JP3506536B2 - Graft-modified propylene polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel graft-modified propylene-based polymer, and more specifically, in hot-melt adhesion with a metal or a polar resin, it has a low-temperature adhesive property and an adhesive force retention property in a high-temperature atmosphere. The present invention relates to a graft-modified propylene polymer having an excellent balance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based polymers such as propylene homopolymers and propylene / α-olefin copolymers are molded by various molding methods and used for various purposes. Further, among the propylene / α-olefin copolymers, those having a low propylene content, that is, those in the so-called elastomer region are also used as impact resistance improving materials for thermoplastic resins. Such a propylene-based polymer may be used for lamination with other resins, metal foils, etc., or blending with other resins. However, the propylene-based polymer has no polar group in the molecule,
Since it is a so-called non-polar resin, it has a poor affinity with various polar substances including metals, and it has been difficult to use for such applications. Therefore, when it is used for applications such as adhesion with a metal or blending with a polar resin, it is necessary to improve the affinity with a polar substance by graft-copolymerizing a polar monomer with a propylene-based polymer. there were.

By the way, in recent years, improvement of productivity and energy saving have been required in many manufacturing fields, and in the case of adhering a graft-modified propylene-based polymer and a metal or the like, from the viewpoint of high speed molding and energy saving, a lower temperature is used. There is a need for a graft-modified propylene-based polymer that can be bonded with (low energy). However, conventionally known graft-modified propylene-based polymers, when using a lower melting point in order to improve low-temperature adhesion,
The adhesive strength in a high temperature atmosphere may be extremely reduced.
Therefore, if a graft-modified propylene-based polymer that has good low-temperature adhesiveness to metals and the like and has little decrease in adhesive strength in a high-temperature atmosphere appears, its industrial value will be extremely great.

As a result of intensive studies conducted by the present inventors in view of such prior art, propylene alone having a high triad tacticity, a small proportion of positional irregular units, and an intrinsic viscosity [η] within a specific range is used. A graft-modified propylene-based polymer in which a polar monomer is graft-copolymerized with the polymer, comprising an ethylene unit in a proportion of 0.5 to 5 mol%, having a high triad tacticity, and a proportion of position irregular units and A graft-modified propylene-based polymer in which a polar monomer is graft-copolymerized with a propylene copolymer having an intrinsic viscosity [η] within a specific range, and an ethylene unit in an amount of 5 to 50 mol%, and has high triad tacticity. , A propylene / ethylene random copolymer having a ratio of position irregular units and an intrinsic viscosity [η] within a specific range is a polar monomer. The graft-modified propylene-based polymer which is graft-copolymerized has been found to have excellent adhesiveness in adhesion to a metal or a polar resin, and also has excellent adhesive force in a high temperature atmosphere, and has completed the present invention. .

[0005]

An object of the present invention is to provide a graft-modified propylene-based polymer which has excellent adhesiveness in adhesion to a metal or a polar resin and an adhesive strength in a high temperature atmosphere.

[0006]

SUMMARY OF THE INVENTION The first graft-modified propylene-based polymer according to the present invention has (i) the triad tacticity of the propylene unit chain portion composed of head-to-tail bonds, which is determined by ¹³ C-NMR, to be 99.0. % Or more, (ii) ¹³
The proportion of regio-irregular units based on 2,1-insertion of propylene monomer in total propylene insertion determined by C-NMR is 0.20% or less, and (iii) intrinsic viscosity measured in decalin at 135 ° C. [Η] is 0.1 to 20 dl /
The polar monomer is graft-copolymerized with the propylene homopolymer in the range of g.

In the present invention, it is desirable that the polar monomer is at least one kind of monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

The second graft-modified propylene-based polymer according to the present invention comprises (i) a propylene unit of 95 to 99.5.
(Ii) the triad tacticity of the chain portion of the propylene unit composed of head-to-tail bonds, which is determined by ¹³ C-NMR, is 95.0. % Or more, and (iii) ¹³ C-NM
The ratio of regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion determined by R is in the range of 0.05 to 0.5%, and (iv) measured at 135 ° C in decalin. Intrinsic viscosity [η] is 0.1-12dl
It is characterized in that a polar monomer is graft-copolymerized with a propylene copolymer in the range of / g.

In the present invention, the polar monomer is preferably at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

The third graft-modified propylene-based polymer according to the present invention comprises (i) 50 to 95 mol% of propylene units and 5 to 50 mol% of ethylene units, and (ii)
The triad tacticity of the chain portion of the propylene unit consisting of the head-to-tail bond was 9 determined by ¹³ C-NMR.
0.03% or more, (iii) 2,3 of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR
1-The ratio of positional irregular units based on insertion is 0.05 to 0.
The polar monomer is graft-copolymerized with a propylene / ethylene random copolymer having an intrinsic viscosity [η] measured in decalin of 135 ° C. and decalin of 0.1 to 12 dl / g in the range of 5%. It is characterized by

In the present invention, the polar monomer is preferably at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, which is derived from the polar monomer. It is desirable that the graft amount of the graft group is 0.1 to 50% by weight.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The graft-modified propylene polymer according to the present invention will be specifically described below.

The graft-modified propylene polymer according to the present invention comprises a propylene homopolymer and an ethylene unit of 0.5.
A polar monomer is graft-copolymerized with a propylene-based polymer such as a propylene copolymer containing 5 to 50 mol% of ethylene unit and a propylene-ethylene random copolymer containing 5 to 50 mol% of ethylene unit.

First, the propylene homopolymer, propylene copolymer and propylene / ethylene random copolymer used in the present invention will be explained. [Propylene Homopolymer] Propylene homopolymer has a triad tacticity (of three arbitrary propylene units in the polymer chain, the direction of methyl branch in the propylene unit is the same, and each propylene unit is head-to-tail). The ratio of 3 chains of propylene units bonded together in (hereinafter sometimes referred to as "mm fraction") is 99.0% or more, preferably 99.2% or more, more preferably 99.5% or more. Desirably, the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is
It is desirable that it is 0.20% or less, preferably 0.18% or less, more preferably 0.15% or less, and 135
The intrinsic viscosity [η] measured in decalin at ℃ is 0.1
20 dl / g, preferably 0.5 to 10 dl / g, more preferably 1 to 5 dl / g.

The proportion of regioregular units based on triad tacticity and 2,1-insertion can be determined by ¹³ C-NMR spectrum of a propylene homopolymer as described later.

Further, in the propylene homopolymer, the proportion of positional disordered units based on the 1,3-insertion of propylene monomer in the total propylene insertion is less than the lower limit of detection by ¹³ C-NMR measurement (less than 0.03%). ) Is preferable, and the value of Mw / Mn, which is an index of the molecular weight distribution, is 1.5 to 3.
5, preferably 2.0 to 3.0, more preferably 2.0.
It is preferably in the range of to 2.5.

Such a propylene homopolymer can be produced, for example, by homopolymerizing propylene in the presence of an olefin polymerization catalyst (1) as described below. Polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, or gas phase polymerization methods.

In the liquid phase polymerization method, an inert hydrocarbon may be used as a solvent, or propylene itself may be used as a solvent. Specifically as the inert hydrocarbon solvent used in the liquid phase polymerization method, butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; benzene, toluene,
Aromatic hydrocarbons such as xylene; petroleum fractions such as gasoline, kerosene, and light oil. Of these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons,
Petroleum fraction and the like are preferable.

The polymerization temperature of propylene is usually -50 to 100 ° C, preferably 0 to 0 when carrying out the suspension polymerization method.
It is preferably in the range of 90 ° C, and when carrying out the solution polymerization method, it is usually 0 to 250 ° C, preferably 20 to 20
It is preferably in the range of 0 ° C. When carrying out the gas phase polymerization method, the copolymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually from atmospheric pressure to 100 kg / cm ² , preferably from atmospheric pressure to 50 kg / cm ² , and the polymerization reaction is carried out by any of a batch system, a semi-continuous system and a continuous system. be able to. In addition, polymerization is performed under different reaction conditions 2
It is also possible to divide into more than one step.

The molecular weight of the resulting propylene homopolymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and / or the polymerization pressure.

[Propylene Copolymer] The propylene copolymer contains a propylene unit in a proportion of 95 to 99.5 mol%, preferably 95 to 99 mol%, more preferably 95 to 98 mol%, and an ethylene unit. 0.5 to 5 mol%,
Preferably 1-5 mol%, more preferably 2-5 mol%
It is a random copolymer of propylene and ethylene contained at a ratio of.

Such a propylene copolymer may contain a constitutional unit derived from an olefin other than propylene and ethylene in an amount of, for example, 5 mol% or less.
The propylene copolymer has a triad tacticity of
It is desirable to be 95.0% or more, preferably 96.0% or more, more preferably 97.0% or more. , 0.05% to 0.5%,
Preferably 0.05 to 0.4%, more preferably 0.0.
5 to 0.3% is desirable, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 12 dl /
g, preferably 0.5 to 12 dl / g, and more preferably 1 to 12 dl / g.

The proportion of regioregular units based on triad tacticity and 2,1-insertion can be determined from the ¹³ C-NMR spectrum of the propylene copolymer as described later.

Further, in the propylene copolymer, it is desirable that the proportion of regio-irregular units based on the 1,3-insertion of propylene monomer in the total propylene insertion is 0.05% or less, which is an index of the molecular weight distribution Mw. The value of / Mn is 1.5
˜3.5, preferably 2.0 to 3.0, and more preferably 2.0 to 2.5.

Such a propylene copolymer can be produced, for example, by copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst (2) described below. The copolymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as described above can be used, and propylene and / or ethylene can also be used as a solvent. The copolymerization temperature of propylene and ethylene is usually -50 to 100 ° C, preferably 0 to 90 ° C when carrying out the suspension polymerization method.
When the solution polymerization method is carried out, it is usually 0 to 250 ° C., preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the copolymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² , and the copolymerization reaction is
It can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the copolymerization in two or more stages under different reaction conditions.

The molecular weight of the resulting propylene copolymer is
It can be adjusted by the presence of hydrogen in the polymerization system or by changing the copolymerization temperature and / or the copolymerization pressure.

[Propylene / Ethylene Random Copolymer] The propylene / ethylene random copolymer contains a propylene unit in a proportion of 50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol%. 5 to 50 mol% of ethylene units, preferably 7 to 4
It is a random copolymer (elastomer) of propylene and ethylene contained in a proportion of 0 mol%, more preferably 10 to 30 mol%.

Such a propylene / ethylene random copolymer may contain a structural unit derived from an olefin other than propylene and ethylene in an amount of, for example, 10 mol% or less.

The propylene / ethylene random copolymer preferably has a triad tacticity of 90.0% or more, preferably 93.0% or more, more preferably 96.0% or more. Proportion of regio-irregular units based on 2,1-insertion of propylene monomer is 0.05 to 0.5%, preferably 0.05 to 0.4%,
It is more preferably 0.05 to 0.3%, and the intrinsic viscosity [η] measured in decalin at 135 ° C is 0.1 to 12 dl / g, preferably 0.5 to 12 dl /.
g, more preferably 1 to 12 dl / g.

The proportion of regioregular units based on triad tacticity and 2,1-insertion can be determined by ¹³ C-NMR spectrum of a propylene / ethylene random copolymer as described later.

Further, in the propylene / ethylene random copolymer, it is preferable that the position irregular unit based on the 1,3-insertion in the total propylene insertion is 0.05% or less, preferably 0.03% or less.

Such a propylene / ethylene random copolymer can be produced, for example, by copolymerizing propylene and ethylene in the presence of an olefin polymerization catalyst (2) described below. The copolymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as described above can be used, and propylene and / or ethylene can also be used as a solvent. The copolymerization temperature of propylene and ethylene is usually -50 to 100 ° C, preferably 0 to 90 ° C when carrying out the suspension polymerization method.
When the solution polymerization method is carried out, it is usually 0 to 250 ° C., preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the copolymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² , and the copolymerization reaction is
It can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the copolymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained propylene / ethylene random copolymer can be adjusted by allowing hydrogen to be present in the polymerization system, or by changing the copolymerization temperature and the copolymerization pressure.

[Olefin Polymerization Catalyst] Next, the olefin polymerization catalyst (1) used for producing the propylene homopolymer, and the olefin polymerization used for producing the propylene copolymer and the propylene / ethylene random copolymer. The catalyst (2) will be described.

The olefin polymerization catalyst (1) comprises (A) a transition metal compound represented by the following formula (I), (B) (B-1) an organoaluminum oxy compound, and /
Alternatively, (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair and, if necessary, (C) an organoaluminum compound.

The transition metal compound (A) (hereinafter sometimes referred to as "component (A)") has the following general formula (I):
Is a transition metal compound represented by.

[0039]

[Chemical 1]

In the formula, M represents a transition metal atom of Groups IV to VIb of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably Titanium, zirconium or hafnium, particularly preferably zirconium.

R ¹ represents one kind of group selected from a hydrocarbon group having 2 to 6 carbon atoms, and specific examples of the hydrocarbon group having 2 to 6 carbon atoms include ethyl, n-propyl and isopropyl. Carbon atoms such as alkyl groups such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl and n-hexyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl and propenyl, etc.
~ 6 hydrocarbon groups.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an ethyl group is particularly preferable. R ² represents one kind of group selected from an aryl group having 6 to 16 carbon atoms, and specific examples of the aryl group having 6 to 16 carbon atoms include phenyl, α-naphthyl, β-naphthyl, anthracenyl, Examples include phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl. , Propylphenyl, biphenyl,
It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as naphthyl, methylnaphthyl, anthracenyl and phenanthryl; an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ¹ and X ^{2, which} may be the same or different from each other, are a hydrogen atom, a halogen atom or a carbon atom of 1
To a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and specifically, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms. Can be exemplified by the same atoms and groups as described above. In addition, examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the above hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom.

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

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Nate, trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO
-, - S -, - SO -, - SO 2 -, - NR 3 -, - P
^{(R 3) -, - P} (O) (R 3) -, - BR 3 - or -AlR ³ - (provided that, R ³ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon Number of atoms 1
20 halogenated hydrocarbon groups), specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-
Alkylene groups such as 1,2-ethylene, 1,3-trimethylene and 1,4-tetramethylene, cycloalkylene groups such as 1,2-cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2 A divalent hydrocarbon group having 1 to 20 carbon atoms such as an arylalkylene group such as ethylene; 2 having 2 to 20 carbon atoms such as chloromethylene
Divalent halogenated hydrocarbon group obtained by halogenating a valent hydrocarbon group; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl Alkylsilylenes such as phenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylenes, arylsilylene groups, tetramethyl-1,2-disilyl, tetraphenyl-1,2- A divalent silicon-containing group such as an alkyldisilyl such as disilyl, an alkylaryldisilyl, an aryldisilyl group; a divalent germanium-containing group obtained by substituting germanium for silicon in the above divalent silicon-containing group, R ^3, the same halogen atom, hydrocarbon group or carbonitrides having 1 to 20 carbon atoms Number of atoms is a halogenated hydrocarbon group of 1 to 20.

Of these, a divalent silicon-containing group and a divalent germanium-containing group are preferable, and a divalent silicon-containing group is more preferable, and alkylsilylene, alkylarylsilylene and arylsilylene are preferable. Particularly preferred.

Specific examples of the transition metal compound represented by the above general formula (I) are shown below. rac-Dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-dimethylsilyl-bis {1- (2-ethyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1 -(2-ethyl-4- (5-
Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4) -(9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- ( 2-Ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl -Bis {1- (2-ethyl-4- (2,3-
Dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,
4-Dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4-
(2,5-Dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4)
-(2,4,6-Trimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-Ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl
-4- (p-Chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4)
-(2,3-Dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl)
-4- (2,6-Dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl- Bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride , Rac-dimethylsilyl-bis {1- (2-ethyl
-4- (4-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4)
-(4-Biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl-4- (4
-Trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n- Propyl-4-
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4- (2
-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4)
-(5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl-4)
-(9-Anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-propyl)
-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- ( 2-i-propyl-4-
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4- (8
-Methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4)
-(5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl-4)
-(9-Anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-propyl)
-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl)
-4-Phenylindenyl)} zirconium dichloride, r
ac-dimethylsilyl-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl-4- (β- Naphthyl)
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2 -s-Butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethyl Silyl-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium Dichloride, rac-dimethylsilyl
-Bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-
Butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl)
-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4- (2
-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4-
(5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4- (9
-Anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-butyl-4- (9
-Phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl) -4- (α-naphthyl)
Indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-i-butyl-4- (5- Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-neopentyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-n-hexyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenyl Silyl-bis {1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-methylphenylsilyl-bis {1- (2-ethyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-Methylphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2-ethyl-4-
(9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4-
Phenylindenyl)} zirconium dichloride, rac-
Diphenylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium Dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-4- (4-biphenylyl)) Indenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl )} Zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-ethylene-bis {1- (2-n-
Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4- (α-
Naphthyl) indenyl)} zirconium dichloride, ra
c-dimethylgermyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride and the like.

In the present invention, in the above compound, zirconium metal is replaced with titanium metal, hafnium metal,
A transition metal compound in which vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal or tungsten metal is substituted can also be used.

The above transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used. The transition metal compound represented by the above formula (I) is a compound of the Journal of Organ.
ometallic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762, and Examples.

The (B-1) organoaluminum oxy compound (hereinafter sometimes referred to as "component (B-1)") may be a conventionally known aluminoxane, and JP-A-2-7.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in 8687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate The method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the organoaluminum compound with adsorption water or crystallization water. (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. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, trialkyl aluminum such as tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum 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 particularly preferable.
Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula (II) can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (II) (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) Such organoaluminum compounds may be used alone or in combination.

As the solvent used for the preparation of 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. Of these solvents, aromatic hydrocarbons are particularly preferable.

(B-2) As a compound which reacts with the above transition metal compound (A) to form an ion pair (hereinafter sometimes referred to as "component (B-2)"), it is described in Japanese Patent Publication No. -50195
No. 0, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No.
179005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-20770
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A No. 4 and US-547718.

As the Lewis acid, a Lewis acid containing a magnesium atom, a Lewis acid containing an aluminum atom,
Examples thereof include a Lewis acid containing a boron atom, and among these, a Lewis acid containing a boron atom is preferable.

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula. BR ^a R ^b R ^c (In the formula, R ^a R ^b and R ^c may be the same or different from each other, and may be a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Or a fluorine atom.) Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron. , Tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.
Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound (A) by reacting with the transition metal compound (A) 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.

Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation and an ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

The ionic compound is preferably a boron atom-containing ionic compound in which the anionic compound is a boron compound, and specific examples thereof include triethylammonium tetra (phenyl) boron and 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, tri (n-butyl) ammonium tetra (o-tri) ) Boron, trialkyl-substituted ammonium salts such as tri (n-butyl) ammonium tetra (4-fluorophenyl) boron; N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) N, N-dialkylanilinium salts such as boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron; di (n-propyl) ammonium tetra (pentafluorophenyl) boron,
Dialkylammonium salts such as dicyclohexylammonium tetra (phenyl) boron; triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) Examples include triarylphosphonium salts such as boron.

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

Further, the following compounds can be exemplified as the ionic compound containing a boron atom. (Note that in the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts, such as 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} dodecachloro dodecaborate,
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.

As the borane compound and carborane compound, the following compounds can be mentioned. These compounds are used as Lewis acids or ionic compounds.

Decaborane (14), 7,8-Dicarbaundecaborane (13), 2,7-Dicarbaundecaborane (1
3), 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 (1
3), 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-
Boranes such as 7-carbaundecaborate, carborane complex compounds or salts of carborane anions; 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-
Dicarba decaborane (14), Dodeca hydride-1-
Carboranes or carboranes such as phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane Salt.

Further, as the borane compound and carborane compound, the following salts of metal carborane and metal borane anion can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl))
It is, but not limited to, ammonium. ) Tri (n-butyl) ammonium bis (nonahydride
-1,3-Dicarbanonaborate) cobaltate (III), 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 (undecahydride-7,8- Dicarbaundecaborate) cubrate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III), tri (n-) Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) Chromate (Chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate)
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-carbaundecaborate) chromate (III), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) Manganate (IV), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) cobaltate (II
I), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbaundecaborate) nickelate (IV), etc.

The compound (B-2) which reacts with the above transition metal compound (A) to form an ion pair can be used as a mixture of two or more kinds. (C) Organoaluminum compound (hereinafter sometimes referred to as "component (C)")
For example, an organoaluminum compound represented by the following general formula (III) can be exemplified.

R ^d _n AlX _3-n (III) (In the formula, R ^d represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n represents 1 to 1).
It is 3. ) In the general formula (III), R ^d has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an 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. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride. , Dialkyl aluminum halides such as diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Chill aluminum dichloride, ethyl aluminum dichloride, alkyl aluminum dihalides such as isopropyl aluminum dichloride, ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the organoaluminum compound (C), a compound represented by the following general formula (IV) can be used. During ^{_{R d n AlL 3-n ...}} (IV) ( wherein, R ^d represents a similar hydrocarbon group in the above formula (III), L is -OR ^e group, -OSiR ^f ₃ group, -OAlR ^g
₂ groups, -NR ^h ₂ group, -SiR ⁱ ₃ group or -N
(R ^j ) AlR ^k ₂ group, n is 1 to 2,
R ^e , R ^f , R ^g and R ^k are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ^h is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group. , Trimethylsilyl group and the like, and R ⁱ and R ^j are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (1) A compound represented by R ^d _n Al (OR ^e ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (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 (OSiEt 3)
(3) a compound represented by R ^d _n Al (OAlR ^g ₂ ) _3-n ,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
l (iso-Bu) _{2 and the} like; (4) a compound represented by R ^d _n Al (NR ^h ₂ ) _3-n , for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ Al
_{NHEt, Et 2 AlN (SiMe 3} ) 2, (iso-Bu) 2
AlN (SiMe ₃ ) _{2 and the} like; (5) R ^d _n Al (SiR ⁱ ₃ ) _3-n represented by compounds such as (iso-Bu) ₂ AlSiMe _{3 and the} like; (6) 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 general formulas (III) and (IV), the general formula R ^d ₃ Al,
_{^{R d n Al (OR e)}} 3-n, R d n Al (OAlR g 2)
A compound represented by _3-n is preferable, and a compound in which R ^d is an isoalkyl group and n = 2 is particularly preferable.

In the olefin polymerization catalyst (1), at least one of the above-mentioned component (A), component (B-1), component (B-2) and component (C) is supported on a fine particle carrier. It may be a solid catalyst formed of

The olefin polymerization catalyst (1) comprises a fine particle carrier, component (A), component (B-1) (or component (B-
It may be a prepolymerization catalyst composed of 2)) and an olefin polymer produced by the prepolymerization and, if necessary, the component (C).

The fine particle carrier used for the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200.
It is a solid in the form of granules or fine particles of μm.

The inorganic carrier is preferably a porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ ,
TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or a mixture thereof such as SiO ₂ —MgO, S
iO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ ,
Examples thereof include SiO ₂ —Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among these, SiO ₂ and Al ₂ O
Those containing at least one component selected from the group consisting of ₃ as a main component are preferable.

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 specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g, it is desirable that the pore volume is 0.3~2.5cm ³ / g. The particulate carrier may be 100 to 1000, if necessary.
It is used after firing at a temperature of 150 ° C, preferably 150 to 700 ° C.

Further, the fine particle carrier has a particle size of 1
A granular or fine particle solid of an organic compound having a particle size of 0 to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-
Examples thereof include (co) polymers formed from an α-olefin having 2 to 14 carbon atoms such as pentene as a main component, or polymers or copolymers formed from vinylcyclohexane and styrene as a main component. .

The olefin polymerization catalyst (2) includes (A ') a transition metal compound represented by the following general formula (Ia), (B) (B-1) an organoaluminum oxy compound, and /
Alternatively, (B-2) a compound which reacts with the transition metal compound (A) to form an ion pair, and, if necessary, (C) an organoaluminum compound.

The transition metal compound (A ') has the following general formula (I
It is a transition metal compound represented by a).

[0085]

[Chemical 2]

In the formula, M represents the same transition metal atom as in the above formula (I), preferably titanium, zirconium or hafnium, and particularly preferably zirconium. R ⁴ is a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups,
A nitrogen-containing group or a phosphorus-containing group is shown, and specifically, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms are represented by the above formula (I). The same atom or group as X ¹ and X ² can be mentioned. Examples of the silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group and phosphorus-containing group include a monohydrocarbon-substituted silyl group such as methylsilyl and phenylsilyl, and dimethyl. Cyril,
Dihydrocarbon-substituted silyl such as diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl,
Trihydrocarbon-substituted silyl such as tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether; silicon-substituted alkyl such as trimethylsilylmethyl. Group, silicon-containing group such as silicon-substituted aryl group such as trimethylphenyl; hydroxy group, alkoxy group such as methoxy, ethoxy, propoxy, butoxy, allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, phenylmethoxy, phenylethoxy An oxygen-containing group such as an arylalkoxy group; a sulfur-containing group such as a substituent in which oxygen of the oxygen-containing group is substituted with sulfur; an amino group, methylamino, dime Alkylamino groups such as ruamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino, nitrogen-containing groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, arylamino groups such as methylphenylamino and alkylarylamino groups; Examples thereof include phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Of these, one group selected from hydrocarbon groups is preferable, and one group selected from hydrocarbon groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl is particularly preferable. Preferably there is.

R ⁵ represents one kind of group selected from an aryl group having 6 to 16 carbon atoms, and the aryl group having 6 to 16 carbon atoms is specifically the same as R ^{2 in the} formula (I). The following groups can be exemplified.

The aryl group 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.

X¹And X²Are the same or different from each other
Optionally, hydrogen atom, halogen atom, carbon atom 1
To hydrocarbon groups, halogenated with 1 to 20 carbon atoms
Represents a hydrocarbon group, an oxygen-containing group or a sulfur-containing group,
Physically, X of the above formula (I) ¹And X²Similar atom to
And groups can be exemplified.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 3 -, - P (R 3) -, - P
^{(O) (R 3) -} , - BR 3 - or -AlR ³ - (provided that, R ³ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms), specifically, a group similar to Y of the formula (I) and silicon of the divalent silicon-containing group. An example is a divalent tin-containing group substituted with tin.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable, and alkylsilylene and alkylarylsilylene are preferred. More preferably, arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (Ia) are shown below. rac-dimethylsilyl-
Bis {1- (4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4--
Phenylindenyl)} zirconium dichloride, rac-
Dimethylsilyl-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium Dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (2-anthracenyl)) Indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilyl-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (p-bromophenyl) indenyl )} Zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-Methyl-4- (o-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) indenyl)} zirconium dichloride, rac -Dimethylsilyl-bis {1- (2-
Methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-
Methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-Methyl-4- (p-benzylphenyl) indenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-
Methyl-4- (m-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4- (p-trimethylsilylphenyl) indenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Methyl-4- (m-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1-
(2-Ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-phenyl-
4-phenylindenyl)} zirconium dichloride, ra
c-Dimethylsilyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilyl-bis {1- (2-methyl-4-phenylindenyl)}
Zirconium dichloride, rac-di- (i-propyl) silyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (n-butyl) silyl-bis {1- (2 -Methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilyl-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- ( 2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl ) Silyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-
4-phenylindenyl)} zirconium dichloride, ra
c-Dimethylgermyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethyltin-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethylsilyl-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilyl-bis {1- (2- Methyl-4-phenylindenyl)} zirconium methyl chloride, rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (trifluoromethanesulfonate), rac-dimethyl Silyl-bis {1- (2-methyl-
4-phenylindenyl)} zirconium di (trifluoromethanesulfonate), rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (p-toluenesulfonate), rac-Dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (methylsulfonate), rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl) } Zirconium di (trifluoromethane sulfinate),
rac-Dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (tolufluoroacetate), rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} Zirconium monochloride (n-butoxide), rac-dimethylsilyl-bis {1- (2-methyl-4-
Phenylindenyl)} zirconium di (n-butoxide), rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (phenoxide) and the like.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal in the above compounds may be used. it can.

The transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used. The olefin polymerization catalyst (2) comprises the above-mentioned component (A ′), component (B-1) and component (B-
It may be a solid catalyst in which at least one component of 2) and component (C) is supported on a fine particle carrier.

The olefin polymerization catalyst (2) comprises a fine particle carrier, a component (A '), a component (B-1) (or a component (B-
It may be a prepolymerization catalyst composed of 2)) and an olefin polymer produced by the prepolymerization and, if necessary, the component (C).

As the component (B-1), the component (B-2), the component (C) and the particulate carrier, the same ones as those used for the olefin polymerization catalyst (1) can be mentioned. [Graft-modified propylene-based polymer] The graft-modified propylene-based polymer of the present invention, in the presence of a radical initiator,
It can be obtained by reacting the above-mentioned propylene-based polymer with a polar monomer as described below.

Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl ester compounds. , Vinyl chloride and the like.

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

The amino group-containing ethylenically unsaturated compound is
A compound having an ethylenic double bond and an amino group,
Examples of such a compound include a vinyl-based monomer having at least one amino group and a substituted amino group represented by the following formula.

[0101]

[Chemical 3]

In the formula, R ⁶ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁷ represents a hydrogen atom or a carbon atom number of 1 to 1.
2, preferably an alkyl group having 1 to 8 or a cycloalkyl group having 6 to 12, preferably 6 to 8 carbon atoms. The above-mentioned alkyl group and cycloalkyl group may further have a substituent.

Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives of allylamine, methacrylamine, N-methylacrylamine, N, N-
Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide; Acrylamide derivatives such as acrylamide and N-methylacrylamide; Aminostyrenes such as p-aminostyrene; 6-Aminohexylsuccinimide, 2- Aminoethyl succinimide or the like is used.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule. Such an epoxy group-containing ethylenically unsaturated compound is Specifically, glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, itaconic acid Mono- and glycidyl esters, butenetricarboxylic acid mono- and diglycidyl esters, citraconic acid mono- and diglycidyl esters, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid mono and ^TM) Glycidyl esters, end - cis - bicyclo [2.2.1] hept-5-ene-2-methyl-2,
3-Dicarboxylic acid (methyl nadic acid ^TM ) mono and diglycidyl ester, allyl succinic acid mono and glycidyl ester and other dicarboxylic acid mono and alkyl glycidyl esters (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms) , Alkyl glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,
4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide And the like.

Examples of the aromatic vinyl compound include compounds represented by the following formula.

[0106]

[Chemical 4]

In the above formula, R ⁸ and R ^{9, which} may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, Mention may be made of propyl and isopropyl groups. R ¹⁰ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. be able to. Further, n is usually 0 to 5, preferably 1 to
Represents an integer of 5.

Specific examples of such an aromatic vinyl compound include 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-isopropenyl pyridine, 2-vinyl quinoline, 3-vinyl isoquinoline, N-vinyl carbazole, N-vinyl pyrrolidone etc. can be mentioned.

As the unsaturated carboxylic acid, acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,
Unsaturated carboxylic acids such as 2,1] hept-2-ene-5,6-dicarboxylic acid, or their acid anhydrides or their derivatives (for example, acid halides, amides, imides, esters, etc.) can be mentioned. Specific examples of the compound include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -
Dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Examples thereof include glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid,
Maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferred.

Examples of vinyl ester compounds are vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, benzoic acid. Examples thereof include vinyl, vinyl pt-butylbenzoate, vinyl salicylate and vinyl cyclohexanecarboxylate.

The polar monomer is used in an amount of usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the propylene polymer. Examples of the radical initiator include organic peroxides and azo compounds.

Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide and 2,5
-Dimethyl-2,5-bis (t-butylperoxy) hexane, 2,
5-Dimethyl-2,5-bis (t-butylperoxy) hexine-
3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide , Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

Such a radical initiator is generally used in an amount of 0.0 to 100 parts by weight of the propylene polymer.
It is preferably used in an amount of 01 to 10 parts by weight. The radical initiator can be used as it is by mixing it with the propylene polymer and the polar monomer, or can be used by dissolving the radical initiator in a small amount of an organic solvent. The organic solvent used here is not particularly limited as long as it is an organic solvent capable of dissolving the radical initiator. Such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane;
Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, Alcohol solvents such as ethanol, n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate. Examples thereof include ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

In the present invention, a reducing substance may be used when graft-modifying the propylene polymer. The reducing substance has a function of improving the graft amount in the obtained graft-modified propylene-based polymer.

Examples of the reducing substance include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine and hydrazine, as well as —SH, SO ₃ H, —NHNH ₂ , CO
Examples include compounds containing groups such as CH (OH)-.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethyl mercaptan, benzenesulfonic acid, p-
Examples include toluene sulfonic acid.

The reducing substance is usually added in an amount of 0.001 to 5 with respect to 100 parts by weight of the propylene-based polymer.
It is used in an amount of parts by weight, preferably 0.1 to 3 parts by weight. Graft modification of the propylene-based polymer can be carried out by a conventionally known method, for example, by dissolving the propylene-based polymer in an organic solvent, then adding a polar monomer, a radical initiator and the like to the solution, and preferably at 70 to 200 ° C. Is 80 ~
At a temperature of 190 ° C. for 0.5 to 15 hours, preferably 1 to
It is carried out by reacting for 10 hours.

The organic solvent used for graft-modifying the propylene-based polymer can be used without particular limitation as long as it is an organic solvent capable of dissolving the propylene-based polymer.

As such an organic solvent, benzene,
Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane and heptane.

Further, the graft-modified propylene-based polymer can be produced by kneading and reacting the propylene-based polymer and the polar monomer in the absence of solvent using an extruder or the like. The reaction temperature is usually the melting point of the propylene-based polymer or higher, specifically in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10
It's a minute.

The graft amount of the graft group derived from the polar monomer in the graft-modified propylene-based polymer thus prepared is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. Is within the range of.

The graft-modified propylene-based polymer of the present invention contains a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, an antiblocking agent, an antifogging agent, within a range not impairing the object of the present invention. Additives such as a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, and an antioxidant may be added if necessary. Further, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

[0123]

INDUSTRIAL APPLICABILITY The graft-modified propylene-based polymer of the present invention has excellent adhesiveness with respect to adhesion to a metal or polar resin, and also has excellent adhesive force in a high temperature atmosphere.

Next, the method of measuring the physical properties used in the present invention will be described. (1) Molecular weight distribution (Mw / Mn) From a chromatograph measured using Gel permeation chromatography (GPC) (150-ALC / GPC) manufactured by Waters, polypropylene conversion by universal method (however, comonomer amount is 10 mol) %, The number average molecular weight (in terms of polystyrene) (M
n) and weight average molecular weight (Mw) were calculated, and Mw / M
n was calculated. The measurement was performed at 140 ° C. using o-dichlorobenzene as a solvent, using a GMH-HT and GMH-HLT type column manufactured by Toyo Soda.

(2) Triad tacticity (mm fraction) Triad tacticity (mm fraction) of propylene copolymer and propylene / ethylene random copolymer
Is defined as the proportion in which the direction of the methyl branch is the same when the propylene unit chain in which three arbitrary head-to-tail bonds in the polymer chain are expressed by a planar zigzag structure, and ¹³ C-NMR
It was determined from the spectrum by the following formula.

[0126]

[Equation 1]

¹³ C-NMR spectrum is obtained by NMR analysis of the sample.
Hexachlorobutadiene in a sample tube (5 mmφ),
About 0.5 ml of o-dichlorobenzene or 1,2,4-trichlorobenzene was dissolved completely in a solvent containing about 0.05 ml of deuterated benzene as a lock solvent.
It was measured by the complete proton decoupling method at 0 ° C. The measurement conditions are a flip angle of 45 ° and a pulse interval of 3.4T.
₁ (T ₁ is the longest value of the spin lattice relaxation time of the methyl group) or more is selected. In polypropylene, the spin-lattice relaxation time of the methyl group is longer than the spin-lattice relaxation time of the methylene group and the methine group, so under this condition, the magnetization recovery of all carbons in the sample is 99% or more. The chemical shift was set such that the third group of the head-to-tail bonded propylene unit 5 chain had a methyl group of 21.593 ppm, and the chemical shifts of other carbon peaks were based on this.

The peak area is the first area (21.1 to 2).
1.9 ppm), second region (20.3 to 21.0 pp)
m) and the third region (19.5 to 20.3 ppm). In the first region, the methyl group of the second unit in the propylene unit 3 chain represented by PPP (mm) resonates.

In the second region, the methyl group at the second unit of the propylene unit 3 chain represented by PPP (mr) resonates,
Further, a methyl group of a propylene unit in which adjacent units are a propylene unit and an ethylene unit (PPE-methyl group)
Resonate.

In the third region, the methyl group at the second unit of the propylene unit 3 chain represented by PPP (rr) resonates,
Further, a methyl group (EPE-methyl group) of a propylene unit in which all the adjacent units are ethylene units resonates.

Here, the propylene copolymer and the propylene / ethylene random copolymer have the following structures (i), (ii) and (iii) as a partial structure containing a position disorder unit.

[0132]

[Chemical 5]

Among the peaks derived from the structures (i), (ii) and (iii), carbon A and carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peak does not appear in the first to third regions. Furthermore, since carbon A and carbon B do not participate in the propylene 3 chain based on the head-to-tail bond, mm
It need not be considered in the calculation of the fraction.

The peaks based on carbon C, the peaks based on carbon D, and the peaks based on carbon D ′ appear in the second region, and the peaks based on carbon E and the peaks based on carbon E ′ appear in the third region.

Therefore, among the peaks appearing in the first to third regions, the peaks not based on the head-to-tail bonded propylene unit 3 chain are the PPE-methyl group (resonance near 20.7 ppm) and the EPE-methyl group (19). Resonance around 0.8 ppm), carbon C, carbon D, carbon D ′, carbon E and carbon E ′.

The peak area based on PPE-methyl group is
It can be determined from the peak area of the PPE-methine group (resonance near 30.6 ppm), and the peak area based on the EPE-methyl group can be determined from the peak area of the EPE-methine group (resonance near 32.9 ppm). it can. The peak area based on carbon C can be obtained from the peak areas of adjacent methine groups (resonance near 31.3 ppm), and the peak area based on carbon D is based on αβ methylene carbon of the above structure (ii). Peak (34.3p
Resonance at resonance near pm and around 34.5 ppm) can be obtained from 1/2 of the sum of peak areas of carbon D '
The peak area based on the methine group adjacent to the methyl group of carbon E ′ of the above-mentioned structure (iii) (33.3 pp).
It can be obtained from the area of resonance at m) and the peak area based on carbon E is calculated as
It can be obtained from the peak area of (resonance near pm),
The peak area based on carbon E ′ can be obtained from the peak areas of the adjacent methine carbons (resonance near 33.3 ppm).

Therefore, when these peak areas are subtracted from the peak areas of the second and third regions, the peak areas of the remaining methyl carbons are all head-to-tail linked propylene unit 3 chains (PPP (mr) and PPP (mr). rr)).

Since the peak areas of PPP (mm), PPP (mr) and PPP (rr) can be obtained by the above, the mm fraction of the propylene unit chain portion consisting of head-to-tail bonds can be obtained according to the above formula. You can

The mm fraction of the propylene homopolymer is such that when the main chain of any three propylene unit chains in the polymer chain is expressed by a plane zigzag structure, the methyl groups have the same direction and the head -Defined as the proportion of tail binding,
It was determined from the ¹³ C-NMR spectrum measured in the same manner as above by the following formula.

[0140]

[Equation 2]

(In the formula, PPP (mm) is the same as above, and ΣIMe represents the peak area based on all methyl groups.) The chemical shift is the third unit of the 5-chain head-to-tail propylene unit. The methyl group of the eye was set as 21.593 ppm, and the chemical shifts of other carbon peaks were based on this.

According to this standard, the peak based on the methyl group of the second unit in the propylene unit 3 chain represented by PPP (mm) appears in the range of 21.1 to 21.9 ppm, and PP
The peak based on the methyl group of the second unit in the propylene unit 3 chain represented by P (mr) is 20.3 to 21.0 ppm.
Within the range of 3 and the PPP (rr) indicated propylene unit 3
The peak based on the methyl group of the second unit in the chain is 1
It appears in the range of 9.5 to 20.3 ppm).

Here, the propylene homopolymer is a moiety containing a regular structure in which propylene units are bonded head-to-tail, as well as a positional disorder unit based on 2,1-insertion as shown in the above structure (i). Has a small amount of structure.

In the disordered structure represented by the above structure (i), carbon A, carbon B and carbon C are the same as the above-mentioned PPP (m
Does not meet the definition of m). However, carbon A and carbon B
Resonates in the region of 16.5 to 17.5 ppm, and carbon C
Resonates in the vicinity of 20.7 ppm (PPP (mr) region) (however, the confirmation of the partial structure containing the position disorder unit is
It is necessary to confirm the peaks of not only these methyl groups but also the adjacent methylene groups and methine groups). Therefore, carbon A, carbon B and carbon C are not included in the PPP (mm) region.

Therefore, the triad tacticity (mm fraction) of the propylene homopolymer can be determined by the above formula. (3) Proportion of regio-irregular units based on 2,1-insertion of propylene monomer During polymerization, propylene monomer makes 1,2-insertion (methylene side bonds with catalyst), but rarely 2,1-insertion. I have something to do. Therefore, the propylene copolymer and the propylene / ethylene random copolymer have a position disorder unit based on the 2,1-insertion as shown in the structures (i), (ii) and (iii). The proportion of the regio-irregular units based on the 2,1-insertion was determined from the following formula using ¹³ C-NMR.

[0146]

[Equation 3]

Here, the peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). In addition, Iαβ and the like indicate peak areas such as αβ peaks. The propylene homopolymer has regio-irregular units based on the 2,1-insertion as shown in the above structure (i).
The proportion of positional irregular units based on this 2,1-insertion is ¹³ C-
It was determined from the following formula using NMR.

[0148]

[Equation 4]

(In the formula, ΣIMe is the same as above.) (4) Proportion of regio disordered unit based on 1,3-insertion of propylene monomer In the propylene homopolymer, 1,3-insertion of propylene occurs. The amount of 3 linkages based was determined from the αδ peak (resonance near 37.1 ppm) and the βγ peak (resonance near 27.4 ppm).

In the propylene copolymer and the propylene / ethylene random copolymer, the amount of three chains based on 1,3-insertion of propylene was determined from the βγ peak (resonance near 27.4 ppm).

(5) Intrinsic viscosity [η] Measured in decalin at 135 ° C. and shown in dl / g. (6) Method for measuring copolymer composition The composition of the propylene copolymer was determined using ¹³ C-NMR.

[0152]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0153]

[Production Example 1] 1.7 liters of toluene were placed in a gas flow type glass polymerization vessel having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, cooled to -30 ° C, and 100 liters of propylene /
The system was sufficiently saturated with hydrogen and hydrogen at a flow rate of 10 l / hr. Then triisobutylaluminum was added to 4.
25 mmol, 8.5 mmol of methylaluminoxane converted to Al atom, rac-dimethylsilyl-bis {1- (2
0.017 mmol of -ethyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atom was added, and polymerization was carried out for 45 minutes while maintaining the system at -30 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 3 liters of methanol to which a small amount of hydrochloric acid was added, and the mixture was sufficiently stirred and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours. The obtained propylene homopolymer was 51.3 g. Table 1 shows the physical properties of the obtained propylene homopolymer.

[0154]

[Production Example 2] 250 ml of toluene was placed in a gas flow type glass polymerization vessel having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, and cooled to 0 ° C., and 160 liter / h of propylene was added.
r and ethylene were circulated at 40 liters / hr to fully saturate the system. Next, 0.25 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane converted into Al atoms, and rac-dimethylsilyl-bis {1
-(2-Ethyl-4-phenylindenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and polymerization was carried out for 10 minutes while keeping the system at 0 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 2 liters of methanol containing a small amount of hydrochloric acid, stirred sufficiently, and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours. The amount of the obtained propylene copolymer was 5.62 g. The physical properties of the resulting propylene copolymer are shown in Table 1.

[0155]

[Production Example 3] Polymerization was carried out in the same manner as in Example 4 except that propylene was 100 liters / hr and ethylene was 100 liters / hr in Production Example 2. The obtained polymerization solution was put into 2 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After sufficiently removing methanol, it was dried at 130 ° C. for 10 hours. The obtained propylene / ethylene random copolymer was 8.95 g. Table 1 shows the physical properties of the obtained propylene / ethylene random copolymer.

[0156]

PRODUCTION EXAMPLE 4 Propylene was homopolymerized using a conventionally known MgCl ₂ -supporting Ti-based catalyst. The physical properties of the resulting propylene polymer are shown in Table 1.

[0157]

Example 1 Toluene was used as a reaction solvent, and 825 g of propylene homopolymer obtained in the above Production Example 1 was dissolved at 160 ° C. per 5.7 liters of toluene. Next, a toluene solution of maleic anhydride (4.13 g / 250 ml) and a toluene solution of dicumyl peroxide (DPC) (0.33 g / 50 ml) were added to the toluene solution.
Were fed gradually from separate conduits over 4 hours.

After the feed yield, the reaction was further continued at 160 ° C. for 30 minutes and then cooled to room temperature to precipitate a polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. for 24 hours to obtain a target modified propylene homopolymer.

The modified propylene homopolymer was subjected to elemental analysis and the grafted amount of maleic anhydride was measured.
It was found that 0 g of maleic anhydride was graft-polymerized. Table 1 shows the physical properties of the modified polymer.

A film was prepared from the obtained modified polymer as follows, and the adhesive strength to Al and the peeling strength at 100 ° C. were measured as follows. The results are shown in Table 1. [Production of Film] A 0.1 mm thick aluminum sheet, a polyethylene terephthalate (PET) sheet and a 100 μm thick aluminum sheet obtained by cutting the center into 15 cm × 15 cm squares were laid in this order on a press plate, and the center ( A sample (modified polymer) of 3.3 g was placed on the cut portion. Then, a PET sheet, an aluminum sheet, and a press plate were further stacked in this order.

The sample sandwiched between the press plates was put in a hot press at 200 ° C., preheated for about 7 minutes, and then,
Pressurized (50 kg / cm ^2- to remove bubbles in the sample
G) The depressurization operation was repeated several times. Then 100 kg /
The pressure was raised to cm ² -G, and pressure heating was performed for 2 minutes. After depressurizing, it was taken out from the press machine of the press plate, transferred to another press machine whose pressure-bonded part was kept at 0 ° C., pressure-cooled at 100 kg / cm ² -G for 4 minutes, and then depressurized to make the sample. I took it out. The obtained film (modified polymer film) has a uniform thickness of about 150 to
The portion having a thickness of 170 μm was used for measuring the adhesion strength to Al and the peeling strength at 100 ° C.

[Measurement of Adhesive Strength to Al] The modified polymer film was sandwiched between two 15 cm × 15 cm square aluminum sheets (thickness: 200 μm), and the aluminum sheet was pressed under the same pressing conditions as in the above “Production of film”. And the modified polymer film were stuck together. The obtained laminate was cut into 15 mm wide strips, and the adhesive interface between the aluminum sheet and the modified polymer film was peeled off in the 180 ° direction.
The peel strength was measured.

[Measurement of 100 ° C. Peel Strength] A modified polymer film was sandwiched between two 15 cm × 15 cm square aluminum sheets (thickness: 200 μm), and the aluminum sheet was pressed under the same pressing conditions as in the above-mentioned “Production of film”. And the modified polymer film were stuck together. The obtained laminate was cut into 15 mm wide strips, attached to a chamber installed in a thermostat kept at 100 ° C., and allowed to stand for 10 minutes, after which the adhesive interface between the aluminum sheet and the modified polymer film was oriented at 180 °. Then, the peel strength was measured.

[0164]

Example 2 A modified polymer was obtained in the same manner as in Example 1 except that the modifying monomer in Example 1 was changed to the one described in Table 1. A film was prepared from this modified polymer in the same manner as in Example 1 and had an adhesive strength to Al and 10
The 0 ° C peel strength was measured. The results are shown in Table 1.

[0165]

Example 3 A modified polymer was obtained in the same manner as in Example 1 except that the propylene homopolymer in Example 1 was replaced with the propylene copolymer produced in Production Example 2. A film was prepared from this modified polymer in the same manner as in Example 1, and the adhesive strength to Al and the peeling strength at 100 ° C. were measured. The results are shown in Table 1.

[0166]

Example 4 A modified polymer was obtained in the same manner as in Example 1 except that the propylene homopolymer was replaced with the propylene / ethylene random copolymer produced in Production Example 3. A film was prepared from this modified polymer in the same manner as in Example 1, and the adhesive strength to Al and the peeling strength at 100 ° C. were measured. The results are shown in Table 1.

[0167]

Comparative Example 1 A modified polymer was obtained in the same manner as in Example 1 except that the propylene homopolymer was changed to the propylene polymer produced in Production Example 4. Table 1 shows the physical properties of the modified polymer thus obtained.

A film was prepared from this modified polymer in the same manner as in Example 1, and the adhesion strength to Al and the peeling strength at 100 ° C. were measured. The results are shown in Table 1.

[0169]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-206947 (JP, A) JP-A-6-206946 (JP, A) JP-A-3-91514 (JP, A) JP-A-2- 173009 (JP, A) JP-A-5-86143 (JP, A) JP-A-7-149833 (JP, A) JP-A-6-128323 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 255/02

Claims (9)

(57) [Claims] 1. A triad tacticity of a chain portion of a propylene unit composed of a head-to-tail bond is 99.0% or more, which is determined by (i) ¹³ C-NMR, and (ii) ¹³ C-N.
The proportion of regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion determined by MR is 0.20% or less, and (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C. ] In the range of 0.1 to 20 dl / g, a polar modified monomer is graft-copolymerized with a propylene homopolymer. 2. The graft-modified propylene-based polymer according to claim 1, wherein the polar monomer is at least one monomer selected from hydroxyl group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives. Coalescing. 3. The graft-modified propylene-based polymer according to claim 1, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight. 4. A head-to-tail obtained by (i) ¹³ C-NMR, comprising (i) a propylene unit in a proportion of 95 to 99.5 mol% and an ethylene unit in a proportion of 0.5 to 5 mol%. The triad tacticity of the propylene unit chain portion composed of a bond is 95.0% or more, and (iii) ¹³ C-NMR
The proportion of regio-irregular units based on the 2,1-insertion of propylene monomer in the total propylene insertion determined by
In the range of 05 to 0.5%, (iv) the intrinsic viscosity [η] measured in decalin at 135 ° C is 0.1 to 12 dl / g.
A graft-modified propylene-based polymer characterized in that a polar monomer is graft-copolymerized with the propylene copolymer in the range. 5. The graft-modified propylene-based polymer according to claim 4, wherein the polar monomer is at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative. Coalescing. 6. The graft-modified propylene-based polymer according to claim 4, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight. 7. (i) It comprises 50 to 95 mol% of propylene units and 5 to 50 mol% of ethylene units, and (ii)
The triad tacticity of the chain portion of the propylene unit consisting of the head-to-tail bond was 9 determined by ¹³ C-NMR.
0.03% or more, (iii) 2,3 of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR
1-The ratio of positional irregular units based on insertion is 0.05 to 0.
A polar monomer is graft-copolymerized with a propylene / ethylene random copolymer having an intrinsic viscosity [η] measured in decalin of 135 ° C. and decalin of 0.1 to 12 dl / g in the range of 5%. A graft-modified propylene-based polymer characterized by the following. 8. The graft-modified propylene-based polymer according to claim 7, wherein the polar monomer is at least one monomer selected from a hydroxyl group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative. Coalescing. 9. The graft-modified propylene-based polymer according to claim 7, wherein the graft amount of the graft group derived from the polar monomer is in the range of 0.1 to 50% by weight.