JPH0977826A - Hydroxylated ethylene-alpha-olefin-nonconjugated polyene radom copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin-based copolymer excellent in both metal and polar resin. SOLUTION: This random copolymer is a modified copolymer obtained by hydroxyl modification of an ethylene-α-olefin-nonconjugated polyene copolymer, being composed of 50-95mol% of ethylene unit, 50-5mol% of a 3-20C α-olefin unit, and >0mol% but <=5mol% of a 5-20C nonconjugated polyene unit, and having the following characteristics: intrinsic viscosity is 0.5-10dl/g; Mw/Mn is <=3; B-value is 1.00-2.00; the intensity ratio of Tαβ to Tαα in<13> C-NMR spectrum is <=0.5; and epoxy group content is 0.01-10mol per 100g of the modified copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer, and more specifically to a hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer having excellent affinity with metals and polar resins. The present invention relates to a conjugated polyene copolymer.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene propylene 7-methyl
-1,6-octadiene copolymer, ethylene / propylene /
Low crystallinity ethylene / α-olefin / non-conjugated polyene copolymers such as ethylidene norbornene copolymers can be used for elastic polymer molding applications and various resin modifiers by taking advantage of their excellent properties. It is used.

However, this ethylene / α-olefin / non-conjugated polyene copolymer is a so-called non-polar resin that does not contain a polar group in the molecule and lacks affinity with metals, polar resins, etc. When used by adhering with or when used by blending with a polar resin, sufficient performance is often not exhibited.

As a method for improving such a drawback of the nonpolar resin, there is a method in which a polar group-containing unsaturated compound is graft-copolymerized with the polar resin in the presence of a radical initiator. However, since the ethylene / α-olefin / non-conjugated polyene copolymer has a radically polymerizable unsaturated bond in the molecule, when the above graft copolymerization is carried out, the molecules are cross-linked and fluidized. The moldability may be deteriorated and the moldability may be extremely deteriorated.

As a result of intensive investigations by the present inventors in view of the above-mentioned conventional techniques, the modified copolymer obtained by hydroxyl-modifying a specific ethylene / α-olefin / non-conjugated polyene copolymer has the above-mentioned problems. The present invention has been completed by finding that the above can be solved.

Among the ethylene / α-olefin / non-conjugated polyene copolymers, ethylene / α-olefin / non-conjugated products obtained by using a conventionally known titanium-based catalyst consisting of a titanium compound and an organoaluminum compound. Many polyene copolymers have a wide molecular weight distribution and composition distribution, and the hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer may have insufficient performance depending on the application. .

Further, a method of hydroxylating the olefinic unsaturated bond in the propylene / non-conjugated diene copolymer is described in JP-A-5-279412, but the modified copolymer obtained is elastic. Is low, and sufficient performance may not be obtained depending on the application.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and it is a hydroxylated ethylene / α-olefin / polymer having excellent affinity with metals and polar resins.
The purpose is to provide a non-conjugated polyene copolymer.

[0009]

SUMMARY OF THE INVENTION Hydroxylated ethylene according to the present invention
The α-olefin / non-conjugated polyene copolymer has ethylene, at least one olefin selected from α-olefins having 3 to 20 carbon atoms, and 5 to 2 carbon atoms.
A modified copolymer in which an ethylene / α-olefin / non-conjugated polyene copolymer obtained from at least one polyene selected from non-conjugated polyene of 0 is hydroxylated and modified (i) derived from ethylene The content of the constituent units is 50 to 95 mol%, and the number of carbon atoms is 3
50 to 50 structural units derived from α-olefin
5 mol%, containing 5 to 20 carbon atoms of a constitutional unit derived from a non-conjugated polyene in a proportion of more than 0 mol% and 5 mol% or less, (ii) in decalin at 135 ° C. Intrinsic viscosity [η] measured at 0.5 to 10 dl
/ G, and (iii) M which is an index of molecular weight distribution
The value of w / Mn is 3 or less, and the B value obtained from (iv) ¹³ C-NMR spectrum and the following formula is 1.00 to 1.00.
B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is a structural unit derived from ethylene in the copolymer) a molar fraction of, [P _O] is a molar fraction of constituent units derived from α- olefin in the copolymer, [P _OE] is the total dyad (dy in the copolymer
ad) is the ratio of α-olefin / ethylene chain number to the chain number) (v) The intensity ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tαβ / Tαα) is 0.5 or less, and (vi) hydroxyl group Is contained in an amount of 0.01 to 10 mol per 100 g of the modified copolymer.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer is at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms in the presence of a metallocene catalyst. Is preferably an ethylene / α-olefin / non-conjugated polyene copolymer obtained by copolymerizing the olefin with at least one polyene selected from the non-conjugated polyenes having 5 to 20 carbon atoms.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention will be specifically described below.

The hydroxylated ethylene / α according to the present invention
The olefin / non-conjugated polyene copolymer has ethylene, at least one olefin selected from α-olefins having 3 to 20 carbon atoms, and 5 to 2 carbon atoms.
A modified copolymer in which an ethylene / α-olefin / non-conjugated polyene copolymer, which is a random copolymer with at least one polyene selected from non-conjugated polyenes of 0, is hydroxylated and modified.

[Ethylene / α-olefin / non-conjugated polyene copolymer] First, the ethylene / α-olefin / non-conjugated polyene copolymer will be described.

The ethylene / α-olefin / non-conjugated polyene copolymer is composed of ethylene and α having 3 to 20 carbon atoms.
-It is obtained by copolymerizing at least one olefin selected from olefins and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene,
1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- 1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-
Examples include hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. These may be used alone or in combination of two or more.

Of these, α having 4 to 10 carbon atoms
-Olefins are preferred, especially 1-butene, 1-hexene, 1
-Octene and the like are preferably used. Specific examples of the non-conjugated polyene having 5 to 20 carbon atoms include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,
6-octadiene, 1,7-octadiene, 1,8-nonadiene,
1,9-decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-
1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-
Dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,
5-heptadiene, 5-ethyl-1,5-heptadiene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,
4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-
Octadiene, 5-methyl-1,5-octadiene, 6-methyl-
1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene,
7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,
8-Undecadiene and other aliphatic polyenes, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,5-
Norbornadiene, 1,4-divinylcyclohexane, 1,3-
Divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallyl Cyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-
Examples thereof include alicyclic polyenes such as isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, and aromatic polyenes such as divinylbenzene and vinylisopropenylbenzene.

These non-conjugated polyenes may be used alone or in combination of two or more. Among these non-conjugated polyenes, non-conjugated polyenes having 7 or more carbon atoms are preferable, for example, 7-methyl-1,6-octadiene (MO
D), ethylidene norbornene (ENB), dicyclopentadiene (DCPD) and the like are preferably used.

The ethylene / α-olefin / non-conjugated polyene copolymer has 50 to 50 structural units derived from ethylene.
95 mol%, preferably 55 to 90 mol%, more preferably 60 to 85 mol% and having 3 carbon atoms.
50 to 50 structural units derived from α-olefin
The content is 5 mol%, preferably 45 to 10 mol%, and more preferably 40 to 15 mol%.

Further, the constituent unit derived from the non-conjugated polyene having 5 to 20 carbon atoms is more than 0 mol% and not more than 5 mol%, preferably 0.5 to 4.5 mol%, more preferably 0 mol%. It is contained in a proportion of 0.5 to 4.0 mol%.

The modified copolymer obtained by hydroxylating the ethylene / α-olefin / non-conjugated polyene copolymer having such a composition has excellent performance when used as, for example, an impact resistance improver for polar resins. Exert.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 10 dl / g, preferably 1.0 to
It is in the range of 8.0 dl / g. The value of Mw / Mn, which is an index of the molecular weight distribution, is 3 or less, preferably 2.8 or less.

Ethylene / α with Mw / Mn value of more than 3
A modified copolymer obtained by hydroxylating an olefin / non-conjugated polyene copolymer may not have sufficient adhesive strength with a metal, a polar resin or the like.

The value of Mw / Mn is determined by gel permeation chromatography (GPC) (150-
Chromatograph measured using ALC / GPC), converted to polypropylene by the universal method (however, converted to polystyrene when the comonomer amount is 10 mol% or more)
Number average molecular weight (Mn) and weight average molecular weight (Mw)
Was calculated and determined. 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.

The B value obtained from the ¹³ C-NMR spectrum and the following formula is in the range of 1.00 to 2.00, preferably 1.00 to 1.80. B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (In the formula, [P _E ] is the content mole fraction of the structural unit derived from ethylene in the copolymer, [P _O ] is the mole fraction of constituent units derived from the α-olefin in the copolymer, and [P _OE ] is the total dyad (dy) in the copolymer.
ad) is the ratio of the number of α-olefin / ethylene chains to the number of chains) This B value is an index representing the distribution state of the structural units derived from ethylene and the structural units derived from α-olefin in the copolymer. , JCRandall (Macromole
cules, 15, 353 (1982)), J. Ray (Macromolecules, 10,
773 (1977)) and others.

The larger the B value, the shorter the block-like chain of the structural unit derived from ethylene and / or the block-like chain of the structural unit derived from α-olefin,
The distribution of the constitutional units derived from ethylene and the constitutional unit derived from the α-olefin is uniform, indicating that the composition distribution of the copolymer is narrow. The B value is 1.00
The smaller the copolymer, the wider the composition distribution of the copolymer, and the modified copolymer obtained by hydroxylating modification of such a copolymer has a higher metal content than the modified copolymer obtained by hydroxylating modification of the copolymer having a narrow composition distribution. , The adhesive strength with polar resins and the like may be poor.

The ethylene / α-olefin / non-conjugated polyene copolymer having a B value in the range of 1.00 to 2.00 is
For example, using a catalyst containing a Group IVB transition metal compound as described below, ethylene and α- having 3 to 20 carbon atoms are used.
It can be obtained by copolymerizing at least one olefin selected from olefins and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms. It should be noted that at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms in the presence of a catalyst other than a catalyst containing a Group IVB transition metal compound as described below, for example, a titanium-based catalyst. And at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms, B
It is difficult to obtain an ethylene / α-olefin / non-conjugated polyene copolymer having a value in the range of 1.00 to 2.00.

The intensity (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum is 0.5 or less, preferably 0.1 or less, more preferably 0.01 or less.

Here, T in the ¹³ C-NMR spectrum
αβ and Tαα are peak intensities of —CH ₂ — units in the constitutional units derived from α-olefins having 3 to 20 carbon atoms, respectively.
It means the peak intensities of two types of —CH ₂ — units having different positions with respect to the primary carbon.

[0029]

Embedded image

The intensity (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum of the ethylene / α-olefin / non-conjugated polyene copolymer.
Can be obtained as follows.

The ¹³ C-NMR spectrum of the ethylene / α-olefin / non-conjugated polyene copolymer was measured by using, for example, a JEOL-GX270 NMR measuring apparatus manufactured by JEOL Ltd., and a sample concentration of 5% by weight of hexachlorobutadiene / d. ₆ -benzene = 2/1 (volume ratio) mixed solution, 67.8MHz,
Measured in benzene (128 ppm) standard - d ₆ at 25 ° C..

Analysis of ¹³ C-NMR spectrum is basically carried out by Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

Here, the strength ratio D will be described more concretely by taking an ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer as an example. ¹³ C-NM of this ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer
In the R spectrum, the peak appearing at 39 to 40 ppm is assigned to Tαα, and the peak appearing at 31 to 32 ppm is assigned to Tαβ.

The intensity ratio D is calculated by the integral value (area) ratio of each peak portion. The intensity ratio D thus obtained is generally the rate at which the 1,1 addition reaction of α-olefins is followed by the 2,1 addition reaction, or the 1,1 addition reaction of 1-butene is followed by the 1,2 addition reaction. It is considered to be a measure of the rate at which an addition reaction occurs. Therefore, the larger the strength ratio D value, the more irregular the binding direction of the α-olefin. Conversely, the smaller the D value, the more regular the binding direction of the α-olefin, and the higher the regularity, the easier the molecular chains are to aggregate, and the ethylene / α-olefin / non-conjugated polyene copolymer is , Strength and the like tend to be excellent.

The ethylene / α-olefin / non-conjugated polyene copolymer having a strength ratio D of 0.5 or less is produced by using ethylene and a carbon atom in a catalyst containing a Group IVB transition metal compound as described below. It can be obtained by copolymerizing at least one olefin selected from α-olefins having 3 to 20 carbon atoms and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms. In addition, in the presence of a catalyst other than a catalyst containing a Group IVB transition metal compound as described below, for example, a vanadium-based catalyst, ethylene and α- having 3 to 20 carbon atoms are used.
Even when copolymerizing at least one olefin selected from olefins and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms, ethylene having a strength ratio D of 0.5 or less. It is difficult to obtain an α-olefin / non-conjugated polyene copolymer.

Next, a method for producing the above ethylene / α-olefin / non-conjugated polyene copolymer will be described. The ethylene / α-olefin / non-conjugated polyene copolymer as described above is, for example, as described below in (A).
A Group IVB transition metal compound, (B) an organoaluminum oxy compound and / or (C) a compound which reacts with the (A) Group IVB transition metal compound to form an ion pair;
If necessary, in the presence of a catalyst composed of (D) an organoaluminum compound, ethylene, at least one olefin selected from α-olefins having 3 to 20 carbon atoms, and 5 to 20 carbon atoms. It can be obtained by copolymerizing with at least one polyene selected from the non-conjugated polyenes.

(A) Group IVB Transition Metal Compound Group IV transition metal compound (A) (hereinafter sometimes referred to as “component (A)”) is specifically represented by the following formula (I). Transition metal compound.

ML _x (I) In the formula, M is a transition metal atom selected from Group IVB of the periodic table, preferably zirconium, titanium or hafnium, and preferably zirconium.

X is the valence of the transition metal atom and represents the number of L coordinated to the transition metal atom M. L is a ligand coordinated to the transition metal atom M, at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is , A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R ¹ group (provided that R ¹ is a carbon atom which may have a substituent such as halogen). 1-8 hydrocarbon groups), halogen atoms, hydrogen atoms and the like.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Alkyl-substituted cyclopentadienyl group such as pentadienyl group, hexylcyclopentadienyl group or indenyl group, alkyl-substituted indenyl group, aryl-substituted indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, etc. Exemplify Door can be. These groups may be substituted with a trialkylsilyl group or a halogen atom.

When the compound represented by the general formula (I) contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton among them are ethylene and propylene. Alkylene groups, such as
It may be bonded via a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically, the alkyl group includes a methyl group, an ethyl group and a propyl group. , Isopropyl group, butyl group, etc., as the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc., as the aryl group, a phenyl group, a tolyl group, etc., and as the aralkyl group, a benzyl group, Examples include neophyll groups.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

The ligand represented by SO ₃ R ¹ is p-
Examples thereof include a toluene sulfonate group, a methane sulfonate group, and a trifluoro methane sulfonate group. The metallocene compound containing a ligand having such a cyclopentadienyl skeleton is more specifically represented by the following general formula (I ′) when the valence of the transition metal is 4.

R ² R ³ R ⁴ R ⁵ M (I ′) In the formula, M is a transition metal atom similar to the above formula (I),
R ² is a group (ligand) having a cyclopentadienyl skeleton
And R ³ , R ⁴ and R ^{5, which} may be the same or different from each other, have a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, A trialkylsilyl group, a SO ₃ R ¹ group, a halogen atom, a hydrogen atom and the like.

In the above general formula (I '), R ² ,
A metallocene compound in which at least two of R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton is preferable. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. It may be connected via. In this case, R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group,
Aryloxy group, trialkylsilyl group, SO ₃ R ¹ ,
Examples include halogen atom and hydrogen atom.

Specific examples of the group IVB transition metal compound represented by the above formula (I) in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) Zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ) Zirconium bis (methanesulfonato), ethylenebis (indenyl) zirconiumbis (p-toluenesulfonato), ethylenebis (indenyl) zircon Umbis (trifluoromethanesulfonato), ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta) Dienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) Rukoniumubisu (trifluoromethanesulfonate), dimethylsilylene-bis (4,5,6,
7-tetrahydroindenyl) zirconium dichloride,
Dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium Dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride , Bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride Domonohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclo Pentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato) Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zil Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride , Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium Mudichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride and the like.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can be used. IV as described above
Among the group B transition metal compounds, a group IVB transition metal compound represented by the general formula (II), (III) or (IV) described below is particularly preferable.

[0050]

Embedded image

In the formula (II), M is a transition metal atom of Group IVB of the periodic table, preferably titanium, zirconium or hafnium, and particularly preferably zirconium.

R ¹¹ is a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.
Examples include alkyl groups such as -butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl, alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different from each other and are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ¹¹ . R ¹³ represents an aryl group having 6 to 16 carbon atoms, specifically, phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl. , Biphenylyl and the like. Of these, phenyl, naphthyl, anthracenyl or phenanthryl is 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, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl,
Hydrocarbon groups having 1 to 20 carbon atoms, such as aryl groups such as acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl;
It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

X ¹ and X ² are a hydrogen atom, a halogen atom, 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. Specific examples of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms include 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 aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. Can be mentioned.

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene 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 17 -,
^{-P (R 17) -, -} P (O) (R 17) -, - BR 17 - or -AlR ¹⁷ - [however, R ¹⁷ is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms Group, a halogenated hydrocarbon group having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1 Alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl
Divalent hydrocarbon group having 1 to 20 carbon atoms such as arylalkylene group such as -1,2-ethylene; Halogenated divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene Halogenated hydrocarbon groups: methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) ) Silylene, di (p-chlorophenyl) silylene and other alkylsilylenes, alkylarylsilylenes, arylsilylene groups, tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl and other alkyldisilyls, alkylaryldisilyls , A divalent silicon-containing group such as an aryldisilyl group; R ¹⁷ is a divalent germanium-containing group substituted with nitrogen, R ¹⁷ is the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Is.

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

Specific examples of the transition metal compound represented by the above general formula (II) are shown below. rac-dimethyl silylene-
Bis {1- (4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (1-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (2-anthracenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (9-anthracenyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-) (Pentafluorophenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-
Tolyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl -4- (p-Ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-biphenyl) indenyl) } Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- ( m-
Trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2-methyl-4-)
Phenylindenyl)} zirconium dichloride, rac
-Di- (i-propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di
-(N-Butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride , Rac-methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-) Phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl)} zirconium dichloride, rac
-Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac -Dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-
Phenylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ M
e, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ M
e,

Rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-Dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-
Naphthyl) indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-ethyl-4- (2,
5-Dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(2,4,6-Trimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethyl Silylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-ethyl-4- (2,6-dichlorophenyl) indenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-n-propyl-4- (β- Naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5- Acenaphthyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl) -4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (8-Methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl- 4- (β-naphthyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- ( α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n -Butyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (5- Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i -Butyl-4- (9-phenanthryl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-methylphenylsilylene
-Bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac- Methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl) } Zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} Zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl) )} Zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl) -4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-methylene-bis {1- ( 2-Ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-
(Α-Naphtyl) 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, r
ac-dimethylgermyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-n-propyl-4-phenylindenyl) )} Zirconium dichloride and the like.

In addition, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can also be mentioned. In the present invention, the racemic body of the above transition metal compound is usually used as the catalyst component, but R type or S type can also be used.

In the present invention, two or more kinds of the above transition metal compounds may be used in combination. Such metallocene compounds are described in Journal of Organometallic Chem.288.
(1985), pp. 63-67, European Patent Application Publication No. 0,320,
It can be produced according to the specification of No. 762.

[0065]

Embedded image

In the formula (III), M is a transition metal atom of Group IVB of the periodic table, preferably titanium, zirconium or hafnium, and particularly preferably zirconium.

R ²¹ and R ²² may be the same or different and each is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

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

As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrocarbyl-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl; silyl of hydrocarbon-substituted silyl such as trimethylsilyl ether Ethers; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl.

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

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

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

Y is the same as Y in the formula (II). Specific examples of the transition metal compound represented by the general formula (III) are shown below. rac-Dimethylsilylene-bis {1
-(2,7-Dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-
n-Butylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl) } Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-n-hexylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethyl) Indenyl)} zirconium dichloride, rac-
Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-
Propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,7-dimethyl-4- i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,7-dimethyl-
4-t-butylindenyl)} zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindene) Nyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7 -Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t- Butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7
-Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,3,7
-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl) )} Zirconium methyl chloride, rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (methanesulfonato), rac
-Dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-
Methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilyl-bis {1- (2-methyl-3-methyl-4-i-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(2-Ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-Phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
(2-Methyl-4-i-propyl-7-methylindenyl)} titanium dichloride, rac-dimethylsilyl-bis {1- (2-
Methyl-4-i-propyl-7-methylindenyl)} hafnium dichloride, among these i-propyl at the 4-position, sec-
Those having a branched alkyl group such as a butyl or tert-butyl group are particularly preferable.

In the present invention, the racemic body of the above-mentioned transition metal compound is usually used as the catalyst component, but R type or S type can also be used. The above-mentioned transition metal compounds are prepared by known methods from indene derivatives, for example, JP-A-4-
It can be synthesized by the method described in Japanese Patent No. 268307.

Next, the transition metal compound represented by the general formula (IV) will be described. Transition metal compounds represented by the following general formula (IV) include EP-549900 and Canada-
It is the compound described in 2084017.

[0076]

Embedded image

In the formula (IV), M is a transition metal atom of Group IVB of the periodic table, preferably titanium, zirconium or hafnium, particularly preferably zirconium.

R ^{31 s} may be the same or different and each is a hydrogen atom, a halogen atom, preferably a chlorine atom or a bromine atom, and has 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
4 alkyl group, a halogenated alkyl group having a carbon number of 1 to 10, carbon atoms 6 to 10, preferably 6 to 8 aryl _{^{group, -NR 30 2, -SR 30,}} -OSiR 30 3, -
SiR ³⁰ ₃ or —PR ³⁰ ₂ group [wherein R ³⁰ is a halogen atom, preferably a chlorine atom, having 1 to 10 carbon atoms,
Preferably 1-3 alkyl groups or 6 carbon atoms
-10, preferably 6-8 aryl groups].

R ^{32 to} R ^{38, which} may be the same or different, each represents the same atom or group as R ^31, and at least two of the groups represented by R ^{32 to} R ³⁸ adjacent to each other. The groups, together with the carbon atoms to which they are attached, may form an aromatic or aliphatic ring.

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

[0081]

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

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

R ³⁹ and R ⁴⁰ may form a ring together with the atom to which they are bonded. M ¹ represents silicon, germanium or tin, preferably silicon or germanium.

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

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

[0087]

[Chemical 6]

(In the formula, M¹Is silicon and R³⁹and
R⁴⁰Are carbon atoms which may be the same or different from each other.
An alkyl group having 1 to 4 carbon atoms or 6 to 10 carbon atoms
A compound which is an aryl group) is preferred, and the substituent R is
³²And R³⁸Is a hydrogen atom, R³³~ R ³⁷Is carbon
Compounds having 1 to 4 alkyl groups or hydrogen atoms
The thing is more preferable.

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

[0090]

[Chemical 7]

(In the formula, M ¹ is silicon, R ³⁹ and R ⁴⁰ may be the same or different, and are an alkyl group having 1 to 4 carbon atoms or 6 to 10 carbon atoms.
Is preferred.

In particular, among the compounds represented by the general formula (IV), M ¹ is zirconium, R ³¹ is a methyl group, R ^{32 to} R ³⁸ are hydrogen atoms, and X is ³ and X ⁴ are chlorine atoms, and Z is

[0093]

Embedded image

(Wherein M ¹ is silicon, R ³⁹ and R ⁴⁰ may be the same or different from each other, and are a methyl group or a phenyl group).

Specific examples of the transition metal compound represented by the above general formula (III) are shown below. Dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2-methyl-α-acenaphthoindenyl)} zirconium dichloride, methylphenylsilylene -Bis {1- (2-methyl-4,
5-benzoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2-methyl-α-acenaphthoindenylcyclopentadienyl)} zirconium dichloride, methylphenylsilylene-bis {1- (4,5 -Benzoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2,6-dimethyl-4,5-benzoindenyl)} zirconium dichloride, methylphenylsilylene-bis {1- (2,4,6 -Trimethyl-4,5-benzoindenyl)} zirconium dichloride and the like.

Further, in the zirconium compound as described above, a compound in which zirconium is replaced by titanium or hafnium can also be mentioned. In the present invention, the racemic body of the above transition metal compound is usually used as the catalyst component, but R type or S type can also be used.

(B) Organoaluminum Oxy Compound (B) The organoaluminum oxy compound may be a conventionally known aluminoxane, and JP-A-2-7868.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Publication No.

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

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

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Trialkyl aluminum such as aluminum, 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 preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following formula (V) can also be mentioned.

[0102] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... (V) ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination.

As the solvent used for 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. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

These organoaluminum oxy compounds (B) can be used alone or in combination of two or more. (C) reacts with the transition metal compound (A) to form an ion pair
Compound (C) to be formed As a compound which reacts with the transition metal compound (A) to form an ion pair (hereinafter sometimes referred to as “ionized ionic compound”), JP-A-1-501950, JP-A-501950 Japanese Patent Laid-Open No. 1-502036 and Japanese Patent Laid-Open No. 3-179.
Examples of Lewis acids, ionic compounds, and carborane compounds described in JP-A-005-179, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106. You can

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

Specific examples of the Lewis acid containing a boron atom include compounds represented by the following formula (VI). BR ^a R ^b R ^c (VI) (In the formula, R ^a , R ^b and R ^c are each independently,
A phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group, or a fluorine atom is shown. ) Specific examples of the compound represented by the above formula (VI) include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoro). Methylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.
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. Such anions include organoboron compound anions,
There are an organic arsenic compound anion, an organic aluminum compound anion and the like, and those which are relatively bulky and stabilize 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.

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

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

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

Hereinafter, one kind of compound selected from the above-mentioned (B) organoaluminum oxy compound and (C) transition metal compound (A) to form an ion pair may be referred to as "activating compound". .

(D) Organoaluminum Compound As the (D) organoaluminum compound that is optionally used, an organoaluminum compound represented by the following formula (VII) can be exemplified.

R ^d _n AlX _3-n (VII) (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 above formula (VII), R ^d is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group. Group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

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

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

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

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

In addition, ethylene and 3 to 20 carbon atoms are included.
The catalyst used for the copolymerization of at least one olefin selected from the α-olefins and at least one polyene selected from the non-conjugated polyene having 5 to 20 carbon atoms is a particulate carrier, (A) Transition metal compounds,
It may be a prepolymerization catalyst comprising (B) an organoaluminum oxy compound [or (C) an ionizable ionic compound] and an olefin polymer formed by prepolymerization, and (D) an organoaluminum compound, if necessary.

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

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

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

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

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

Such a particulate carrier may contain surface hydroxyl groups and / or water. In the presence of the above catalyst, ethylene and α having 3 to 20 carbon atoms are used.
-When copolymerizing at least one olefin selected from olefins and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms, the transition metal compound (A) has a polymerization volume of 1 Approximately 0.0000 in terms of transition metal atoms per liter
5 to 0.1 mmol, preferably about 0.0001 to 0.0
Used in an amount of 5 mmol.

Organoaluminum oxy compound (B)
The aluminum atom is usually about 1 to 10,000 relative to 1 mol of the transition metal atom in the transition metal compound (A).
It can be used in an amount such that it is preferably 10 to 5,000 mol.

In the ionizable ionic compound (C), the boron atom is usually about 0.5 to 20 mol, preferably 1 to 1 mol, based on 1 mol of the transition metal atom in the transition metal compound (A).
It is used in an amount such that it is 0 mol.

Further, the organoaluminum compound (D) is
The amount is usually about 0 to 1000 mol, preferably about 0 to 500 mol, per 1 mol of the aluminum atom in the organoaluminum oxy compound (B) or the boron atom in the ionized ionic compound (C). Used as needed.

Using the above catalyst, ethylene and
When at least one olefin selected from α-olefins having 3 to 20 carbon atoms and at least one polyene selected from non-conjugated polyene having 5 to 20 carbon atoms are copolymerized, excellent polymerization is achieved. Active with ethylene / α-
An olefin / non-conjugated polyene copolymer can be obtained.

Ethylene and α-having 3 to 20 carbon atoms
When at least one olefin selected from olefins and at least one polyene selected from a non-conjugated polyene having 5 to 20 carbon atoms are copolymerized, the above transition metal compound (A) constituting a catalyst, The organoaluminum oxy compound (B), the ionized ionic compound (C) and the organoaluminum compound (D) may be separately supplied to the polymerization reactor, or a catalyst containing the transition metal compound (A) in advance. May be prepared and then subjected to a copolymerization reaction.

When preparing the catalyst, a hydrocarbon medium which is inactive with the catalyst components can be used. Specific examples of the inert hydrocarbon medium include propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclopentane,
Alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane can be used. These may be used in combination.

The transition metal compound (A), the organoaluminum oxy compound (B), the ionized ionic compound (C) and the organoaluminum compound (D) are usually
Mixing contact can be performed at 100 to 200 ° C, preferably -70 to 100 ° C.

In the present invention, ethylene and 3 carbon atoms are included.
At least one α-olefin selected from
Olefin and non-conjugated polyene having 5 to 20 carbon atoms
The copolymerization with at least one polyene selected from
Usually 40 to 200 ° C, preferably 50 to 150 ° C, particularly preferred
60 to 120 ° C, atmospheric pressure to 100 kg / cm ²
Preferably from atmospheric pressure to 50 kg / cm²Particularly preferably large
Atmospheric pressure-30kg / cm ²Can be performed under the conditions of
You.

This copolymerization reaction can be carried out by various polymerization methods, but solution polymerization is preferred. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent.

The copolymerization can be carried out by any of batch method, semi-continuous method and continuous method, but continuous method is preferred. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The molecular weight of the resulting ethylene / α-olefin / non-conjugated polyene copolymer can be adjusted by changing the polymerization conditions such as the polymerization temperature, and the amount of hydrogen (molecular weight modifier) used is controlled. It can also be adjusted by

The product immediately after polymerization is recovered from the polymerization solution and dried by a conventionally known separation / recovery method to obtain a solid ethylene / α-olefin / non-conjugated polyene copolymer.

[Hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer] The hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention has the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer. It is a modified copolymer in which the conjugated polyene copolymer is hydroxylated.

As a method for modifying the ethylene / α-olefin / non-conjugated polyene copolymer by hydroxylation, the following methods can be exemplified. (1) Diborane, 9-BBN (9-borabicycline) was added to ethylene / α-olefin / non-conjugated polyene copolymer in a solvent.
A method of adding hydroborane such as o [3,3,1] nonane), performing a hydroboration reaction, and then oxidizing with hydrogen peroxide. (2) A method of adding a mixture of an organic acid such as formic acid or acetic acid and hydrogen peroxide to an ethylene / α-olefin / non-conjugated polyene copolymer in a solvent and oxidizing the copolymer. in this way,
Hydroxylation and epoxidation proceed simultaneously to obtain a monohydroxyl monoesterified modified ethylene / α-olefin / non-conjugated polyene copolymer. This ester group can be converted into a hydroxyl group by saponification, whereby a dihydroxylated modified ethylene / α-olefin / non-conjugated polyene copolymer is obtained. (3) A method in which an organic peroxide such as peracetic acid or m-chloroperbenzoic acid is added to an ethylene / α-olefin / non-conjugated polyene copolymer in a solvent to epoxidize it, followed by hydrolysis.

In the method (1), the ethylene / α-olefin / non-conjugated polyene copolymer is used in an amount of 5 to 200 g / liter (solvent), preferably 10 to 100 g / liter (solvent). Hydroborane is used in an amount of 1 to 10 mol, preferably 2 to 5 mol, based on 1 mol of the unsaturated bond in the ethylene / α-olefin / non-conjugated polyene copolymer. Is used in an amount of 1 to 10 mol, preferably 2 to 5 mol, per 1 mol of hydroborane. The temperature of the hydroboration reaction and the oxidation reaction is -20 to 20.
The temperature is 80 ° C, preferably 0 to 70 ° C, and the reaction time is 0.
It is 5 to 20 hours, preferably 1 to 10 hours.

In the method (2), the ethylene / α-olefin / non-conjugated polyene copolymer is used in an amount of 5 to 400 g / liter (solvent), preferably 10 to 300 g / liter (solvent). The organic acid is 10 to 200 mol, preferably 5 to 100 mol, based on 1 mol of the unsaturated bond in the ethylene / α-olefin / non-conjugated polyene copolymer.
Hydrogen peroxide is used in an amount to be 100 mol.
1 to 50 mol, preferably 2 to 1 mol of unsaturated bond in the ethylene / α-olefin / non-conjugated polyene copolymer
It is used in an amount such that it is about 20 mol. The reaction temperature is 0 to 80 ° C., preferably 10 to 70 ° C., and the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours.

In the method (3), the ethylene / α-olefin / non-conjugated polyene copolymer is used in an amount of 5 to 400 g / liter (solvent), preferably 10 to 300 g / liter (solvent). The organic peroxide is
1 to 10 mol, preferably 1 to 1 mol of unsaturated bond in the ethylene / α-olefin / non-conjugated polyene copolymer
It is used in an amount such that it is -5 mol. The reaction temperature is 0 to 100 ° C., preferably 10 to 80 ° C., and the reaction time is 0.1 to 10 hours, preferably 0.5 to 5 hours.

In the hydrolysis, the acid concentration is 0.5
~ 5N, preferably 1-4N aqueous solution of ethylene.α-
10 per 1 g of olefin / non-conjugated polyene copolymer
~ 100 ml, preferably 5-50 ml is added. The reaction temperature is 20 to 100 ° C., preferably 40 to 80.
The reaction time is 1 to 20 hours, preferably 2-1.
0 hours.

Solvents used for the hydroxylation modification of the ethylene / α-olefin / non-conjugated polyene copolymer include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as ethyl ether, tetrahydrofuran and dioxane, and acetic acid. Examples thereof include organic acid esters such as ethyl.

By the above method, ethylene.α-
The carbon / carbon double bond existing in the side chain of the olefin / non-conjugated polyene copolymer is hydroxylated to obtain a modified copolymer having a hydroxyl group in the side chain.

As described above, ethylene / α-olefin /
The hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer obtained by hydroxylating and modifying the non-conjugated polyene copolymer has a hydroxyl group content of 0.01 to 10 mol per 100 g of the modified copolymer. , Preferably in the range of 0.02 to 8 mol. In addition, the content ratio of the structural unit derived from ethylene and the number of carbon atoms are 3 to 20.
The content ratio of the structural unit derived from the α-olefin and the content ratio of the structural unit derived from the non-conjugated polyene having 5 to 20 carbon atoms are the same as those before the modification.

The hydroxylated ethylene / α according to the present invention
-The olefin / non-conjugated polyene copolymer has an intrinsic viscosity [η] of 0.5 to 10 measured in decalin at 135 ° C.
dl / g, preferably 1.0 to 8 dl / g, Mw / Mn value of 3 or less, preferably 2.8 or less, and B value of 1.00 to 2.00, preferably 1 .00
The ratio (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα is 0.5 or less, preferably 0.1 or less, more preferably 0.01 or less.

If desired, known additives may be added to the hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer of the present invention within the range not impairing the object of the present invention. Such additives include weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifog agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antiaging agents, hydrochloric acid. Examples include absorbents and antioxidants.

Since the hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer of the present invention has a highly reactive hydroxyl group in the molecule, it may be reacted with various compounds having reactivity with the hydroxyl group. Is possible. Examples of such compounds include carboxylic acids such as acetic acid and propionic acid, epoxies such as ethylene oxide and propylene oxide, and isocyanates such as methyl isocyanate.

Further, the hydroxylated ethylene of the present invention
The α-olefin / non-conjugated polyene copolymer can be cross-linked by adding a compound having two or more functional groups reactive with a hydroxyl group in one molecule as a cross-linking agent. A cross-linking agent may be added for cross-linking, or the cross-linking agent may be contacted for cross-linking after molding. Examples of such cross-linking agents include polyfunctional isocyanate compounds and melamine compounds.

Examples of the polyfunctional isocyanate compound include aliphatic diisocyanates, alicyclic diisocyanates, aliphatic diisocyanates having an aromatic ring, aromatic diisocyanates, dimers and trimers of these diisocyanates, and tri- or higher functional isocyanate compounds. , And these phenol block products.

More specifically, examples of the aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexa Methylene diisocyanate, heptamethylene diisocyanate, 2,2'-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5'-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1, 5-diisocyanate, nonamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexane diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate , Tetradecamethylene diisocyanate, pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, and the like. As the alicyclic diisocyanate, cyclopropane-1,2-diisocyanate, cyclopropane-1,2-
Bis (carbonyl isocyanate), cyclopropane-
1,2-bis (methyl diisocyanate), cyclohexane
-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-
Methylcyclohexane-2,4-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω'-diisocyanate, 1,4 -Dimethylcyclohexane-ω, ω'-diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propylcyclorohexane-1ω, 2ω-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethylmethane-4 4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,2 '
-Dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3'-dimethyldicyclohexylmethane-4,4'-diisocyanate, 3,3 ', 5,5'-tetramethyldicyclohexylmethane-4,4'-diisocyanate, 2,2,4,4-tetramethyl-1,3-cyclobutane-4,4'-diisocyanate, 2,2,
4,4-Tetraethyl-1,3-cyclobutane-4,4'-diisocyanate, 2,2-dibutyl-2,4-diethyl-1,3-cyclobutane diisocyanate, 2,4-diethyl-2,4-dimethyl- 1,3-cyclobutane diisocyanate, 2,4-dimethyl-2,4-dipropyl-1,3-cyclobutane diisocyanate, 2,4-diethyl-2,4-dioctyl-1,3-cyclobutane diisocyanate and the like, aromatic Examples of the aliphatic diisocyanate having an aromatic ring include 1,3- or 1,4-xylylene diisocyanate, 1,4-diethylbenzene-ω, ω'-diisocyanate, m-phenylene bis (isopropyl isocyanate), p-phenylene bis (Isopropyl isocyanate), 4,4'-diphenylmethane diisocyanate, 1,3-
Diphenylpropane-1,3-diisocyanate, 1,4- or 1,5-dimethylnaphthalene-ω, ω'-diisocyanate,
Diphenyl ether-4,4'-bismethyl isocyanate,
4,4'-n-propylbiphenyl-ω, ω'-diisocyanate, anthracene-9,10-bismethylisocyanate, dihydroanthracene-9,10-diisocyanate, bis (2-
Isocyanate ethyl) terephthalate, bis (2-isocyanate ethyl) isophthalate, bis (2-isocyanate ethyl) -p-phenylenediacetate, and the like, and aromatic diisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4 ,
4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4- or 2,6-tolylene diisocyanate and the like can be mentioned, and as the trifunctional or higher functional isocyanate compound, 1-methylbenzene-2,4,6- Triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4, 4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethylphenylmethane-2,2 ', 5,5'-tetraisocyanate, triphenylmethane-4,4', 4 ″ -triisocyanate and the like can be mentioned.

Further, as the melamine compound, specifically, dimethylolmelamine, trimethylolmelamine and the like can be mentioned. Since the hydroxylated ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention has excellent affinity with metals and polar resins, it can be used as an adhesive between these materials and polyolefin, and also polar resin. Can be used as an impact resistance improving agent, a compatibilizing agent for polar resin and polyolefin, a dispersion aid when blending a pigment, glass fiber, inorganic fine particles and the like with polyolefin, and an additive for paint.

[0153]

EFFECT OF THE INVENTION Hydroxylated ethylene according to the present invention
The α-olefin / non-conjugated polyene copolymer has excellent affinity with metals and polar resins.

[0154]

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

The zirconium compounds used in the following examples are shown.

[0156]

Embedded image

[0157]

[Production Example 1] [Preparation of catalyst solution] A predetermined amount of the zirconium compound A and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) were placed in a dark place at room temperature, Mixing was performed by stirring for 30 minutes to prepare a toluene solution in which the zirconium compound A and methylalumoxane were dissolved. The Zr concentration of this toluene solution is 0.002 mmol / ml, and the methylalumoxane concentration is 1.2 mg atom / ml in terms of aluminum atom.

Next, to this toluene solution was added hexane with a volume five times that of toluene under stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, which was used for the polymerization reaction. Used as a catalyst.

Zr concentration: 0.00033 mmol / ml
= 0.33 mmol / liter Methylalumoxane concentration (converted to Al atom): 0.20 mmol / ml = 200 mmol / liter [Polymerization] Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, Continuously ethylene, propylene, 7-
Copolymerization with methyl-1,6-octadiene (hereinafter sometimes abbreviated as "MOD") was performed.

That is, first, from the top of the polymerization vessel into the polymerization vessel,
3.17 liters per hour of dehydrated and purified hexane, 0.03 liters per hour of the catalyst solution obtained above, 0.3 liters per hour of a hexane solution of triisobutylaluminum (concentration; 17 mmol / liter), 7-methyl- Hexane solution of 1,6-octadiene (concentration: 0.15 liter /
Liter) was continuously fed at 1.5 liter per hour.

Further, 200 liters of ethylene and 200 liters of propylene were continuously fed into the polymerization vessel from the upper portion of the polymerization vessel, respectively. This copolymerization reaction is 6
It was carried out at 0 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

Then, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
After the copolymer was separated from the solvent by steam stripping treatment, it was dried at 100 ° C. under reduced pressure (100 mmHg) for 24 hours.

With the above operation, ethylene / propylene / M
OD copolymer was obtained in an amount of 330 g / h. The obtained copolymer has a ratio of a constitutional unit derived from ethylene to a constitutional unit derived from propylene (ethylene / propylene) of 70/30, and a constitution derived from 7-methyl-1,6-octadiene. The unit content is 3.6 mol%, the intrinsic viscosity [η] is 2.6 dl / g, the Mw / Mn value is 2.1, the B value is 1.02, and Tαβ / Tα
The value of α was less than 0.01.

[0164]

[Production Example 2] In Production Example 1, as the non-conjugated polyene
Instead of 7-methyl-1,6-octadiene, ethylidene norbornene (hereinafter sometimes abbreviated as “ENB”) was used, and the concentration of the hexane solution of the non-conjugated polyene was 0.05 liter / liter. A copolymer was prepared in the same manner as in Example 1.

With the above operation, ethylene / propylene / E
The NB copolymer was obtained in an amount of 70 g / h. In the obtained copolymer, the ratio of the constitutional unit derived from ethylene and the constitutional unit derived from propylene (ethylene / propylene) was 72/28, and the content of the constitutional unit derived from ethylidene norbornene was 3.2. Mol%, intrinsic viscosity [η] is 2.3 dl / g, Mw / Mn value is 2.1, B value is 1.04, Tαβ / Tαα
Was less than 0.01.

[0166]

[Production Example 3] [Preparation of catalyst solution] A predetermined amount of the zirconium compound B and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom),
The mixture was stirred at room temperature in the dark for 30 minutes to prepare a toluene solution in which the zirconium compound B and methylalumoxane were dissolved. The Zr concentration of this toluene solution was 0.004 mmol / ml, and the methylalumoxane concentration was 1.2 in terms of aluminum atoms.
It is milligram atom / ml.

Then, to this toluene solution, hexane, which is a solution 5 times as much as that of toluene, was added with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, and this was subjected to a polymerization reaction. It was used as a catalyst.

Zr concentration: 0.00067 mmol / ml
(0.67 mmol / l) Methylalumoxane concentration (converted to Al atom): 0.
20 mmol / ml (200 mmol / l) [Polymerization] Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, ethylene, 1-butene, and 7-methyl-1,6-octadiene were continuously added. Was copolymerized.

That is, first, from the upper part of the polymerization vessel into the polymerization vessel,
3.185 liters of dehydrated and purified hexane per hour, 0.015 liters per hour of the catalyst solution obtained above, 0.3 liters per hour of a hexane solution of triisobutaluminum (concentration: 17 mmol / liter), and 7-methyl -1,6-
A hexane solution of octadiene (concentration: 0.15 liter / liter) was continuously supplied at 1.5 liters per hour.

From the top of the polymerization vessel, ethylene was added at an hour of 20.
0 liter and 1-butene of 155 liter per hour were continuously supplied. The copolymerization reaction is 90 ° C., and the average residence time is 1 hour (that is, a polymerization scale of 5 liters).
It was done so that

On the other hand, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
After the copolymer was separated from the solvent by steam stripping treatment, it was dried at 100 ° C. under reduced pressure (100 mmHg) for 24 hours.

With the above operation, ethylene / 1-butene / MO
D copolymer was obtained in an amount of 280 g / h. The obtained copolymer had a ratio of a structural unit derived from ethylene to a structural unit derived from 1-butene (ethylene / 1-butene) of 79/21, and 7-methyl-1,6-octadiene. The content of the constitutional unit derived from is 2.3 mol%, the intrinsic viscosity [η] is 2.4 dl / g, and the value of Mw / Mn is 2.
2, the B value was 1.08, and the value of Tαβ / Tαα was less than 0.01.

[0173]

Production Example 4 In Production Example 3, the non-conjugated polyene was used.
Except that ethylidene norbornene was used instead of 7-methyl-1,6-octadiene, the concentration of the hexane solution of the non-conjugated polyene was 0.20 liter / liter, and the supply amount of 1-butene was 100 liters / hour, A copolymer was prepared in the same manner as in Example 3.

With the above operation, ethylene / 1-butene / EN
The B copolymer was obtained in an amount of 250 g / h. The obtained copolymer had a ratio of the structural unit derived from ethylene to the structural unit derived from 1-butene (ethylene / 1-butene) of 88/12, and the content of the structural unit derived from ethylidene norbornene. Is 1.9 mol%, the intrinsic viscosity [η] is 2.6 dl / g, and the value of Mw / Mn is 2.
2, the B value was 1.01, and the value of Tαβ / Tαα was less than 0.01.

[0175]

[Production Example 5] In Production Example 3, as α-olefin
1-octene was used in place of 1-butene, the amount of 1-octene (liquid) supplied was 1.5 liters per hour, and the polymerization temperature was 7
A copolymer was prepared in the same manner as in Example 3 except that the temperature was 0 ° C.

With the above operation, ethylene / 1-octene / M
The OD copolymer was obtained in an amount of 130 g / h. The obtained copolymer had a ratio of a structural unit derived from ethylene to a structural unit derived from 1-octene (ethylene / 1-octene) of 89/11, and showed that 7-methyl-1,6-octadiene Is 2.5 mol%, the intrinsic viscosity [η] is 2.0 dl / g, the Mw / Mn value is 2.2, and the B value is 1.11. , Tαβ / Tα
The value of α was less than 0.01.

[0177]

Production Example 6 [Preparation of Titanium Catalyst] 2 g of tetrabutoxytitanium and 20 g of anhydrous magnesium chloride were placed in a stainless steel pot having an internal volume of 800 ml containing stainless steel balls (total weight 2.8 kg), and the stainless steel pot was placed in the pot. By vibrating, titanium tetrabutoxy and anhydrous magnesium chloride were co-ground for 8 hours. The co-milling was performed in a nitrogen atmosphere. The obtained co-ground product was transferred into 200 ml of ethylene dichloride and heated at 80 ° C. for 2 hours.
Then, the co-ground product was filtered and washed with n-decane until no free titanium tetrachloride was detected. In 1 g of the titanium catalyst thus obtained, 21 mg of titanium atoms were supported.

[Polymerization] Ethylene, 1-butene, and 5-ethylidene-2 were continuously added using a 2-liter continuous polymerization apparatus.
-Copolymerized with norbornene.

That is, 1 liter / hour of purified decane,
Ethyl aluminum sesquichloride was continuously supplied at a rate of 5 mg atom per hour in terms of aluminum atom, and the titanium catalyst obtained above at a rate of 0.25 mg atom per hour in terms of titanium atom. At the same time, 300 liters of ethylene per hour, 100 liters of 1-butene per hour,
-2-Norbornene was continuously fed at a rate of 70 g / h. The copolymerization reaction is carried out at a polymerization temperature of 110 ° C and a normal pressure and a residence time of 1
The conditions were such that the polymer concentration was 22 g / liter for an hour.

The produced polymer solution was continuously withdrawn from the polymerization vessel, the polymerization was stopped by adding a small amount of methanol, and the polymer solution was transferred into a large amount of methanol, and the precipitated polymer was heated at 80 ° C. for 12 hours. It was dried under reduced pressure.

The resulting ethylene / 1-butene / ENB copolymer had a ratio of the structural units derived from ethylene to the structural units derived from 1-butene (ethylene / 1-butene) of 8
9/11, the content of constitutional units derived from ethylidene norbornene was 1.9 mol%, and the intrinsic viscosity [η] was
Is 1.3 dl / g, the Mw / Mn value is 6.8, the B value is 0.85, and the Tαβ / Tαα value is 0.
It was less than 01.

[0182]

Example 1 150 ml of toluene, 1.5 g of the ethylene / propylene / MOD copolymer obtained in Production Example 1 was placed in a 300 ml glass round-bottomed flask with sufficient nitrogen substitution.
Formic acid 11.96 g and hydrogen peroxide aqueous solution (concentration: 35
%) 2.52 g was charged and the temperature was raised to 70 ° C. After further reacting at 70 ° C. for 6 hours, it was cooled to 25 ° C., and then the reaction solution was poured into 1.5 liter of acetone to precipitate a polymer. The precipitated polymer is filtered and filtered to 100
After being washed twice with ml of water, it was further washed twice with 100 ml of acetone and dried. Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer as follows, and the adhesive strength to Al was 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 3.3 g sample (modified copolymer) was placed in the cut-out portion). Then, a PET sheet, an aluminum sheet, and a press plate were further stacked in this order.

The sample sandwiched by the above-mentioned press plates was placed in a hot press at 180 ° C., preheated for 10 minutes, and then,
Pressurized (50 kg / cm ^2- to remove air bubbles in the sample
G) The depressurization operation was repeated several times. Then 50 kg / c
The pressure was raised to m ² -G and heated under pressure for 4 minutes. After depressurizing, it was taken out of the press machine of the press plate, transferred to another press machine where the pressure-bonded part was kept at 0 ° C., pressure-cooled at 50 kg / cm ² -G for 6 minutes, and then depressurized to give the sample. I took it out. The obtained film (modified copolymer film) has a uniform thickness of about 150 to 1
The portion having a thickness of 70 μm was used for measuring the adhesion strength to Al.

[Measurement of Adhesive Strength Against Al] The modified copolymer film was cut into 25 mm wide strips, which were cut to a width of 25 mm.
It was sandwiched between two pieces of aluminum foil having a thickness of 50 μm and heat-sealed. Heat seals the lower temperature of the heat sealer to 7
The temperature of the upper hot plate was 0 ° C., the temperature of the upper hot plate was 200 ° C., the heat sealing pressure was 1 kg / cm ² , and the heat sealing time was 1 second.
The obtained laminate was cut into 15 mm wide strips and left overnight in a thermostatic chamber at 25 ° C., after which the heat seal strength was measured.

The heat-sealing strength was 2 at 180 ° in the adhesive interface between the upper aluminum foil of the laminate and the modified copolymer.
It was determined by measuring the stress when peeling at a speed of 00 mm / min.

[0187]

Example 2 The procedure of Example 1 was repeated except that the ethylene / propylene / MOD copolymer obtained in Production Example 1 was replaced with the ethylene / propylene / ENB copolymer obtained in Production Example 2. A modified copolymer was obtained in the same manner as in Example 1. Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0189]

Example 3 In Example 1, except that the ethylene / 1-butene / MOD copolymer obtained in Production Example 3 was used in place of the ethylene / propylene / MOD copolymer obtained in Production Example 1. A modified copolymer was obtained in the same manner as in Example 1.
Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0191]

Example 4 In Example 1, except that the ethylene / 1-butene / END copolymer obtained in Production Example 4 was used in place of the ethylene / propylene / MOD copolymer obtained in Production Example 1. A modified copolymer was obtained in the same manner as in Example 1.
Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0193]

Example 5 In Example 1, except that the ethylene / 1-octene / MOD copolymer obtained in Production Example 5 was used in place of the ethylene / propylene / MOD copolymer obtained in Production Example 1. A modified copolymer was obtained in the same manner as in Example 1. Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0195]

Comparative Example 1 A film was prepared from the ethylene / propylene / MOD copolymer obtained in Production Example 1 in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0196]

Comparative Example 2 In Example 1, except that the ethylene / propylene / MOD copolymer obtained in Production Example 1 was replaced by the ethylene / 1-butene / ENB copolymer obtained in Production Example 6. A modified copolymer was obtained in the same manner as in Example 1.
Table 1 shows the properties of the obtained modified copolymer.

A film was prepared from the obtained modified polymer in the same manner as in Example 1, and the adhesive strength to Al was measured in the same manner as in Example 1. The results are shown in Table 1.

[0198]

[Table 1]

Claims (2)

[Claims] 1. Ethylene and α having 3 to 20 carbon atoms
Ethylene obtained from at least one olefin selected from olefins and at least one polyene selected from non-conjugated polyenes having 5 to 20 carbon atoms;
It is a modified copolymer in which the α-olefin / non-conjugated polyene copolymer is hydroxylated and modified, and contains (i) a constitutional unit derived from ethylene in a proportion of 50 to 95 mol% and having a carbon atom number of Containing 50 to 5 mol% of structural units derived from 3 to 20 α-olefins, more than 0 mol% and 5 mol% of structural units derived from non-conjugated polyene having 5 to 20 carbon atoms. % Or less, and (ii) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 10 dl / g, (ii)
i) the value of Mw / Mn, which is an index of the molecular weight distribution, is 3 or less, (iv) the B value obtained from the ¹³ C-NMR spectrum and the following formula is in the range of 1.00 to 2.00, and B Value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the molar fraction of the constituent units derived from ethylene in the copolymer, and P _O ] is the mole fraction of constituent units derived from α-olefin in the copolymer, and [P _OE ] is the total dyad (dy) in the copolymer.
ad) is the ratio of α-olefin / ethylene chain number to the chain number) (v) The intensity ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tαβ / Tαα) is 0.5 or less, and (vi) hydroxyl group Is in the range of 0.01 to 10 mol per 100 g of the modified copolymer, the hydroxylated ethylene / α-olefin /
Non-conjugated polyene copolymer. 2. The ethylene / α-olefin / non-conjugated polyene copolymer is ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms in the presence of a metallocene catalyst. And a hydroxylated ethylene / α-olefin / non-conjugated polyene according to claim 1, which is obtained by copolymerizing with a polyene having 5 to 20 carbon atoms. Copolymer.