkyl group having 1 to 4 carbon atoms or 6 to 1 carbon atoms.
Compounds having 0 aryl groups) are preferred.

In particular, among the compounds represented by the general formula (IV), M ³ is zirconium, R ³¹ is a methyl group, R ^{32 to} R ³⁸ are hydrogen atoms, and X is ⁴ and X ⁵ are chlorine atoms, and Z ² is

[0089]

Embedded image

(Wherein M ³ is silicon, R ³⁹ and R ⁴⁰ may be the same or different from each other, and are a methyl group or a phenyl group).

Specific examples of the racemate of the transition metal compound represented by the above formula (V) include racemates of the following compounds. Dimethylsilylene-bis {1- (2-
Methyl-4,5-benzoindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-α-acenaphthoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2-methyl- 4,5-Benzoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2-methyl-α-acenaphthoindenylcyclopentadienyl)} zirconium dichloride, methylphenylsilylene-bis {1- (4 , 5-Benzoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2,6-dimethyl-4,5-benzoindenyl)}
Zirconium dichloride, methylphenylsilylene-bis {1- (2,4,6-trimethyl-4,5-benzoindenyl)}
Zirconium dichloride, etc.

Further, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. The organoaluminum oxy compound (B-1) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be prepared, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. trialkylaluminum; tricyclohexylaluminum, tricyclooctylaluminum, etc. Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following formula (VI) can also be mentioned.

[0097] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... (VI) ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination.

As the solvent used for preparing the aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

These organoaluminum oxy compounds (B-1) can be used alone or in combination of two or more kinds. (B-2) A compound that reacts with the transition metal compound (A-1) to form an ion pair (hereinafter referred to as “ionized ionic compound”).
That is the case)
Japanese Laid-Open Patent Publication No. 1-502036, Japanese Laid-Open Patent Publication No. 3-1
79005, JP-A-3-179006, JP-A-3-207703, and JP-A-3-207704.
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in JP-A No. 547718 and the like.

Examples of the Lewis acid include magnesium-containing Lewis acid, aluminum-containing Lewis acid and boron-containing Lewis acid. Of these, boron-containing Lewis acid is preferable.

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following formula (VII). BR ^a R ^b R ^c (VII) (wherein R ^a , R ^b and R ^c are each independently,
A phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group, or a fluorine atom is shown. ) Specific examples of the compound represented by the above formula (VII) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron and tris (4-fluoro). Examples thereof include methylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron. Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound (A-1) by reacting with the transition metal compound (A-1) and stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable.
As the cation, a metal cation, an organometallic cation,
Examples thereof include carbonium cation, tripium cation, oxonium cation, sulfonium cation, phosphonium cation, and ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

Of these, ionic compounds containing a boron compound as an anion are preferable, and specifically,
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron,
Trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl)
Boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron,
Examples thereof include tri (n-butyl) ammonium tetra (o-tolyl) boron and tri (n-butyl) ammonium tetra (4-fluorophenyl) boron. Examples of N, N-dialkylanilinium salts include N, N -Dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like, dialkylammonium salts Are, for example, di (n-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, etc., triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, Tri (methylphenyl) phosphonium tetra (phenyl) pho Element, such as tri (dimethylphenyl) phosphonium tetra (phenyl) boron and the like.

Further, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Ferrocenium tetra (pentafluorophenyl) borate can also be mentioned.

The following compounds can also be exemplified.
(In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Salts of anions, for example, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (N-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc .; borane As the carborane complex compound and carborane anion salt, for example, decaborane (14), 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-7,8- Dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-
2,7-Dicarbaundecaborane, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl)
Ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13),
Tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8- Methyl 7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7, 9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride-8-allyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,
8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc .; examples of carborane and carborane salts include 4-carbanonaborane (14), 1, 3-dicarbano naborane (13), 6,9-dicarbadecaborane (14),
Dodeca hydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane Further, the following compounds can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl) ammonium, but is not limited thereto.) Examples of metal carborane salts and metal borane anions include, for example, tri (n-butyl) ammonium bis. (Nona hydride-1,3-dicarbanonaborate) Cobaltate (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Deca hydride-7,8-dicarbaundecaborate) cubrate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal Bounce carbate) Nickelate (IV) and the like.

Hereinafter, one compound selected from the above-mentioned (B-1) organoaluminum oxy compound and (B-2) transition metal compound (A-1) which forms an ion pair is "activated". Sometimes referred to as a compound.

As the organoaluminum compound (C) used as necessary, an organoaluminum compound represented by the following formula (VIII) can be exemplified. During ^{_{R d n AlX 3-n ...}} (VIII) ( wherein, R ^d represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
It is 3. In the above formula (VIII), R ^d is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group. Group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (C)
Specifically, the following compounds may be mentioned.
Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminumchloride, diethylaluminumchloride Dialkylaluminum halides such as diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkyl alkyls such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Bromide sesquihalide; methyl aluminum dichloride, ethyl aluminum dichloride,
Alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide; Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (C), a compound represented by the following formula (IX) can also be used. During ^{_{R d n AlY 3-n ...}} (IX) ( wherein, R ^d are as defined above, Y is -OR ^e group, -
OSiR ^f ₃ group, -OAlR ^g ₂ group, -NR ^h ₂ group, -S
indicates iR ⁱ ₃ group or -N (R ^j) AlR ^k ₂ group, n is ^{1~2, R e, R f,} R g and R ^k are each methyl, ethyl, isopropyl, isobutyl, A cyclohexyl group, a phenyl group, etc., R ^h is a hydrogen atom,
A methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ⁱ and R ^j are a methyl group, an ethyl group and the like. ) Specifically, as such an organoaluminum compound,
The following compounds may be mentioned. (1) R ^d _n Al (OR ^e ) _3-n represented by compounds such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (2) R ^d _n Al (OSiR ^f ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu)
₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiE
t _{3), ^{etc.; (3) R d n Al}} (OAlR g 2) compound represented by the _3-n, e.g., _{Et 2 AlOAlEt 2, (iso-} Bu) 2
AlOAl (iso-Bu) _{2 and the} like; (4) Compounds represented by R ^d _n Al (NR ^h ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me.
₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-
Bu) ₂ AlN (SiMe ₃ ) _{2 and the} like; (5) a compound represented by R ^d _n Al (SiR ⁱ ₃ ) _3-n ,
For example, (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) a compound represented by R ^d _n Al (N (R ^j ) AlR ^k ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ ,
(Iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above formula (VIII) or (IX), the compound represented by the formula R ^d ₃ Al is preferable, and the compound in which R ^d is an isoalkyl group is particularly preferable.

Such an organoaluminum compound (C)
Can be used alone or in combination of two or more. (A-1) transition metal compound as described above, (B-1)
At least one of the organoaluminum oxy compound, the (B-2) ionized ionic compound and the (C) organoaluminum compound can be used by being supported on a fine particle carrier.

Such a fine particle carrier is an inorganic or organic compound, and is a granular or fine particle solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm.

Among these, porous oxides are used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O_Three, MgO, Z
rO₂, TiO₂, B₂O_Three, CaO, ZnO, BaO, T
hO ₂Or a mixture thereof, such as SiO₂-
MgO, SiO₂-Al₂O_Three, SiO₂-TiO₂, SiO₂
-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-MgO
And the like. Among these SiO₂Oh
And / or Al₂O_ThreeThe main component is preferably.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
_It does not matter if it contains a carbonate, a sulfate, a nitrate or an oxide component such as ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier differ depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably in the range of 100 to 700 m ² / g,
It is desirable that the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The fine particle carrier may be 100 to
It is used by firing at a temperature of 1000 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
Granular or particulate solids of organic compounds having a size of 0 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers containing α-olefins having 2 to 14 carbon atoms such as pentene as a main component, or polymers or copolymers containing vinylcyclohexane and styrene as a main component.

Such a particulate carrier may contain surface hydroxyl groups and / or water. The olefin polymerization catalyst (1) may be a catalyst comprising (A-1) a transition metal compound-supported fine particle carrier and (B) an activating compound, and (A-1) a transition metal compound. , (B) activating compound may be a solid catalyst supported on a fine particle carrier, in the presence of (A-1) a transition metal compound, (B) activating compound and a fine particle carrier. It may be a prepolymerization catalyst obtained by prepolymerizing an olefin.

The solid catalyst comprises the (A-1) transition metal compound and
It can be prepared by mixing and contacting the activating compound (B), the particulate carrier and, if necessary, the organoaluminum compound (C) in an inert hydrocarbon medium or an olefin medium.

Specific examples of the inert hydrocarbon medium used for preparing the olefin polymerization catalyst include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The order in which the above components are mixed and contacted is arbitrarily selected, but preferably the particulate carrier and the activating compound (B) are mixed and contacted, and then the transition metal compound (A-
1) are mixed and brought into contact with each other, or the mixture of the activating compound (B) and the transition metal compound (A-1) is brought into mixed and brought into contact with the particulate carrier, or the particulate carrier and the activating compound (B) are brought into contact. And water are mixed and contacted, and then the transition metal compound (A-1) is mixed and contacted.

As a method for supporting the transition metal compound (A-1) on the fine particle carrier, a method of mixing and contacting the transition metal compound (A-1) and the fine particle carrier in a hydrocarbon medium is usually used. To be When the above components are brought into contact with each other, the organoaluminum compound (C) may be mixed and contacted.

More specifically, the following method may be mentioned. (1) The activating compound (B) is added to a particulate carrier suspended in a hydrocarbon medium, mixed, and then the medium is removed by filtration, and the solid component thus obtained is suspended or dissolved in a hydrocarbon solvent. A method of contacting the transition metal compound (A-1).

(2) The activating compound (B) is added to the particulate carrier suspended in the aromatic hydrocarbon medium, and after mixing, the aliphatic hydrocarbon is further added, and the aromatic hydrocarbon is added under reduced pressure. Remove. By this operation, the organoaluminum oxy compound is deposited on the particulate carrier. Next, a solid component obtained by removing aliphatic hydrocarbons by filtration and a transition metal compound (A-) suspended or dissolved in a hydrocarbon medium.
1) How to contact with.

(3) The activating compound (B) and the transition metal compound (A-1) are added to a fine particle carrier suspended in a hydrocarbon medium.
A method in which the hydrocarbon medium is removed by filtration or an evaporator after adding and mixing.

When the above components are mixed, the transition metal compound (A-1) is usually added in an amount of 10 per 1 g of the fine particle carrier.
^{-6 to} 5 × 10 ^-3 mol, preferably 3 × 10 ^-6 to 10 ^-3 mol, and the concentration of the transition metal compound (A-1) is
It is in the range of about 5 × 10 ^{−6 to} 2 × 10 ⁻² mol / liter, preferably 10 ⁻⁵ to 10 ⁻² mol / liter. An organoaluminum oxy compound (B-
When 1) is used, an organoaluminum oxy compound (B-
The atomic ratio (Al / transition metal) between aluminum in 1) and the transition metal in the transition metal compound (A-1) is usually 10 to 10.
It is 3000, preferably 20 to 2000. When the ionizing ionic compound (B-2) is used as the activating compound (B), the molar ratio of the transition metal compound (A-1) to the ionizing ionic compound (B-2) [(A-1) / ( B-2)) is usually in the range of 0.01 to 10, preferably 0.1 to 5. When the organoaluminum compound (C) is used, the atomic ratio (Al / transition metal) of aluminum in the organoaluminum compound (C) to the transition metal in the transition metal compound (A-1) is usually 10 to 3000, Preferably 20-20
00.

The mixing temperature at the time of mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The transition metal compound (A-1) can be loaded on the particulate carrier in the presence of zeolite or an organic amine. As the zeolite, for example, the following general formula M _{2 / n} O · Al ₂ O ₃ · xSiO ₂ · yH ₂ O (wherein M represents Na, K, Ca or Ba, n represents the valence of M, x represents Is 2 to 10, and y is 2 to 7.), and Molecular Sieve ^TM is preferable.

As the organic amine, methylamine, ethylamine, n-propylamine, isopropylamine, n-
Butylamine, t-butylamine and other monoalkylamines; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-t-
Dialkylamines such as butylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-
Examples include trialkylamines such as butylamine.

Zeolite is used for 1 g of the fine particle carrier.
Usually, 1 × 10 ^-2 to 1 × 10 ² g, preferably 1 × 10
It is preferably used in an amount of ^{-1 to} 10 g. The organic amine is usually 1 × 10 ⁻⁷ per 1 g of the particulate carrier.
˜2 × 10 ⁻² mol, preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻²
It is preferably used in molar amounts.

When a zeolite or an organic amine is used in preparing a solid catalyst, the transition metal compound (A
It is possible to prepare a solid catalyst carrying -1). The solid catalyst obtained as described above is 1 g of a fine particle carrier.
Per transition metal atom, 10 ^-6 to 10 ^-3 gram atom,
Preferably, the transition metal compound (A-1) having 2 × 10 ^{−6 to} 3 × 10 ⁻⁴ gram atom is supported, and the amount thereof is about 10 ⁻³ to 10 ⁻¹ gram atom, preferably 2 × 10 ^{−3 in} terms of aluminum atom. ~
It is desirable that 5 × 10 ^-2 g atom of the organoaluminum oxy compound (B-1) [or the organoaluminum compound (C)] is supported. Further, the ionized ionic compound (B-2) is used as a boron atom in the ionized ionic compound (B-2) in an amount of 10 ^{−7 to} 0.
It is desirable to support the amount of 1 gram atom, preferably 2 × 10 ^{−7 to} 3 × 10 ⁻² gram atom.

The prepolymerization catalyst is prepared by using (A-1) a transition metal compound, (B) an activating compound and a fine particle carrier,
If necessary, it can be prepared by prepolymerizing a small amount of an olefin in an inert hydrocarbon medium or an olefin medium in the coexistence of an organoaluminum compound (C). The transition metal compound (A-1), the activating compound (B) and the particulate carrier preferably form the above solid catalyst.

As the inert hydrocarbon solvent used for preparing the prepolymerization catalyst, the same ones as described above can be mentioned.
In preparing the prepolymerization catalyst, the transition metal compound (A
-1) is usually 10 ^{-6 to} 5 × 10 per 1 g of the particulate carrier.
^-3 mol, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol, and the concentration of the transition metal compound (A-1) is about 5 × 10 ⁻⁶ to.
2 × 10 ^-2 mol / liter (medium), preferably 10 ^-5
It is in the range of -10 ^-2 mol / liter (medium). An organoaluminum oxy compound (B-
When 1) is used, an organoaluminum oxy compound (B-
The atomic ratio (Al / transition metal) between aluminum in 1) and the transition metal in the transition metal compound (A-1) is usually 10 to 10.
It is 3000, preferably 20 to 2000. When the ionizing ionic compound (B-2) is used as the activating compound (B), the molar ratio of the transition metal compound (A-1) to the ionizing ionic compound (B-2) [(A-1) / ( B-2)] is usually in the range of 0.01 to 10, preferably 0.1 to 5. The organoaluminum compound (C), which is used as necessary, has a normal atomic ratio (Al / transition metal) between aluminum in the organoaluminum compound (C) and the transition metal in the transition metal compound (A-1). It is 10 to 3000, preferably 20 to 2000.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours. The olefin used for the prepolymerization is selected from the olefins used for the polymerization, and is preferably the same monomer as the polymerization or a mixture of the same monomer and olefin as the polymerization.

The prepolymerization catalyst obtained as described above is 10 ^{-6 in} terms of transition metal atom per 1 g of the particulate support.
-10 ^-3 gram atom, preferably 2 × 10 ^{-6 -3} × 10
^-4 g atom of transition metal compound (A-1) is supported, and is about 10 ^-3 to 10 ^-1 gram atom, preferably 2 × 10 ^{-3 to} 5 × 10 ^-2 gram atom of organic aluminum in terms of aluminum atom. It is desirable that the oxy compound (B-1) is supported. Further, the ionized ionic compound (B-2) is 1 in terms of boron atom in the ionized ionic compound (B-2).
0 ^{−7 to} 0.1 gram atom, preferably 2 × 10 ^{−7 to} 3 ×
It is preferably loaded in an amount of 10 ^-2 gram atom. Further, it is desirable that the amount of the polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g, and particularly preferably 1 to 100 g, per 1 g of the particulate carrier.

The olefin polymer (Q) can be produced by polymerizing an olefin or copolymerizing two or more kinds of olefins in the presence of such an olefin polymerization catalyst (1).

Examples of the olefins used for the polymerization include α-olefins having 2 to 20 carbon atoms, cyclic olefins having 3 to 20 carbon atoms, styrene, vinylcyclohexane and dienes as described above. further,
An olefin having a branched structure similar to the above, having 4 to 4 carbon atoms
Twenty diene compounds can be used.

In the present invention, propylene is preferably used alone or in combination with propylene and an α-olefin other than propylene. During the polymerization, the transition metal compound (A-1) is converted into the transition metal compound (A-
The concentration of transition metal atoms in 1) is usually 10 ⁻⁸ to 10
It is desirable to use an amount of ^-3 gram atom / liter, preferably 10 ^-7 to 10 ^-4 gram atom / liter.
When the organoaluminum oxy compound (B-1) is used as the activating compound (B), aluminum in the organoaluminum oxy compound (B-1) and the transition metal compound (A-
The atomic ratio (Al / transition metal) to the transition metal in 1) is usually in the range of 5 to 10000, preferably 10 to 5000. When the ionizing ionic compound (B-2) is used as the activating compound (B), the molar ratio of the transition metal compound (A-1) to the ionizing ionic compound (B-2) [(A-1) /
(B-2)] is usually 0.01 to 10, preferably 0.5.
The range is from 5 to 5. When the organoaluminum compound (C) is used, the atomic ratio (Al / transition metal) of aluminum in the organoaluminum compound (C) to the transition metal in the transition metal compound (A-1) is usually 5 to 10,000, It is preferably in the range of 10 to 5000.

When a solid catalyst or a prepolymerization catalyst is used, the (B-1) organoaluminum oxy compound, (B-2) ionized ionic compound or (C) organoaluminum compound supported on a fine particle carrier is used. In addition, a compound selected from the group consisting of unsupported organoaluminum oxy compound (B-1), ionized ionic compound (B-2) or organoaluminum compound (C) can be used.

When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 1
It is preferably in the range of 00 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2.

The molecular weight of the obtained olefin polymer (Q) can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. The olefin polymerization catalyst (2) includes (Ia) a solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components, (II) an organometallic catalyst component (b), and III) A silicon compound (c) represented by the following formula (i) or a compound (d) having two or more ether bonds existing through a plurality of atoms.

[0141] In _{^{R p n -Si- (OR q)}} 4-n ... (i) ( wherein, n is 1, 2 or 3, when n is 1, R
^p represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^{p represents} a secondary or tertiary hydrocarbon group and the other is a hydrocarbon group, and R ^p may be the same or different, and R ^q is a carbon number of 1 to
When 4 is a hydrocarbon group of 4 and 4-n is 2 or 3, R ^q may be the same or different. ) Solid titanium catalyst component (a) which is the catalyst component (Ia)
Can be prepared by contacting the following magnesium compound, titanium compound and electron donor.

Used in the preparation of solid titanium catalyst component (a)
Specific examples of the titanium compound include
The tetravalent titanium compound represented by Ti (OR)_nX_4-n (Wherein, R represents a hydrocarbon group, X represents a halogen atom)
And n is 0 ≦ n ≦ 4) As such a titanium compound, specifically, TiCl
_Four, TiBr_Four, TiI_Four Tetrahalogenated titanium such as
Ti (OCH_Three) Cl_Three, Ti (OC₂H_Five) Cl_Three,
Ti (On-C_FourH₉) Cl_Three, Ti (OC₂H_Five) Br_Three, T
i (O-iso-C_FourH₉) Br_ThreeTrihalogenated al such as
Coxy titanium; Ti (OCH_Three)₂Cl₂, Ti (OC₂H
_Five)₂Cl₂, Ti (On-C_FourH₉)₂Cl ₂, Ti (OC₂H
_Five)₂Br₂Dialkoxytitanium dihalide such as T;
i (OCH_Three)_ThreeCl, Ti (OC₂H_Five)_ThreeCl, Ti
(On-C_FourH₉)_ThreeCl, Ti (OC₂H_Five)_ThreeBr etc.
Monohalogenated trialkoxy titanium; Ti (OC
H_Three)_Four, Ti (OC₂H_Five)_Four, Ti (On-C_FourH₉)_Four, T
i (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhexyl)
_FourExamples include tetraalkoxy titanium
it can.

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, and the like. it can. These magnesium compounds may be used alone or may form a complex compound with an organic metal compound described later. Further, these magnesium compounds may be liquid, solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can be derived from metallic magnesium during the catalyst preparation using the above-mentioned method.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride;
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxy magnesium, n-octoxy magnesium, 2-
Examples thereof include alkoxy magnesium such as ethylhexoxy magnesium; phenoxy magnesium, allyloxy magnesium such as dimethylphenoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is used as a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. It may be contacted with a compound having an active carbon-oxygen bond, such as a ketone, an aldehyde or the like.

In the present invention, the magnesium compound may be a complex compound, a complex compound or a complex compound of the above-mentioned magnesium compound with another metal, in addition to the above-mentioned reducible magnesium compound and non-reducible magnesium compound. It may be a mixture with a metal compound. Furthermore, you may use the said compound in combination of 2 or more types.

As the magnesium compound used for the preparation of the solid titanium catalyst component (a), many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component (a), , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are particularly preferable.

The solid titanium catalyst component (a) used in the present invention is formed by bringing the above-mentioned magnesium compound into contact with the above-mentioned titanium compound and electron donor.

Specific examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include the following compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Amines such as tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine;
Pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygen-containing compounds such as coumaran, phthalane, tetrahydropyran, pyran and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol,
C1-C18 alcohols such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol,
Nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone, benzoquinone and the like having 3 to 15 carbon atoms Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, Ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, tetrahydrophthalic acid Diisopropyl, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate,
Di-2-ethylhexyl phthalate, γ-butyrolactone, δ-
C2-30 organic acid esters such as valerolactone, coumarin, phthalide, and ethyl carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl Ether, isopropyl ether,
Butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane, etc. with 2 to 2 carbon atoms
0 ethers; 2-isopentyl-2-isopropyl-1,3-
Dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisopentyl -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-
Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,
3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo- [2,2,1] -heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane Diethers such as 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane and 9,9-dimethoxymethylfluorene; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; acetonitrile, benzonitrile, tolunitrile Nitriles such as; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride, etc. are used.

In addition to these, water, anionic, cationic and nonionic surfactants can also be used.
Further, as the organic acid ester, a polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0154]

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In the above formula, R ¹¹ is a substituted or unsubstituted hydrocarbon group, R ¹² , R ¹⁵ and R ¹⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ¹³ and R ¹⁴ are hydrogen or a substituted hydrocarbon group. Alternatively, it is an unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R ¹³ and R ¹⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{11 to} R ¹⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C—O—C, COOR, COOH, OH, SO.
_It has groups such as ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate and isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Diisopropyl ethyl succinate, diaryl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconic acid, dioctyl citraconic acid, and other aliphatic polycarboxylic acid esters, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl Diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; And rocyclic polycarboxylic acid esters.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Long chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate can be mentioned.

Further, as the electron donor, a silicon compound represented by the general formula (i) described below can be used. Two or more of these compounds can be used in combination.

When the titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, the carrier compound as described below can be used to prepare the carrier-supported solid titanium catalyst component (a). .

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Z
Examples thereof include resins such as nO, ZnO ₂ , SnO ₂ , BaO, ThO, and a styrene-divinylbenzene copolymer. Among these carrier compounds, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like are preferable.

The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum. The solid titanium catalyst component (a) can be produced by bringing the above titanium compound, magnesium compound and electron donor into contact with each other, and any known method can be adopted. it can.

The specific method for producing the solid titanium catalyst component (a) will be briefly described below by giving some examples. (1) A method in which a solution comprising a magnesium compound, an electron donor, and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or a contact reaction is performed with a titanium compound while the solid is precipitated.

(2) A method in which a complex comprising a magnesium compound and an electron donor is subjected to a catalytic reaction with an organometallic compound, and then a titanium compound is subjected to a catalytic reaction. (3) In the contact substance between the inorganic carrier and the organomagnesium compound,
A method in which a titanium compound and preferably an electron donor are contacted and reacted. At this time, the contacted product may be brought into contact with a halogen-containing compound and / or an organometallic compound in advance.

(4) A magnesium compound-supported inorganic or organic carrier is obtained from a mixture of a solution containing a magnesium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier. How to contact.

(5) magnesium compound, titanium compound,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound in a catalytic reaction. At this time, the electron donor is used at least once. (7) A method in which a liquid state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound.
At this time, the electron donor is used at least once.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (9) A method comprising contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor with a titanium compound.

(10) A method of bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then contacting with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. In this method, the electron donor is preferably used at least once.

(12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to precipitate a solid magnesium-titanium complex.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor and a titanium compound.

(15) A method of treating a solid material obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon. In this method,
It may include a step of pulverizing only the magnesium compound, the complex compound consisting of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds.

(16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction.

(17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of contacting a reaction product of a metal oxide, an organomagnesium, and a halogen-containing compound, preferably with an electron donor and a titanium compound.

(19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex,
Then, a method of reacting an electron donor and a titanium compound.

The amount of each of the above components used in preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.01 per mol of the magnesium compound. It is used in an amount of from 10 to 10 mol, preferably from 0.1 to 5 mol, and the titanium compound is from 0.01 to 1000 mol, preferably from 0.1 to 200 mol.
It is used in molar amounts.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is in the range of about 2-200, preferably about 4-100, and the electron donor / titanium (molar ratio) is about 0.0.
1-100, preferably in the range of about 0.2-10,
Desirably, the magnesium / titanium (atomic ratio) is in the range of about 1-100, preferably about 2-50.

Such solid titanium catalyst component (a)
The [catalyst component (Ia)] is a prepolymerized catalyst component (Ib) obtained by prepolymerizing an olefin in the presence of the solid titanium catalyst component (a) and the following organometallic catalyst component (b). It can also be used for polymerization.

(Ib) As the organometallic catalyst component (b) used in the preparation of the prepolymerization catalyst component, organometallic compounds of Group I to Group III metals of the Periodic Table are used. Compounds such as

(B-1) An organoaluminum oxy compound similar to the organoaluminum oxy compound (B-1) and an organoaluminum compound similar to the organoaluminum compound (C).

(B-2) A complex alkyl compound of a Group I metal represented by the following formula and aluminum. M ³ AlR ¹⁷ ₄ (in the formula, M ³ represents Li, Na, and K, and R ¹⁷ represents a hydrocarbon group containing usually 1 to 15, preferably 1 to 4 carbon atoms) (b-3) A dialkyl compound of Group II or Group III represented by the following formula.

R ¹⁷ R ¹⁸ M ⁴ (In the formula, M ⁴ represents Mg, Zn or Cd, R ¹⁷ is the same as above, and R ¹⁸ has usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Indicated by the number of hydrocarbon groups contained therein) Among these, organoaluminum compounds are preferably used.

(Ib) The olefin used for preparing the prepolymerization catalyst component is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene. , 1-hexadecene, 1-
Linear olefins such as octadecene and 1-eicosene;
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-Hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. have a branched structure Examples include olefins.

In the prepolymerization, a catalyst having a much higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (a) in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atom, per liter of an inert hydrocarbon medium described later. It is desirable to be in the range.

The amount of the organometallic catalyst component (b) may be such that 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component (a). The amount is usually about 0.1 to 100 mmol, preferably about 0.5 to 50 mmol, per mol of titanium atom in the solid titanium catalyst component (a).

When carrying out the prepolymerization, an electron donor (e) may be used in addition to the solid titanium catalyst component (a) and the organometallic catalyst component (b). As the electron donor (e), specifically, the electron donor previously used in preparing the solid titanium catalyst component (a), the silicon compound (c) represented by the formula (i) described later, and A compound (d) having two or more ether bonds existing through a plurality of atoms, and further, an organosilicon compound represented by the following formula (ci) can be mentioned.

R _n —Si— (OR ′) _4-n (ci) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
As the organosilicon compound represented by the general formula (ci), specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis
o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyl Trimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n -Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, Lee butyl, trimethyl phenoxy silane, methyl tri Lilo carboxylate (Allyloxy) silane, vinyltris (beta-methoxyethoxy silane),
Examples thereof include vinyltriacetoxysilane and dimethyltetraethoxydisiloxane.

These electron donors (e) can be used alone or in combination of two or more. The electron donor (e) is 0.1 to 50 mol, preferably 0.5 to 30 mol, per 1 mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 1 mole, more preferably 1 to 20 moles.

Prepolymerization is preferably carried out under mild conditions by adding the above olefin and the above catalyst component to an inert hydrocarbon medium. Specific examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and contact products thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The reaction temperature in the prepolymerization may be a temperature at which the resulting prepolymer does not substantially dissolve in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about-. 20 to + 80 ° C, more preferably 0 to +
It is preferably in the range of 40 ° C.

A molecular weight modifier such as hydrogen may be used in the prepolymerization. Such a molecular weight modifier has an intrinsic viscosity [η] of a polymer obtained by prepolymerization measured in decalin at 135 ° C. of about 0.2 dl.
/ G or more, preferably about 0.5 to 10 dl / g.

The prepolymerization is desirably carried out so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component (a) as described above.

Such prepolymerization can be carried out batchwise or continuously. Olefin polymerization catalyst (2)
Is the solid titanium catalyst component (Ia) or (Ib)
Prepolymerization catalyst component, (II) organometallic catalyst component, (II
I) a silicon compound (c) or a compound (d) having two or more ether bonds existing through a plurality of atoms.

As the (II) organometallic catalyst component, the same as the (b) organometallic catalyst component used in the preparation of the (Ib) prepolymerization catalyst component can be used. The silicon compound (c) used as the component (III) is a compound represented by the following formula (i).

[0196] In _{^{R p n -Si- (OR q)}} 4-n ... (i) ( wherein, n is 1, 2 or 3, when n is 1, R
^p represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^{p represents} a secondary or tertiary hydrocarbon group, and the other represents a hydrocarbon group. ^{May be} the same or different, and ^Rq has 1 to 1 carbon atoms.
When 4 is a hydrocarbon group of 4 and 4-n is 2 or 3, R ^q may be the same or different. ) In the silicon compound (c) represented by the formula (i),
Examples of the secondary or tertiary hydrocarbon group include a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, these groups having a substituent, or a hydrocarbon group in which carbon adjacent to Si is secondary or tertiary. Can be mentioned. More specifically, the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,
Examples thereof include a cyclopentyl group having an alkyl group such as a 3,5-trimethylcyclopentyl group, a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes 2-methylcyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples include cyclopentenyl group, cyclopentenyl group having an alkyl group such as 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclopentenyl group, and tetraethylcyclopentenyl group. it can.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is secondary carbon include i-propyl group, s-butyl group, s-amyl group and α-methylbenzyl group. Examples of the hydrocarbon group whose carbon adjacent to is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, and an admantyl group.

When n is 1, the silicon compound (c) represented by the formula (i) includes cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, and 2,3-dimethylcyclopentyltrimethoxysilane. Silane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane,
Examples thereof include trialkoxysilanes such as cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, and 2-norbornanetriethoxysilane.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples of dialkoxysilanes include t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

When n is 2, the silicon compound (c) represented by the formula (i) is preferably a dimethoxy compound represented by the following formula (ii).

[0203]

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In the formula, R ^p and R ^s are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is secondary carbon or tertiary carbon is shown.

Examples of the silicon compound represented by the formula (ii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane and di (2- Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane,
Di (2,3-dimethylcyclopentyl) dimethoxysilane,
Di (2,4-dimethylcyclopentyl) dimethoxysilane,
Di (2,5-dimethylcyclopentyl) dimethoxysilane,
Di (2,3-diethylcyclopentyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane , Di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclo) Pentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3, 4-trimethylcyclopentenyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxy Silane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) ) Dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethyl) Dicyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4 , 5-Tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) ) Dimethoxysilane, di (1,2,
3,4,5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane, di-s-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Examples include monoalkoxysilanes such as cyclopentyldimethylethoxysilane.

Of these, dimethoxysilanes, particularly dimethoxysilanes represented by the formula (ii), are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane. , Di (3-methylcyclopentyl) dimethoxysilane and di-t-amyldimethoxysilane are preferable.

Two or more kinds of these silicon compounds (c) can be used in combination. In the compound (d) having two or more ether bonds existing through a plurality of atoms used as the component (III) (hereinafter sometimes referred to as a polyether compound), the atoms existing between these ether bonds are carbon atoms. , At least one selected from the group consisting of silicon, oxygen, sulfur, phosphorus, and boron, and the number of atoms is 2 or more. Among these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more and having a linear, branched or cyclic structure,
More preferably, a substituent having a branched or cyclic structure is bonded. In addition, the atom existing between two or more ether bonds has a plurality of atoms, preferably 3 to 2 atoms.
Compounds containing 0, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are preferred.

As such a polyether compound,
For example, a compound represented by the following formula can be mentioned.

[0210]

Embedded image

In the formula, n is an integer of 2 ≦ n ≦ 10, and R
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and may have a substituent other than a carbon atom in the main chain. Atoms may be included.

As the polyether compound as described above,
Specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1 , 3-Dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3- Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl) -1,3-
Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (pt-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl
-2-Cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-Diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-
1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-
Isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di
-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isopentyl-
1,3-dimethoxypropane, 2-phenyl-2-isopropyl-
1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-
Dimethoxypropane, 2-benzyl-2-isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-dimethoxymethylfluorene, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4- Diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-
Dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (p -Chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1 , 5-Dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran , 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxy Ethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimetho Shipuropan, 2,2-pentamethylene -
1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,5] undecane, 3,7
-Dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2- Methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-
Diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-
Dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2 -Cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,
3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
Tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, cyclohexyl-t- Butylbis (methoxymethyl) silane, i-propyl-t-butylbis (methoxymethyl) silane and the like can be mentioned.

Of these, 1,3-diethers are preferably used, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2, 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene are preferably used.

Two or more kinds of these polyether compounds (d) can be used in combination. The olefin polymer (Q) can be produced by polymerizing an olefin or copolymerizing two or more kinds of olefins in the presence of such an olefin polymerization catalyst (2).

Examples of the olefins used for the polymerization include α-olefins having 2 to 20 carbon atoms as described above, cyclic olefins having 3 to 20 carbon atoms, styrene, vinylcyclohexane and dienes. further,
An olefin having a branched structure similar to the above, having 4 to 4 carbon atoms
Twenty diene compounds can be used.

In the present invention, propylene is preferably used alone or in combination with propylene and an α-olefin other than propylene. In the polymerization, the solid titanium catalyst component (Ia) or the prepolymerization catalyst component (Ib) is used as titanium atom in the solid titanium catalyst component (Ia) or titanium in the prepolymerization catalyst component (Ib) per liter of the polymerization volume. Converted to atoms, usually about 0.000
It is used in an amount of 1 to 50 mmol, preferably about 0.001 to 10 mmol. In addition, the (II) organometallic catalyst component usually contains about 1 to 2000 metal atoms contained in the (II) organometallic catalyst component per 1 mol of titanium atom in the polymerization system.
It is used in an amount such that it is a mole, preferably about 2-500 moles. Further, (III) the silicon compound (c) or the polyether compound (d) is usually about 0.001 to 50 mol, per 1 mol of the metal atom in the (II) organometallic catalyst component,
It is preferably used in an amount of about 0.01 to 20 mol.

During polymerization, solid titanium catalyst component (a)
The electron donor used in the preparation of and / or the organosilicon compound represented by the above formula (ci) can be used in combination.

When hydrogen is used during the polymerization, an olefin polymer having a high melt flow rate is obtained, and the molecular weight of the olefin polymer obtained can be adjusted by adjusting the hydrogenation amount.

The polymerization reaction is usually carried out in the form of slurry or in the gas phase. When carrying out slurry polymerization, as the reaction solvent, an inert hydrocarbon similar to the inert hydrocarbon used in the preparation of the above-mentioned (Ib) prepolymerization catalyst component can be used.

The polymerization temperature is usually about -50 to 200 ° C,
It is preferably about 20 to 100 ° C., and the polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably about 2 to 50.
kg / cm ² .

Polymerization can be carried out by any of batch, semi-continuous and continuous methods. Propylene Homopolymer (R) The propylene homopolymer (R) has an intrinsic viscosity [η] of 0.
5-10 dl / g, preferably 1.0-5.0 dl / g
And the value of mr / (mm + rr) in the Dyad distribution measured by NMR is 0.7 to 1.3, preferably 0.8 to 1.2.

Here, the values of mr, mm and rr in the diad distribution measured by ¹³ C-NMR were determined as follows. That is, 50 to 70 mg of a sample is
Completely in an MR sample tube (5 mmφ) in a solvent containing about 0.5 ml of hexachlorobutadiene, o-dichlorobenzene or 1,2,4-trichlorobenzene and about 0.05 ml of deuterated benzene as a lock solvent. After dissolving,
It was measured at 120 ° C. by a complete proton decoupling method.
The measurement conditions were a flip angle of 45 ° and a pulse interval of 3.
4T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) is selected. Since T ₁ of the methylene group and the methine group is shorter than that of the methyl group, the recovery of the magnetization is 99% or more under this condition. The chemical shift was set at 21.59 ppm for the methyl group in the third unit of five propylene units in which the head-to-tail bond and the direction of methyl branching were the same.

The spectrum relating to the methyl carbon region (19 to 23 ppm) has a peak region in the first region (21.1 to 2).
1.9 ppm), the second region (20.3 to 21.0 pp)
m) and the third region (19.5 to 20.3 ppm). Each peak in the spectrum is described in the literature (Po
lymer, 30 (1989) 1350).

It should be noted that mr, mm and rr are each a propylene unit 3 bonded by head-to-tail represented by the following formula.
Indicates a chain.

[0225]

[Chemical 12]

Olefin polymer (R) as described above
Are, for example, (A-2) a meso form of the transition metal compound represented by the formula (I), (B) (B-1) an organoaluminumoxy compound, or (B-2) the transition metal compound ( Propylene is polymerized in the presence of an olefin polymerization catalyst (3) consisting of a compound that reacts with A) to form an ion pair and, if necessary, (C) an organoaluminum compound, or (A- 3) An ion pair is formed by reacting a transition metal compound represented by the following formula (II) with (B) (B-1) an organoaluminum oxy compound or (B-2) the transition metal compound (A). It can be produced by polymerizing propylene in the presence of an olefin polymerization catalyst (4) comprising the compound (1) and, if necessary, (C) an organoaluminum compound.

Next, the olefin polymerization catalyst (3) and the olefin polymerization catalyst (4) will be specifically described. The olefin polymerization catalyst (3) includes (A-2) a meso form of the transition metal compound represented by the formula (I), (B) (B-1) an organoaluminum oxy compound, and / or (B- 2) A compound that reacts with the transition metal compound (A-1) to form an ion pair, and, if necessary, (C) an organoaluminum compound.

The transition metal compound (A-2) has the formula (I)
It is a meso form of a transition metal compound represented by. Specific examples of such a transition metal compound (A-2) include a meso form of the compound represented by the above formula (I).

In the present invention, in the meso form of the transition metal compound represented by the above formula (I), the above formulas (III) and (I
It is preferable to use the meso form of the transition metal compound represented by V) or (V).

(B-1) an organoaluminum oxy compound used in the olefin polymerization catalyst (3), (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair, and (C ) An organoaluminum compound is (B-1) an organoaluminum oxy compound used in the olefin polymerization catalyst (1), (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair, And (C) organoaluminum compound.

A propylene homopolymer (C) can be produced by polymerizing propylene in the presence of such an olefin polymerization catalyst (3). During the polymerization, the transition metal compound (A-2) has a concentration of transition metal atoms derived from the transition metal compound (A-2) in the polymerization system of usually 10 ^-8 to 10 ^-3 g atom / liter, preferably 1
Desirably, it is used in an amount of 0 ^-7 to 10 ^-4 gram atoms / liter. When the organoaluminum oxy compound (B-1) is used as the activation compound (B), the atomic ratio of aluminum in the organoaluminum oxy compound (B-1) to the transition metal in the transition metal compound (A-2) (Al / transition metal) is usually 5 to 10000, preferably 10 to 50.
The range is 00. When the ionized ionic compound (B-2) is used as the activation compound (B), the molar ratio of the transition metal compound (A-2) to the ionized ionic compound (B-2) [(A-2) / ( B-2)] is usually in the range of 0.01 to 10, preferably 0.5 to 5. When the organoaluminum compound (C) is used, the organoaluminum compound (C)
The atomic ratio (Al / transition metal) of aluminum in the transition metal to the transition metal in the transition metal compound (A-2) is usually 5 to 100.
00, preferably 10 to 5000.

When producing the propylene homopolymer (R), a liquid phase polymerization method is usually used. The polymerization temperature is usually 0 to 250 ° C., preferably 20 to 200 ° C. The polymerization pressure is usually atmospheric pressure to 10
The pressure is 0 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² .

The molecular weight of the resulting propylene homopolymer (R) can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. The olefin polymerization catalyst (4) includes (A-3) a transition metal compound represented by the following formula (II), (B) an organoaluminum oxy compound (B-1), or (B-2) the transition metal compound. It is formed from a compound which reacts with the compound (A) to form an ion pair, and, if necessary, (C) an organoaluminum compound.

The transition metal compound (A-3) has the following formula (II):
Is a compound represented by.

[0235]

Embedded image

In the formula, M ² represents a Group IVB transition metal atom, specifically a titanium, zirconium or hafnium atom. Cp is a cyclounsaturated hydrocarbon group or chain such as cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group. Shows a unsaturated hydrocarbon group.

X ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An alkylaryl group, an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms is shown.

Z ¹ is SiR ⁷ ₂ , CR ⁷ ₂ , SiR ⁷ ₂ Si
R ⁷ ₂ , CR ⁷ ₂ CR ⁷ ₂ , CR ⁷ ₂ CR ⁷ ₂ CR ⁷ ₂ , CR ⁷ = C
Shows the _{^{R 7, CR 7 2 SiR 7}} 2 or GERR ⁷ _2. Y
^{2, -N (R 8) -,} - O -, - S- or -P
(R ⁸ )-is shown.

R ⁷ is a group selected from a hydrogen atom or an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or a combination thereof, and R ⁸ is a carbon number. An alkyl group having 1 to 10 or an aryl group having 6 to 10 carbon atoms, or 1
Fused ring systems of up to 30 non-hydrogen atoms with one or more R ⁷ may be formed.

W represents 1 or 2. Specific examples of the compound represented by the general formula (II) include (tert-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (methyl amide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (tert-butylamido) dimethyl (tetra Methyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η
⁵ -cyclopentadienyl) silane titanium dichloride,
(Phenyl phosphide) dimethyl (tetramethyl-η ^5-
Examples include cyclopentadienyl) silane zirconium dibenzyl.

(B-1) an organoaluminumoxy compound used in the olefin polymerization catalyst (4), (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair, and (C ) An organoaluminum compound is (B-1) an organoaluminum oxy compound used in the olefin polymerization catalyst (1), (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair, And (C) organoaluminum compound.

A propylene homopolymer (R) can be produced by polymerizing propylene in the presence of such an olefin polymerization catalyst (4). During the polymerization, the transition metal compound (A-3) has a concentration of transition metal atoms derived from the transition metal compound (A-3) in the polymerization system of usually 10 ^-8 to 10 ^-3 g atom / liter, preferably 1
Desirably, it is used in an amount of 0 ^-7 to 10 ^-4 gram atoms / liter. When the organoaluminum oxy compound (B-1) is used as the activation compound (B), the atomic ratio of aluminum in the organoaluminum oxy compound (B-1) to the transition metal in the transition metal compound (A-3) (Al / transition metal) is usually 5 to 10000, preferably 10 to 50.
The range is 00. When the ionized ionic compound (B-2) is used as the activation compound (B), the molar ratio of the transition metal compound (A-3) to the ionized ionic compound (B-2) [(A-3) / ( B-2)] is usually in the range of 0.01 to 10, preferably 0.5 to 5. When the organoaluminum compound (C) is used, the organoaluminum compound (C)
The atomic ratio (Al / transition metal) of aluminum in the transition metal compound to the transition metal in the transition metal compound (A-3) is usually 5 to 100.
00, preferably 10 to 5000.

When producing the propylene homopolymer (R), a liquid phase polymerization method is usually used. The polymerization temperature is usually 0 to 250 ° C., preferably 20 to 200 ° C. The polymerization pressure is usually atmospheric pressure to 10
The pressure is 0 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² .

The molecular weight of the resulting propylene homopolymer (R) can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Examples of the elastomer (S) elastomer include an olefin elastomer and a styrene thermoplastic elastomer.

Examples of the olefin elastomers include elastomers obtained by copolymerizing α-olefins such as ethylene, propylene, 1-butene and 1-pentene, and elastomers obtained by copolymerizing these with non-conjugated dienes. .

As the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene,
Examples thereof include methylene norbornene and 5-ethylidene-2-norbornene.

Specific examples of such olefinic elastomers include 1-ethylene / propylene copolymer elastomer, ethylene / 1-butene copolymer elastomer,
Ethylene / propylene / 1-butene copolymer elastomer, ethylene / propylene / non-conjugated diene copolymer elastomer, ethylene / 1-butene-non-conjugated diene copolymer elastomer, ethylene / propylene / 1-butene-non-conjugated diene copolymer An amorphous elastic copolymer containing an olefin as a main component such as a polymer elastomer can be mentioned.

Melt flow rate (MFR) measured at 230 ° C. of the above olefinic elastomer
Is 0.01 to 50 g / 10 minutes, preferably 0.01 to 1
It is desirable that the amount is 0 g / 10 minutes, more preferably 0.01 to 5 g / 10 minutes.

The iodine value (unsaturation) of the olefin elastomer is preferably 16 or less. Examples of the styrene-based thermoplastic elastomer include a block copolymer of a styrene-based compound and a conjugated diene compound.

Examples of the styrene compound include styrene, α-methylstyrene, p-methylstyrene, alkylstyrene such as pt-butylstyrene, p-methoxystyrene, vinylnaphthalene and the like. Of these, styrene is preferred.

As the conjugated diene compound, butadiene,
Isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-
Examples include diethyl-1,3-octadiene. Among these, butadiene and isoprene are preferred.

These compounds may be used in combination of two or more kinds. In the styrene-based thermoplastic elastomer used in the present invention, the weight ratio of the unit derived from the styrene compound and the unit derived from the conjugated diene compound is preferably 10/90 to 65/35, and 2
It is more preferably 0/80 to 50/50.

The molecular structure of the styrene thermoplastic elastomer may be linear, branched, radial or a combination thereof. Specific examples of such styrene-based thermoplastic elastomers include styrene / butadiene diblock copolymers, styrene / butadiene / styrene triblock copolymers, styrene / isoprene diblock copolymers, styrene / isoprene /
Styrene triblock copolymer, hydrogenated styrene / butadiene diblock copolymer, hydrogenated styrene / butadiene / styrene triblock copolymer, hydrogenated styrene / isoprene diblock copolymer, styrene / A hydrogenated product of an isoprene / styrene triblock copolymer can be mentioned.

The styrene thermoplastic elastomer used in the present invention preferably has a melt flow rate measured at 230 ° C. under a load of 2.16 kg of 1 to 100 g / 10 minutes.

Modified olefin polymer (T) The modified olefin polymer (T) is an olefin polymer such as an olefin homopolymer or an olefin copolymer,
It is obtained by heating an unsaturated compound having a polar group in the molecule in the presence of a radical initiator for graft modification.

Examples of the olefin-based polymer include the polymers described above as the olefin polymer (Q) and the elastomer (S), and specific examples thereof include a propylene homopolymer and a propylene / ethylene block copolymer. Polymer, crystalline propylene / ethylene random copolymer, ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / propylene / 1-butene copolymer rubber, ethylene / propylene / non-conjugated diene Examples thereof include a copolymer rubber, an ethylene / 1-butene / non-conjugated diene copolymer rubber, and an ethylene / propylene / 1-butene / non-conjugated diene copolymer rubber. High-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, poly 1-butene, poly 4-methyl 1-
A penten or the like can also be used.

Among these, a propylene homopolymer and a crystalline propylene / ethylene random copolymer containing a unit derived from ethylene in an amount of 10 mol% or less are preferably used.

Examples of the unsaturated compound having a polar group in the molecule include a compound having a polar group such as a carboxyl group and an acid anhydride group, and an aromatic vinyl compound. Specific examples of the unsaturated compound having a carboxyl group or an acid anhydride group in the molecule include acrylic acid, methacrylic acid, α
-Ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, maleic anhydride, itaconic anhydride,
Α, β such as citraconic anhydride and tetrahydrophthalic acid
-Unsaturated carboxylic acid anhydride, bicyclo [2.2.1] hept-
Mention may be made of anhydrides of unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid anhydride. Among these, acrylic acid, maleic acid, itaconic acid, maleic anhydride,
Itaconic anhydride is preferred.

As the aromatic vinyl compound, styrene,
α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl- 2-Vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-
Examples thereof include vinylcarbazole and N-vinylpyrrolidone.

The unsaturated compounds having these polar groups are
It is also possible to use two or more types in combination. In producing the modified olefin polymer, an organic peroxide, an azo compound or the like can be used as a radical initiator.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valalate, 2,2-
Peroxyketals such as bis (t-butylperoxy) butane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α, α'-
Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylper) (Oxy) hexyne-3 and other dialkyl peroxides, acetyl peroxide, isobutyryl peroxide,
Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide,
Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexano Ate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy)
Hexane, t-butyl peroxymaleic acid, t-
Peroxyesters such as butyl peroxyisopropyl carbonate, cumyl peroxy octate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide Examples thereof include oxides and hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide.

Among these, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide and 2,5-dimethyl-2 , 5-Bis (t-butylperoxy) hexane, 2,5
-Dimethyl-2,5-bis (t-butylperoxy) hexine-
3, Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, t-butylperoxy-2-ethylhexanoate and the like are preferably used.

Examples of the azo compound include azobisisobutyronitrile. Two or more kinds of such radical initiators can be used in combination. When the olefin polymer is graft-modified, the unsaturated compound having a polar group in the molecule as described above is usually 0.01 to 100 parts by weight with respect to 100 parts by weight of the olefin polymer.
It is used in an amount of 50 parts by weight, preferably 0.1-40 parts by weight.

The radical initiator is usually used in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the olefin polymer.
It is preferably used in an amount of 0.05 to 8 parts by weight. The graft modification can be performed by a known method. Specifically, for example, the following method is used. (I) A method of melt-kneading the above-mentioned olefin polymer and an unsaturated compound having a polar group in the molecule in the presence of a radical initiator. (Ii) A method in which an unsaturated compound having a polar group in the molecule and a radical initiator are added to an organic solvent solution of the above olefin polymer and heated. (Iii) A method in which an unsaturated compound having a polar group in the molecule and a radical initiator are added to an aqueous dispersion of the olefin polymer and heated. (Iv) the above olefin polymer and an unsaturated compound having a polar group in the molecule, in the presence of a radical initiator,
A method of heating at a temperature below the melting point of the olefin polymer.

The temperature below the melting point of the olefin polymer is, specifically, 165 ° C. or less for the propylene polymer and 140 ° C. or less for the ethylene polymer. The intrinsic viscosity [η] of such a modified olefin polymer in decalin is such that the modified olefin polymer is a propylene homopolymer, a crystalline propylene / ethylene random copolymer, or a crystalline propylene / ethylene block copolymer. In the case of a modified olefin-based polymer obtained by modifying a propylene-based polymer such as the above, usually 0.1 to 1 dl / g, preferably 0.15 to 0.8 dl / g, more preferably 0.2 to It is 0.6 dl / g.

Further, the olefin polymer is high density polyethylene, medium density polyethylene, high pressure method low density polyethylene, linear low density polyethylene, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, ethylene. -In the case of a modified olefin polymer obtained by modifying an ethylene copolymer such as a polar group-containing unsaturated compound copolymer, it is usually 0.05 to 1 dl / g, preferably 0.08 to 0. It is 6 dl / g, more preferably 0.1 to 0.5 dl / g.

Thermoplastic Resin Composition The thermoplastic resin composition is the above-mentioned thermoplastic resin (P): 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight.
And the olefin polymer (Q); 5 to 80% by weight, preferably 10 to 70% by weight, more preferably 15 to 50% by weight, and the propylene homopolymer (R); 5 to 80% by weight, preferably 5 to 50% by weight, more preferably 5 to 30% by weight, the elastomer (S); 0 to 50% by weight, preferably 0 to 40% by weight, more preferably 0 to 30% by weight, the modified olefin System polymer (T); 0.5 to 20% by weight based on 100 parts by weight of the total amount of the thermoplastic resin (P), olefin polymer (Q), propylene homopolymer (R) and elastomer (S), Preferably 2.0-18
% By weight, more preferably 5.0 to 15% by weight.

Examples of the method for preparing such a thermoplastic resin composition include the following methods. A thermoplastic resin (P), an olefin polymer (Q),
Propylene homopolymer (R) and elastomer (S)
And a modified olefin polymer (T) are melt-kneaded. After preparing an olefin polymer composition by melt-kneading the olefin polymer (Q) and the propylene homopolymer (R), the olefin polymer composition, the thermoplastic resin (P), and the elastomer (S ), A method of melt-kneading the modified olefin polymer (T). An olefin polymer (Q) and a propylene homopolymer (R) are obtained by polymerizing an olefin containing propylene in a single-stage polymerization step in the presence of at least two kinds of catalysts.
And preparing an olefin polymer composition, and then melt-kneading the olefin polymer composition, the thermoplastic resin (P), the elastomer (S), and the modified olefin polymer (T).

As a method of melt-kneading each component, a conventionally known method can be widely adopted. As the melt-kneading device, a mixing roll, an intensive mixer,
For example, a Banbury mixer, kneader, single-screw or twin-screw extruder can be used.

Mixing and kneading is usually carried out at a temperature of 150 to 280 ° C., preferably 170 to 240 ° C. for usually 1 to 20 minutes.
It is desirable to carry out for 1 to 10 minutes. After being melt-kneaded in this manner, the composition is usually obtained in the form of pellets.

When the olefin polymer composition is prepared by the method of above, at least one catalyst (catalyst selected from the above-mentioned olefin polymerization catalyst (1) and olefin polymerization catalyst (2) is used as at least two catalysts. -1,2)
And at least one catalyst (catalyst-3, 4) selected from the olefin polymerization catalyst (3) and the olefin polymerization catalyst (4).

[0272] Catalyst-1,2 used in polymerization, and catalyst-
The ratio of 3,4 is the sum of the transition metal atom in the olefin polymerization catalyst (1) and the titanium atom in the olefin polymerization catalyst (2) and the transition metal in the olefin polymerization catalyst (3). Atomic ratio to the total of atoms and transition metal atoms in the olefin polymerization catalyst (4) (catalyst-1,2 /
Catalyst-3,4), 1/10000 to 1/1, preferably 1
It is preferably in the range of / 1000 to 1/10.

Olefin polymerization catalyst (1), olefin polymerization catalyst (3) and olefin polymerization catalyst (4)
When the olefin polymer composition is produced in combination with at least one catalyst selected from the group consisting of the transition metal compounds, the total amount of the transition metal compounds is usually 10 as the concentration of the transition metal atoms in the transition metal compound in the polymerization system. ^-8 to 10 ^-3 g atom /
It is desirable to use it in an amount of liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter. When the organoaluminum oxy compound (B-1) is used as the activating compound (B), the atomic ratio of the aluminum in the organoaluminum oxy compound (B-1) and the total amount of transition metals in the transition metal compound (Al / Transition metal) is usually 5 to 1000
The range is 0, preferably 10 to 5000. When the ionized ionic compound (B-2) is used as the activating compound (B), the molar ratio of the total amount of transition metal compounds to the ionized ionic compound (B-2) [transition metal compound / (B-2) ]
Is usually 0.01 to 10, preferably 0.5 to 5. When the organoaluminum compound (C) is used,
The atomic ratio of the aluminum in the organoaluminum compound (C) to the total amount of transition metals in the transition metal compound (Al /
(Transition metal) is usually 5 to 10,000, preferably 10
It is in the range of 5000.

When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 1
It is preferably in the range of 00 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2.

Olefin polymerization catalyst (2), olefin polymerization catalyst (3) and olefin polymerization catalyst (4)
In the case of producing an olefin polymer composition by combining at least one catalyst selected from the group consisting of a transition metal compound and a solid titanium catalyst component, the transition metal compound and the solid titanium catalyst component are a solid metal and a transition metal compound in the transition metal compound in the polymerization system. The total concentration of titanium atoms in the titanium catalyst component is usually 10 ^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7 to 10 ^-4 gram atom / liter. When the organoaluminum oxy compound (B-1) is used as the activating compound (B), aluminum in the organoaluminum oxy compound (B-1), the transition metal in the transition metal compound and titanium in the solid titanium catalyst component are used. The atomic ratio (Al / transition metal + Ti) with the atom is usually 5 to 1000.
The range is 0, preferably 10 to 5000. When the ionized ionic compound (B-2) is used as the activation compound (B), the molar ratio of the transition metal compound and the solid titanium catalyst component to the ionized ionic compound (B-2) [transition metal compound + Ti / (B-2)] is usually 0.01 to 1
It is 0, preferably in the range of 0.5 to 5. When the organoaluminum compound (C) is used, the atomic ratio (Al / transition metal + Ti) of aluminum in the organoaluminum compound (C) to the titanium atom in the transition metal in the transition metal compound and the solid titanium catalyst component is , Usually 5 to 1000
The range is 0, preferably 10 to 5000.

When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 1
It is preferably in the range of 00 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2.

The thermoplastic resin composition according to the present invention contains a softening agent, a filler, and a softening agent within a range that does not impair the object of the present invention.
Pigments, stabilizers, plasticizers, flame retardants, lubricants, antistatic agents,
An electrical property improver and the like may be contained as necessary.

Specific examples of the filler include carbonates such as precipitated calcium carbonate, ground calcium carbonate and magnesium carbonate; aluminum hydroxide, magnesium hydroxide,
Hydroxides such as magnesium oxide; zinc oxide, zinc white,
Oxides such as magnesium oxide; natural silicic acid or silicates such as kaolinite, calcined clay, pyrophyllite, sericite, talc (fine powder), wollastonite, hydrous calcium silicate, hydrous aluminum silicate,
Powdered fillers represented by synthetic silicic acid or silicates such as hydrous silicic acid and anhydrous silicic acid, flaky fillers such as mica, sepiolite, PMF (Processed Mineral Fi)
ber), xonotlite, potassium titanate, elestadite,
Fibrous fillers such as basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, balun fillers such as glass balun and fly ash balun, and organic fillers such as high styrenes, lignin, and re-rubber. .

These fillers are usually used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the olefin polymer composition.

[0280]

The thermoplastic resin composition of the present invention has a high elastic modulus and impact strength.

[0281]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the following examples, the composition and physical properties of polymers were measured as follows. Melt flow rate (MFR) 230 ° C. in accordance with ASTM D1238-65T,
It was measured under a load of 2.16 kg.

Intrinsic viscosity [η] Measured in decahydronaphthalene at 135 ° C. Flexural Modulus (FM) According to ASTM D790, an FM test piece punched out from a 2 mm thick press sheet molded at 200 ° C.
The test was performed at 3 ° C., a span interval of 32 mm, and a bending speed of 5 mm / min.

Izod impact strength (IZ) Measured according to ASTM D256. Test piece (with notch): 12.7 mm (width) x 6.4 mm
(Thickness) x 64 mm (Length)

[0285]

[Production Example 1] [Preparation of solid aluminoxane component (a)] 300 ml reactor with a stirrer capable of reducing pressure, 67 m containing methylaluminoxane corresponding to 100 mmol of aluminum atom
After adding 1 l of a toluene solution (methylaluminoxane manufactured by Schering), 100 ml of purified n-decane was added at room temperature with stirring for about 0.5 hour to precipitate methylaluminoxane. Next, the temperature inside the reactor was raised to 35 ° C. over about 3 hours while reducing the pressure inside the reactor to 4 Torr using a vacuum pump, thereby removing toluene in the reactor and further precipitating methylaluminoxane. .
The reaction solution was filtered using a filter to remove the liquid phase portion, and then the solid portion was resuspended in n-decane to give a 0.18 mmol-Al / ml aluminoxane suspension [solid aluminoxane component (a)]. Got

[Preparation of Solid Catalyst Component (b)] 100 ml of n-hexane was charged into a 400 ml reactor which had been sufficiently replaced with nitrogen, and the solid aluminoxane component (a) obtained above was mixed with A
10.5 mmol in terms of 1 atom, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride in terms of Zr atom, 0.07 mmol Was added and stirred for 20 minutes. After adding 100 ml of n-hexane and then adding 0.9 mmol of triisobutylaluminum and stirring for 10 minutes, propylene gas (2.2 liter / hr) was added for 4 hours at 20 ° C.
And propylene was preliminarily polymerized. The supernatant solution is removed by decantation and decanted 150
Washed 3 times with ml. As a result, Z per 1 g of solid catalyst
A solid catalyst component (b) carrying r; 0.010 mmol and Al; 4.3 mmol was obtained.

[Polymerization] In a stainless steel autoclave having an internal volume of 2 liters, 500 g of propylene and 4.5 liters of hydrogen were charged at room temperature, the temperature was raised to 40 ° C., and then 0.5 mmol of triisobutylaluminum, The solid catalyst component (b) is converted to zirconium atom to 0.00
4 mmol was added and polymerization was carried out at 50 ° C. for 25 minutes.

The propylene polymer (HPP) thus obtained had an intrinsic viscosity [η] of 2.4 dl / g, a melting point (Tm) of 161 ° C. and an MFR of 3.0 g / 10 minutes.

[0289]

[Production Example 2] Purified toluene (800 ml) was charged into a glass reactor having an internal volume of 2 liters, which had been sufficiently purged with nitrogen, and propylene (200 liters / hour) was passed through the reactor to give 80
It was kept at 50 ° C. for 10 minutes while stirring at 0 rotation. Then, 2.88 mg of triisobutylaluminum in terms of aluminum was charged. Further, methylaluminoxane (manufactured by Schering Co.) was converted into aluminum atoms at 5.60 milligram atoms, and (tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride was converted into titanium atoms at 0.016. Toluene solution containing milligram atom 4ml
Charged. After polymerizing at 50 ° C. and normal pressure for 1 hour,
A small amount of isobutanol was added to terminate the polymerization.

After the reaction, 400 m of dilute hydrochloric acid in methanol
The reaction solution was put into 1 to remove the solvent residue, and the obtained polymer was dried under reduced pressure overnight. The obtained propylene homopolymer (APP) was 47 g, and the intrinsic viscosity [η] was 1.83 dl / g. The results are shown in Table 1.

[0291]

[Table 1]

[0292]

Example 1 The propylene polymer (HP
P) 24 parts by weight and propylene homopolymer (APP) 8
Parts by weight, ethylene-butene copolymer (EBR) [ethylene content 82 mol%, intrinsic viscosity [η] 1.4 dl / g] 8
0.2 parts by weight of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as an antioxidant and calcium stearate as a hydrochloric acid absorber in an amount of 0.1 part by weight. 1 part by weight was added, and this was used at 200 ° C. using a Labo Plastomill with an internal volume of 50 ml
Melt kneading was carried out for 5 minutes at a rotation speed of 50 rpm to obtain an olefin polymer composition.

Next, 60 parts by weight of polyamide (PA) [trade name: Ube nylon 61013B manufactured by Ube Industries, Ltd.], 40 parts by weight of the olefin polymer composition, and anhydrous maleated polypropylene (MPP) [Mitsui Sekiyu] Chemical Industry Co., Ltd., maleic acid addition amount: 8% by weight] 10 parts by weight of a mixture, and tetrakis [methylene-3 as an antioxidant.
(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (0.2 parts by weight) and calcium stearate (0.1 parts by weight) as a hydrochloric acid absorbent were added, and an internal volume of 50 ml of Laboplast mill was added. Was melt-kneaded for 5 minutes at 200 ° C. and a rotation speed of 50 rpm to obtain a thermoplastic resin composition.

The flexural modulus and Izod impact strength of the resulting thermoplastic resin composition were measured. Table 2 shows the results.

[0295]

[Example 2] Polystyrene (PS) [Mitsui Toatsu Co., Ltd.
57.2 parts by weight of trade name: Topolex 550], 30 parts by weight of the olefin polymer composition prepared in Example 1, ethylene-butene copolymer (EBR) (ethylene content 82 mol%, intrinsic viscosity [Η] 1.4 dl / g) 4
2.9 parts by weight and styrene-grafted polypropylene (S
PP) [manufactured by Mitsui Petrochemical Industry Co., Ltd., styrene unit content: 20% by weight] in 10 parts by weight of a mixture, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxy) as an antioxidant. 0.2 parts by weight of phenyl) propionate] methane and 0.1% of calcium stearate as a hydrochloric acid absorbent.
Parts by weight were added, and this was melt-kneaded for 5 minutes at 200 ° C. and a rotation speed of 50 rpm using a Labo Plastomill having an internal volume of 50 ml to obtain a thermoplastic resin composition.

The flexural modulus and Izod impact strength of the resulting thermoplastic resin composition were measured. Table 2 shows the results.

[0297]

Comparative Example 1 A mixture of 100 parts by weight of the olefin polymer composition prepared in Example 1 and 10 parts by weight of maleated anhydride polypropylene (manufactured by Mitsui Petrochemical Industry Co., Ltd., maleic acid addition amount: 8% by weight) was used. 0.2 parts by weight of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as an antioxidant and 0.1 parts by weight of calcium stearate as a hydrochloric acid absorbent were added. This was melt-kneaded for 5 minutes at 200 ° C. and a rotation speed of 50 rpm using a Labo Plastomill having an internal volume of 50 ml to obtain a thermoplastic resin composition.

The flexural modulus and Izod impact strength of the resulting thermoplastic resin composition were measured. Table 2 shows the results.

[0299]

Comparative Example 2 100 parts by weight of the olefin polymer composition prepared in Example 1 and styrene-grafted polypropylene [manufactured by Mitsui Petrochemical Industry Co., Ltd., styrene unit content: 20]
Wt%] to 10 parts by weight of the mixture, 0.2 parts by weight of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as an antioxidant and stearic acid as a hydrochloric acid absorbent. 0.1 parts by weight of calcium phosphate was added, and this was melt-kneaded for 5 minutes at 200 ° C. and a rotation speed of 50 rpm using a Labo Plastomill having an internal volume of 50 ml to obtain a thermoplastic resin composition.

The flexural modulus and Izod impact strength of the resulting thermoplastic resin composition were measured. Table 2 shows the results.

[0301]

[Table 2]

Claims (2)

[Claims] 1. A thermoplastic resin (P); 10 to 90% by weight.
And (Q) (q-1) the intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, and (q-2) the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC). Temperature (Tm) is 1
Olefin polymer having a temperature of 00 ° C or higher; 5 to 80% by weight
And (R) (r-1) intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, and (r-2) in the diad distribution measured by NMR, the value of mr / (mm + rr) is 0. Propylene homopolymer in the range of 0.7 to 1.3; 5 to 80% by weight; (S) elastomer; 0 to 50% by weight; (T) modified olefin polymer; the (P) thermoplastic resin , (Q) olefin polymer, (R) propylene homopolymer, and (S) elastomer in an amount of 0.5 to 20% by weight based on 100 parts by weight in total. 2. The olefin polymer (Q) has an (a-1) intrinsic viscosity [η] in the range of 0.5 to 10 dl / g.
-2) The temperature (Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 100 ° C or higher, and (a-3) the structural unit derived from propylene is 80 to
It is contained in a proportion of 100 mol%, the constituent unit derived from ethylene is contained in a proportion of 0 to 10 mol%, and the constituent unit derived from an α-olefin having 4 to 12 carbon atoms is 0 to 15 mol. The thermoplastic resin composition according to claim 1, which is a propylene polymer contained in a ratio of%.