JPH09241316A - Production of olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an olefin copolymer having a wide molecular weight distribution, improved molding and processing characteristics, and a good comonomer composition distribution by using a specified inexpensive catalyst system. SOLUTION: Olefins are copolymerized in the presence of the product (A) of contact between a complex component represented by the formula [X-(R<1> )r - Cp]n (Cp)m -MY4-m-n or R<2> [X-(R<1> )r -Cp](Cp)MY2 (wherein CP is substituted or unsubstituted cyclopentadienyl; M is Ti, Zr or Hf; X is an ester, amino, alkyl or arylcarbonyl group; Y is H, halogeno, a 1-20C hydrocarbon group, an amide group or a trifluoromethanesulfonic acid group; R<1> is an optionally substituted alkylene group or a silylene group; R<2> is a covalently bonding divalent crosslinking group containing a group 14 element; 0<n<=2 and 0<=m<2, provided 1<=m+n<=2; and r is 0 or 1) and a magnesium compound and an organoal uminum compound (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin copolymer. More specifically, the present invention provides a method for producing an olefin copolymer having a uniform comonomer composition distribution and good so-called copolymerizability by using a specific catalyst.

[0002]

2. Description of the Related Art As a catalyst for producing an olefin copolymer, a Ziegler-Natta catalyst has been conventionally known. In recent years, a new catalyst system comprising a metallocene compound and an aluminoxane has been developed (Japanese Patent Publication No. 4-1283, JP-A-60-35007, etc.). Compared with conventional Ziegler-Natta catalysts, this new catalyst has a higher polymerization activity per transition metal, a narrower molecular weight distribution, and a uniform comonomer composition distribution during copolymer production. It is known that

[0003]

However, in this new catalyst system, the molecular weight distribution (Q value) is narrow, so that the moldability is poor, and since the expensive aluminoxane is used, the catalyst cost is high, and further improvement is required. Was wanted.

[0004]

The present inventors have studied various catalysts in order to solve the above-mentioned problems, and as a result, have found that a catalyst obtained by bringing a specific transition metal compound into contact with a magnesium compound. The present invention has been accomplished by finding that a catalyst having a wide molecular weight distribution, good copolymerizability, uniform comonomer composition distribution, and low cost can be obtained by combining the component and the organoaluminum compound component.

That is, the method for producing an olefin copolymer according to the present invention is characterized by copolymerizing olefins in the presence of a catalyst in which the following components (A) and (B) are combined. . Component (A): The following component (A-1) and component (A-2)
A contact product of Component (A-1): a compound represented by the following general formula [1] or [2],

[0006]

## STR2 ## [X- _(R ¹⁾ _r -Cp] _{n (Cp) m MY 4-} mn (1) R ² [X- _(R ¹⁾ _r -Cp] (Cp) MY ₂ [2]

(Here, Cp represents a substituted or unsubstituted cyclopentadienyl group, and when a plurality of substituents are present on the same Cp ring, the adjacent substituents are bonded to each other to form a ring. M may form titania, zirconium or hafnium, X represents an ester group, an amino group, an alkylcarbonyl group or an arylcarbonyl group, and Y represents a hydrogen atom, a halogen atom or a carbon number of 1 to 2.
A hydrocarbon group, an alkoxy group, an aryloxy group, an amide group or a trifluoromethanesulfonic acid group of 0, Y
If there is more than one, they may be the same or different,
R ¹ represents an optionally substituted alkylene group or silylene group, R ² represents a divalent covalent crosslinkable group containing an element of Group 14 of the periodic table, n is 0 <n ≦ 2, and m is 0 ≦ m <
2 and 1 ≦ m + n ≦ 2, and r represents 0 or 1, respectively), Component (A-2): Magnesium compound Component (B): Organoaluminum compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an olefin copolymer according to the present invention is characterized in that olefins are copolymerized in the presence of a catalyst comprising a combination of specific components (A) and (B). It is a thing. <Olefin Polymerization Catalyst> The catalyst used in the present invention is
It is a combination of specific components (A) and (B). Here, "combined" does not mean that the components are only those listed above (that is, the component (A) and the component (B)), and is a range that does not impair the effects of the present invention. Does not exclude that other components coexist.

Component (A) The component (A) of the catalyst of the present invention is
It is a contact product of a specific transition metal component [component (A-1)] and a magnesium compound of component (A-2).
Such component (A) of the present invention does not exclude the coexistence of other purposeful components other than the above-mentioned two essential components. Component (A-1) The component (A-1) used in the present invention is represented by the following general formula [1].
Or a compound represented by [2].

[0010]

Embedded image [X- _(R ¹⁾ _r -Cp] _{n (Cp) m MY 4-} mn (1) R ² [X- _(R ¹⁾ _r -Cp] (Cp) MY ₂ [2]

(Here, Cp represents a substituted or unsubstituted cyclopentadienyl group, and when a plurality of substituents are present on the same Cp ring, adjacent substituents are bonded to each other to form a ring. M may represent titania, zirconium, hafnium, X is an ester group, an amino group, an alkylcarbonyl group or an arylcarbonyl group, and Y is a hydrogen atom, a halogen atom, or a carbon number of 1 to 20.
Represents a hydrocarbon group, an alkoxy group, an aryloxy group, an amide group or a trifluoromethanesulfonic acid group of, and when there are a plurality of Y, they may be the same or different, and R ¹ may be substituted. ² is a good alkylene group or silylene group, and R ² is a group ² element containing a group 14 element of the periodic table.
Represents a valent covalent cross-linking group, n is 0 <n ≦ 2, and m is 0
≦ m <2 and 1 ≦ m + n ≦ 2, and r represents 0 or 1, respectively.

In the above general formula [1] or [2], X
Is an ester group, an amino group, an alkyl or arylcarbonyl group, and specifically (i) an ester group includes a methyloxycarbonyl group, an ethyloxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, n-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n
A -heptyloxycarbonyl group, an n-octyloxycarbonyl group, and a mixed alkyloxycarbonyl group having 1 to 20 carbon atoms, preferably a methyloxycarbonyl group and an ethyloxycarbonyl group.

The (b) amino group includes an amino group, a methylamino group, an ethylamino group, an n-propylamino group,
Isopropylamino group, n-butylamino group, t-butylamino group, trimethylsilylamino group, dimethylamino group, diethylamino group, diisopropylamino group, piperidyl group, piperazyl group, preferably amino group, methylamino group, ethyl An amino group, an n-propylamino group, an n-butylamino group, a dimethylamino group, and a diethylamino group.

(C) As the alkyl or arylcarbonyl group, a methylcarbonyl group, an ethylcarbonyl group, an isopropylcarbonyl group, a t-butylcarbonyl group, a phenylcarbonyl group, a 4-methylphenylcarbonyl group, a 4-fluorophenylcarbonyl group, Examples thereof include a pentafluorophenylcarbonyl group, and among them, a methylcarbonyl group, an ethylcarbonyl group, a phenylcarbonyl group and the like are preferable.

Y is hydrogen, a halogen, an alkoxy group, an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, an amide group or a trifluoromethanesulfonic acid group, and there are plural Y's. In some cases, they may be the same or different. Specific examples of Y include hydrogen atom, halogen atom such as chlorine and bromine, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl. Base, n
-Pentyl, n-hexyl group, cyclohexyl group, n-
C1-C20 hydrocarbon groups such as heptyl group, n-nonyl group, n-decyl group, phenyl group and 4-methylphenyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; An aryloxy group such as a group, 4-methylphenoxy group and pentamethylphenoxy group; an amide group such as a dimethylamide group, a diethylamide group, a diisopropylamide group, a diphenylamide group and a dicyclohexylamide group; and trifluoromethanesulfonic acid. Among these, chlorine, hydrogen atom, methyl group, methoxy group, dimethylamide group, diethylamide group, and trifluoromethanesulfonic acid group are preferable.

R ¹ represents an optionally substituted alkylene group, an arylene group, an alkylidene group or a silylene group, and r is 0 or 1. Specifically, a methylene group,
Ethylene group, ethylidene group, isopropylidene group, 1,
Examples include 3-propylene group, 1,4-butylene group, 1,2-butylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, difluoromethylene group, tetrafluoroethylene group, 1,4-phenylene group. . Of these, an alkylene group, an alkylidene group and a silylene group are preferable, and an alkylene group and an alkylidene group are particularly preferable.

R ² is a covalent bond-linking group containing an element of Group 14 of the periodic table, such as carbon, silicon or germanium, which bonds the cyclopentadienyl ring. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dialkyl group Propylsilylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group,
Silicon-containing cross-linking groups such as methylphenylsilylene group, methylisopropylsilylene group, methyl (t-butyl) silylene group, dimethylgermylene group, diethylgermylene group, dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group Examples thereof include a germanium-containing crosslinking group such as a group, a methylethylgermylene group, a methylphenylgermylene group, a methylisopropylgermylene group, and a methyl (t-butyl) germylene group. Of these, an alkylene group, an alkylidene group, and a silicon-containing bridging group are preferably used, and a methylene group, an ethylene group, a diphenylmethylene group, a dimethylsilylene group, and a diphenylsilylene group are particularly preferably used. Hereinafter, the compounds represented by the general formulas [1] and [2] will be specifically exemplified when M is titanium.

1- (Methyloxycarbonylmethyl) cyclopentadienyltitanium trichloride, 1- (ethyloxycarbonylmethyl) cyclopentadienyltitanium trichloride, 1- (isopropyloxycarbonylmethyl) cyclopentadienyltitanium trichloride , 1- (n-butyloxycarbonylmethyl) cyclopentadienyl titanium trichloride, 1- (n
-Hexyloxycarbonylmethyl) cyclopentadienyltitanium trichloride, 1- (cyclohexyloxycarbonylmethyl) cyclopentadienyltitanium trichloride, 1- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyltitanium trichloride, 1- ( Phenyloxycarbonylmethyl) cyclopentadienyl titanium trichloride, 1- {2
-(Methyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium trichloride, 1- {2-
(Ethyloxycarbonyl) ethane-1-yl} cyclopentadienyl titanium trichloride,

1- {2- (isopropyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium trichloride, 1- {2- (n-butyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium Trichloride, 1- {2- (n-hexyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium trichloride, 1- {2- (cyclohexyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium Trichloride, 1- {2- (cyclohexylmethyloxycarbonyl) ethane-1-yl} cyclopentadienyltitanium trichloride, 1- {2-
(Phenyloxycarbonyl) ethane-1-yl} cyclopentadienyl titanium trichloride, 1- {dimethyl (methyloxycarbonyl) methyl} cyclopentadienyl titanium trichloride, 1- {dimethyl (ethyloxycarbonyl) methyl} cyclo Pentadienyltitanium trichloride, 1- {dimethyl (isopropyloxycarbonyl) methyl} cyclopentadienyltitanium trichloride, 1- {dimethyl (n-butyloxycarbonyl) methyl} cyclopentadienyltitanium trichloride,

1- {Dimethyl (n-hexyloxycarbonyl) methyl} cyclopentadienyl titanium trichloride, 1- {Dimethyl (cyclohexyloxycarbonyl) methyl} cyclopentadienyl titanium trichloride, 1- {Dimethyl (cyclohexylmethyl) Oxycarbonyl) methyl} cyclopentadienyltitanium trichloride, 1- {dimethyl (phenyloxycarbonyl) methyl} cyclopentadienyltitanium trichloride, 1- {4- (methyloxycarbonyl) butan-1-yl} cyclopenta Dienyltitanium trichloride, 1- {6- (methyloxycarbonyl) hexan-1-yl} cyclopentadienyltitanium trichloride, 1- (methyloxycarbonylmethyl) cyclopentadienylti Bromide trimethyl 1- (ethyloxycarbonylmethyl) cyclopentadienyl titanium trimethyl, 1- (isopropyloxycarbonyl methyl) cyclopentadienyl titanium trimethyl, 1
-(N-butyloxycarbonylmethyl) cyclopentadienyl titanium trimethyl,

1- (n-hexyloxycarbonylmethyl) cyclopentadienyltitanium trimethyl, 1-
(Cyclohexyloxycarbonylmethyl) cyclopentadienyl titanium trimethyl, 1- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl titanium trimethyl, 1- (phenyloxycarbonylmethyl) cyclopentadienyl titanium trimethyl, 1- (methyloxycarbonyl Methyl) cyclopentadienyl titanium trihydride, 1- (ethyloxycarbonylmethyl) cyclopentadienyl titanium trihydride, 1- (isopropyloxycarbonylmethyl) cyclopentadienyl titanium trihydride, 1- (n-butyloxycarbonyl) Methyl) cyclopentadienyltitanium trihydride, 1- (n-hexyloxycarbonylmethyl) cyclopentadienyltitanium Umm birds hydride, 1-
(Cyclohexyloxycarbonylmethyl) cyclopentadienyltitanium trihydride,

1- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyltitanium trihydride, 1- (phenyloxycarbonylmethyl) cyclopentadienyltitanium trihydride, 1-
(Methyloxycarbonylmethyl) cyclopentadienyl titanium tris (dimethylamide), 1- (methyloxycarbonylmethyl) cyclopentadienyl titanium tris (diethylamide), 1- (methyloxycarbonylmethyl) cyclopentadienyl titanium trimethoxy 1- (methyloxycarbonylmethyl) cyclopentadienyl titanium triphenoxide, 1-
(Methyloxycarbonylmethyl) cyclopentadienyl titanium tris (triflate), bis {1- (methyloxycarbonylmethyl) cyclopentadienyl}
Titanium dichloride, bis {1- (ethyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, bis {1- (isopropyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride,

Bis {1- (n-butyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, bis {1- (n-hexyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, bis {1- (cyclohexyloxy) Carbonylmethyl) cyclopentadienyl} titanium dichloride, bis {1
-(Cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, bis {1
-(Phenyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, bis [1- {2- (methyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, bis [1- {2-
(Ethyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, bis [1-
{2- (isopropyloxycarbonyl) ethane-1-
Il} cyclopentadienyl] titanium dichloride,
Bis [1- {2- (n-butyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, bis [1- {2- (n-hexyloxycarbonyl) ethane-1-yl} cyclopenta Dienyl] titanium dichloride,

Bis [1- {2- (cyclohexyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, bis [1- {2- (cyclohexylmethyloxycarbonyl) ethane-1-yl}
Cyclopentadienyl] titanium dichloride, bis [1- {2- (phenyloxycarbonyl) ethane-1
-Yl} cyclopentadienyl] titanium dichloride, bis [1- {dimethyl (methyloxycarbonyl)
Methyl} cyclopentadienyl] titanium dichloride, bis [1- {dimethyl (ethyloxycarbonyl)
Methyl} cyclopentadienyl] titanium dichloride, bis [1- {dimethyl (isopropyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, bis [1- {dimethyl (n-butyloxycarbonyl) methyl} cyclopentadienyl ] Titanium dichloride, bis [1- {dimethyl (n-hexyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, bis [1- {dimethyl (cyclohexyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, bis [ 1- {dimethyl (cyclohexylmethyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride,

Bis [1- {dimethyl (phenyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, bis [1- {4- (methyloxycarbonyl) butan-1-yl} cyclopentadienyl] titanium dichloride, Bis [1- {6- (methyloxycarbonyl) hexan-1-yl} cyclopentadienyl]
Titanium dichloride, bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, bis [1- (ethyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, bis [1-
(Isopropyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, bis [1- (n-butyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, bis [1- (n-hexyloxycarbonylmethyl) cyclopentadienyl ] Titanium dimethyl, bis [1- (cyclohexyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl,
Bis [1- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl,

Bis [1- (phenyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1-
(Ethyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1- (isopropyloxycarbonylmethyl) cyclopentadienyl]
Titanium dihydride, bis [1- (n-butyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1- (n-hexyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1- (Cyclohexyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, bis [1- (phenyloxycarbonylmethyl) cyclopentadienyl] Titanium dihydride, bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium bis (dimethylamide),

Bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium bis (diethylamide), bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium dimethoxide,
Bis [1- (methyloxycarbonylmethyl) cyclopentadienyl] titanium diphenoxide, bis [1-
(Methyloxycarbonylmethyl) cyclopentadienyl] titanium bis (triflate), dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- (methyloxycarbonyl) Methyl) cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- (ethyloxycarbonylmethyl) cyclopentadienyl] titanium dichloride, dimethylsilanediylbis {2- (isopropyloxycarbonylmethyl) cyclopentadienyl} titanium Dichloride, dimethylsilanediylbis {2- (n
-Butyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, dimethylsilanediylbis {2- (n-hexyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride,

Dimethylsilanediylbis {2- (cyclohexyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, dimethylsilanediylbis {2- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, dimethylsilanediylbis {2- (Phenyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, dimethylsilanediylbis [2- {2- (methyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2- (ethyloxycarbonyl) ethane-
1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2- (isopropyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2 -(N-Butyloxycarbonyl)
Ethan-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2-
(N-Hexyloxycarbonyl) ethane-1-yl}
Cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2- (cyclohexyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {2- (cyclohexylmethyl) (Oxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride,

Dimethylsilanediylbis [2- {2-
(Phenyloxycarbonyl) ethane-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {dimethyl (methyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {Dimethyl (ethyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {dimethyl (isopropyloxycarbonyl)
Methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {dimethyl (n-
Butyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {dimethyl (n-hexyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride,
Dimethylsilanediylbis [2- {dimethyl (cyclohexyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {dimethyl (cyclohexylmethyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethyl Silanediylbis [2- {dimethyl (phenyloxycarbonyl) methyl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- {4- (methyloxycarbonyl) butane-
1-yl} cyclopentadienyl] titanium dichloride,

Dimethylsilanediylbis [2- {6-
(Methyloxycarbonyl) hexane-1-yl} cyclopentadienyl] titanium dichloride, dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl] titaniumdimethyl, dimethylsilanediylbis [2- (ethyloxy Carbonylmethyl) cyclopentadienyl] titanium dimethyl,
Dimethylsilanediylbis [2- (isopropyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, dimethylsilanediylbis [2- (n-butyloxycarbonylmethyl) cyclopentadienyl] titaniumdimethyl, dimethylsilanediylbis [2 −
(N-Hexyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, dimethylsilanediylbis [2- (cyclohexyloxycarbonylmethyl)
Cyclopentadienyl] titanium dimethyl, dimethylsilanediylbis [2- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl, dimethylsilanediylbis [2- (phenyloxycarbonylmethyl) cyclopentadienyl] titanium dimethyl , Dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl]
Titanium dihydride,

Dimethylsilanediylbis [2- (ethyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2
-(Isopropyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2- (n-butyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2- (n- Hexyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2-
(Cyclohexyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2- (cyclohexylmethyloxycarbonylmethyl) cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2- (phenyloxycarbonylmethyl) ) Cyclopentadienyl] titanium dihydride, dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl] titanium bis (dimethylamide), dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopenta Dienyl] titanium bis (diethylamide), dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl] titanium dimethoxide

Dimethylsilanediylbis [2- (methyloxycarbonylmethyl) cyclopentadienyl] titanium diphenoxide, dimethylsilanediylbis [2
-(Methyloxycarbonylmethyl) cyclopentadienyl] titanium bis (triflate), dimethylsilanediylbis {2- (methyloxycarbonylmethyl)
Indenyl} titanium dichloride, dimethylsilanediylbis {2- (methyloxycarbonylmethyl) 4,
5,6,7-Tetrahydroindenyl} titanium dichloride, diphenylsilanediylbis {2- (methyloxycarbonylmethyl) cyclopentadienyltitanium dichloride, dimethylsilanediylbis {2- (diethylaminomethyl) cyclopentadienyltitanium dichloride Ethylenebis {2- (methyloxycarbonylmethyl) cyclopentadienyl titanium dichloride, ethylenebis {2- (ethyloxycarbonylmethyl) cyclopentadienyl} titanium dichloride, ethylenebis {2- (n-butyloxycarbonylmethyl) ) Cyclopentadienyl} titanium dichloride, ethylenebis {2- (diethylaminomethyl) cyclopentadienyl} titanium dichloride,

Ethylenebis {2- (methyloxycarbonylmethyl) indenyl} titanium dichloride, ethylenebis {2- (methyloxycarbonylmethyl) 4,
5,6,7-Tetrahydroindenyl} titanium dichloride, bis {1- (methyloxycarbonylmethyl)
Indenyl} titanium dichloride, bis {1- (methyloxycarbonylmethyl) -4,5,6,7-tetrahydroindenyl} titanium dichloride, bis {2-
(Methyloxycarbonylmethyl) indenyl} titanium dichloride, bis {2- (methyloxycarbonylmethyl) -4,5,6,7-tetrahydroindenyl}
Titanium dichloride, bis {1- (methyloxycarbonylmethyl) -3-methylcyclopentadienyl} titanium dichloride, bis {1- (methyloxycarbonylmethyl) -2,4-dimethylcyclopentadienyl} titanium dichloride, { 1- (methyloxycarbonylmethyl) cyclopentadienyl} cyclopentadienyltitanium dichloride, {1- (methyloxycarbonylmethyl) cyclopentadienyl} indenyltitanium dichloride,

Dimethylsilanediyl {2- (methyloxycarbonylmethyl) cyclopentadienyl} (cyclopentadienyl) titanium dichloride, dimethylsilanediyl {2- (methyloxycarbonylmethyl) cyclopentadienyl} (indenyl) titanium Dichloride, 1- (methyloxycarbonyl) cyclopentadienyltitanium trichloride, bis {1- (methyloxycarbonyl) cyclopentadienyl} titanium dichloride 1- (diethylamino) cyclopentadienyltitanium trichloride, bis {1- (Diethylamino) cyclopentadienyltitanium dichloride, 1- (acetyl) cyclopentadienyltitanium trichloride, bis {(1-acetyl) cyclopentadienyl} dichloride, dimethyl Silanediylbis {3- (methyloxycarbonyl) cyclopentadienyltitanium dichloride, dimethylsilanediylbis {2- (methyloxycarbonyl) indenyl} titanium dichloride,

Dimethylsilanediylbis {2- (methyloxycarbonyl) -4,5,6,7-tetrahydroindenyl} titanium dichloride, ethylenebis {2-
(Methyloxycarbonyl) indenyltitanium dichloride, ethylenebis {2- (methyloxycarbonyl) -4,5,6,7-tetrahydroindenyl} titanium dichloride, and the like. Further, as the compound of zirconium or hafnium, a compound in which titanium of the above-exemplified compound is replaced with zirconium or hafnium can be given.

Component (A-2) As the magnesium compound used in the present invention, magnesium dihalide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylic acid. Salt etc. are mentioned. Among these, Mg (OR ³ ) such as magnesium dihalide and dialkoxy magnesium
_2-a X _a (wherein R ³ is a hydrocarbon group, preferably having about 1 to 10 carbon atoms, X is halogen, preferably chlorine, and a is 0 ≦ a ≦ 2). The magnesium compound represented by is preferable, and magnesium dihalide is particularly preferable.

Further, when the component (A) is produced, it can be produced by using an electron donor as an internal donor. Examples of electron donors (internal donors) that can be used for the production of this component (A) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides. ,
Examples include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as isopropylbenzyl alcohol, (b) phenol, cresol,
6 to 2 carbon atoms which may have an alkyl group such as xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol and naphthol
5 phenols, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other ketones having 3 to 15 carbon atoms, (d)
C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde;

(E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
γ-butyrolactone, α-valerolactone, coumarin,
Organic acid monoesters such as phthalide, or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2- Dimethyl carboxylate, cyclopropane-1,2-dicarboxylic acid-n-hexyl,
C2-C20 organic acid esters of organic acid polyvalent esters such as diethyl 1,1-cyclobutanedicarboxylate,

(F) Inorganic acid esters such as ethyl silicate, butyl silicate, and silicates such as phenyltriethoxysilane, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride,
C2 to C15 acid halides such as phthaloyl chloride and phthaloyl isochloride; (T) methyl ether, ethyl ether, isopropyl ether, butyl ether;
C2-C20 ethers such as amyl ether, tetrahydrofuran, anisole and diphenyl ether, acid amides such as (li) acetic acid amide, benzoic acid amide and toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine , Piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine and other amines,

(L) acetonitrile, benzonitrile,
Nitriles such as trinitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, ethyl 2- (t-butoxymethyl) -benzoate, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate ,
Ethyl 3-ethoxy-2-s-butylpropionate, 3
-Alkoxy ester compounds such as ethyl ethoxy-2-t-butylpropionate, (wa) ethyl 2-benzoylbenzoate, ethyl 2- (4'-methylbenzoyl) benzoate, 2-benzoyl-4,5-dimethyl Examples thereof include keto ester compounds such as ethyl benzoate. Two or more of these electron donors can be used.

Manufacture of Component (A) Although the contact conditions of the respective components constituting the above-mentioned component (A) need to be carried out in the absence of water and oxygen, any contact condition can be obtained as long as the effect of the present invention is recognized. Can be one,
Generally, the following conditions are preferred. The contact temperature is -50
To about 200 ° C, preferably 0 to 100 ° C. Examples of the contacting method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent.
Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, and polysiloxanes.

The ratio of the amounts of the components constituting the component (A) to be used may be arbitrary as long as the effect of the present invention can be recognized, but in general, the following range is preferable. Ingredient (A-
The amount of 1) used is 0.0001 to 10 in molar ratio with respect to the amount of the magnesium compound of the component (A-2) used.
The range of 00 is preferable, and the range of 0.01 to 10 is preferable. When using an electron donor, the amount used
The molar ratio with respect to the amount of the magnesium compound used is preferably in the range of 0.001 to 10, preferably 0.01.
-5. The component (A) is the component (A-1),
By the contact with the component (A-2), if necessary, other components such as an electron donor may be used, for example, by the following production method.

(A) A method of bringing the magnesium halide into contact with an electron donor, if necessary, and the component (A-1). (B) A method of treating alumina or magnesia with a phosphorus halide compound, and contacting it with a magnesium halide, an electron donor, a silicon compound, and the component (A-1). (C) A reaction product obtained by contacting a titanium halogen compound and / or a silicon halogen compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound with an inert organic solvent. After washing, the silicon compound and the component (A-
Method of contacting 1) or contacting each separately.
As the polymer silicon compound, a compound represented by the following formula is suitable.

[0045]

Embedded image

(Here, R ⁴ is a hydrocarbon group having about 1 to 10 carbon atoms, and q is a polymerization degree such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Examples include methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9. -Pentamethylcyclopentasiloxane and the like are preferable.

(D) A method in which a magnesium compound is dissolved with titanium tetraalkoxide and / or an electron donor, and a solid component precipitated with a halogenating agent or a titanium halogen compound is contacted with component (A-1). (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donor is brought into contact therewith, and then the component (A-1) is brought into contact therewith.

(F) A method of bringing the halogenating agent and the component (A-1) into contact with the alkoxymagnesium compound in the presence or absence of an electron donor, or separately bringing them into contact with each other. Among these production methods, (a), (c), (d) and (f) are preferable. Component (A) is an intermediate and / or last component of its preparation, which is an inert organic solvent such as an aliphatic or aromatic hydrocarbon solvent (eg, hexane, heptane, toluene, cyclohexane, etc.), or a halogenated hydrocarbon solvent ( For example, it can be washed with n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

Component (A) used in the present invention is a compound containing a carbon-carbon unsaturated bond, such as olefins,
It can also be used as it has undergone a prepolymerization step of contacting and polymerizing a diene compound, styrene and the like. Specific examples of the olefins used in performing the prepolymerization include, for example, those having about 2 to 20 carbon atoms,
Specifically, ethylene, propylene, 1-butene, 3-methylbutene-1,1-pentene, 1-hexene, 4-methylpentene-1,1-octene, 1-decene, 1-undecene, 1-eicocene, etc. There are, as specific examples of the diene compound, 1,3-budadiene, isoprene, 1,
4-hexadiene, 1,5-hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,4-pentadiene, 2,6-octadiene, cis-2, trans
-4-hexadiene, trans-2, trans-4
-Hexadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 1,9-decadiene, 1,13
-Tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, dicyclopentadiene and the like. In addition, as specific examples of styrenes,
Examples include styrene, α-methylstyrene, allylbenzene, and chlorostyrene.

These compounds can be prepolymerized by using the component (A) and the organoaluminum compound described later. The reaction conditions of the titanium component and the above compounds may be arbitrary as long as the effect of the present invention is recognized, but generally, the following range is preferable. The amount of the prepolymerized carbon-carbon unsaturated bond-containing compound is 0.001 to 100 g, preferably 0.1 to 50 g, and more preferably 0.5 to 10 g per 1 g of the titanium solid component.
Within the gram range. The reaction temperature during prepolymerization is -15.
It is 0 to 150 ° C, preferably 0 to 100 ° C. Then, a "main polymerization", that is, a polymerization temperature lower than the polymerization temperature at the time of the polymerization of the α-olefin is preferable. The reaction is generally preferably carried out under stirring, at which time an inert solvent such as n-hexane or n-heptane can be present. The resulting component (A) is used as a catalyst component for olefin polymerization and is in a solid or liquid state, preferably a solid state, and is dissolved or wet in the same or different solvent used for the polymerization, Alternatively, it can be used for the polymerization of α-olefin in the state of a slurry dispersed in a solvent, but can also be used in the form of a powder after being dried.

Component (B) The organoaluminum compound as a component of the organoaluminum compound used in the present invention is R ⁵ _3-b AlX _b or R ⁶ _3-c Al (OR ⁷ ) _C (where R ⁵ and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R
⁷ is a hydrocarbon group, preferably a hydrocarbon group having 1 to 20 carbon atoms, X is halogen, and b and c are 0 respectively.
≦ b <3 and 0 <c <3. ). Specifically, (a) tolmethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum,
Trialkyl aluminum such as tridecyl aluminum, (b) diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, alkyl aluminum halide such as ethyl aluminum dichloride, (c) diethyl aluminum hydride, alkyl aluminum such as diisobutyl aluminum hydride Examples thereof include hydrides, alkyl aluminum alkoxides such as (d) diethyl aluminum ethoxide, and diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (i) to (iv), other organometallic compounds such as R ⁸ _3-d Al (O
R ⁹ ) _d (wherein R ⁸ and R ⁹ are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different, and d is 0 <
d ≦ 3. )) Can also be used in combination. For example, combined use of triethylaluminum and diethylaluminum ethoxide, combined use of diethylaluminum monochloride and diethylaluminum ethoxide, combined use of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum, diethylaluminum ethoxide and diethylaluminum monochloride. And the like. In addition, methylalumoxane, ethylalumoxane, etc.

[0053]

Embedded image

Organoaluminum having a bond can also be used. Among these, it is preferable to use the trialkylaluminum of (a). The ratio of the organoaluminum compound to the titanium component in the solid catalyst is generally Al / metal component in component (A) = 1 to 1000 mol / mol, preferably Al / metal in component (A). Ingredient =
It is used in a proportion of 10 to 500 mol / mol.

<Copolymerization of Olefin> The copolymerization of olefin of the present invention is applied to solution polymerization using a hydrocarbon solvent, slurry polymerization, liquid phase solventless polymerization or gas phase polymerization substantially without solvent. It A hydrocarbon solvent such as pentane, hexane, heptane, or cyclohexane is used as a polymerization solvent in the case of solution or slurry polymerization. The polymerization method employed may be any method such as continuous polymerization, batch polymerization or multi-stage polymerization. Polymerization temperature is usually 3
About 0 to 200 ° C, preferably 50 to 150 ° C,
Hydrogen can then be used as molecular weight regulator.

The olefins used in the present invention are represented by the general formula R ¹⁰ --CHCH ₂ (wherein R ¹⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and has a branched group). May also be used). Specifically ethylene,
Propylene, butene-1, pentene-1, hexene-
Examples include 1,4-methylpentene-1,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

Specific examples of the copolymerization include ethylene and propylene, butene-1, hexene-1, etc., and α of C ₃ or more.
-Copolymerization with olefin, copolymerization of propylene with ethylene, butene-1, hexene-1, etc. or α-olefin having C ₄ or more, and terpolymer of ethylene, propylene, butene-1, ethylene, butene -1, hexene-1 terpolymer, propylene, butene-1, hexene terpolymer, and the like.

For example, in an ethylene / α-olefin copolymer, the content of α-olefin having 3 to 20 carbon atoms is 1 to
It is within the range of 70% by weight. In that case, the optimum α-olefin content varies depending on the intended use, but for example, in an elastomer, the α-olefin content is in the range of 30% by weight to 60% by weight.

[0059]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited by these examples without departing from the gist thereof. The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used is Molecular Sieve-4A.
It was dehydrated and purified in.

Example 1 <Production of Component (A)> Internal volume 300 sufficiently replaced with nitrogen.
Ingredients (A
The MgCl ₂ 20 g -2) was added. Then, to 50 ml of sufficiently purified toluene, 1-of the component (A-1)
0.2 mol of (methyloxycarbonylmethyl) cyclopentadienyl titanium trichloride was dissolved and added to the flask at room temperature. Then, the temperature was raised to 110 ° C. and the reaction was carried out for 2 hours. After completion of the reaction, the temperature was returned to room temperature and the solid component was thoroughly washed with toluene to obtain a component (A). When a part of the obtained component (A) was taken out and the composition was analyzed, the carrying rate of the component (A-1) was 0.033.
It was mmol / g component (A).

<Ethylene-hexene-1 Copolymerization> Heptane 9 was added to a 0.5 liter flask which had been sufficiently purged with nitrogen.
0 ml was introduced, and then triisobutylaluminum (hereinafter abbreviated as TiBA) was added as component (B) at 1 mmo.
1 and 0.0 as the titanium component.
1 mmol respectively was introduced. Next, 10 ml of hexene-1 was added, the temperature was raised to 40 ° C., the introduction of ethylene was started, and the polymerization was carried out at normal pressure for 15 minutes. As a result, 0.
56 grams of copolymer were obtained. The physical properties of the copolymer are shown in Table 1.

Tm represents melting point and ΔH represents melting entropy, which was measured by DSC 220C manufactured by Seiko. The crystallinity is described in J. Polym. Phys. Ed. ,
Vol. 13, 1417- (1975) and calculated from ΔH. Mn represents the number average molecular weight and Mw represents the weight average molecular weight.
C-7100 "using Showa Denko's SHODEX U
It measured using the T-806L column. The cross-fractionation chromatograph (hereinafter abbreviated as CFC) is
It was measured by T-150A manufactured by Mitsubishi Chemical. The comonomer content and comonomer composition distribution in the copolymer are ¹³ C
It was measured using -nmr.

Examples-2 to 4 In the ethylene-hexene-1 copolymerization of Example-1, polymerization was carried out in exactly the same manner except that the amount of hexene-1 used and the polymerization temperature were changed. Table 1 shows the results. In addition, the ethylene-hexene obtained in Example-4
The comonomer distribution in the 1-copolymer was good.

Examples-5 to 6 <Ethylene-hexene-1 copolymerization> Polymerization was carried out under the same conditions as in Example-1, except that the amount of TiBA used as the component (B) was changed. It was The results are shown in Table-2.

Examples-7 to 8 <Ethylene-hexene-1 copolymerization> Under the polymerization conditions of Example-1, triethyl aluminum (hereinafter abbreviated as TEA) was used in place of TiBA as the component (B). Was polymerized under exactly the same conditions. The results are shown in Table-2.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

EFFECT OF THE INVENTION The olefin copolymer obtained by the method of the present invention has a broader molecular weight distribution compared to the molecular weight distribution (Q value) of olefin copolymers obtained by using a conventional metallocene catalyst, It has improved sex. Further, the obtained olefin copolymer has excellent copolymerizability and comonomer composition distribution, and an olefin copolymer can be efficiently produced without using alumoxane as a cocatalyst.

[Brief description of drawings]

FIG. 1 is intended to help understanding of the technical content of the present invention regarding a Ziegler catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kim ▲ Shou ▼ Soo 18-1 Asahidai, Tatsunokuchi-cho, Nomi-gun, Ishikawa Prefecture 1-323 (72) Inventor Takashi Fujita 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Incorporated company Yokkaichi Research Institute

Claims (1)

[Claims] 1. A process for producing an olefin copolymer, which comprises copolymerizing olefins in the presence of a catalyst in which the following components (A) and (B) are combined. Component (A): The following component (A-1) and component (A-2)
(A-1): a compound represented by the following general formula [1] or [2]: [X- (R ¹ ) _r -Cp] _n (Cp) _m MY _{4- mn} [1] R ² [X- (R ¹ ) _r -Cp] (Cp) MY ₂ [2] (wherein Cp represents a substituted or unsubstituted cyclopentadienyl group, and plural Cp rings may be present on the same Cp ring. When the substituent is present, adjacent substituents may be bonded to each other to form a ring, M is titanium, zirconium or hafnium, X is an ester group, an amino group or an alkylcarbonyl group. A group or an arylcarbonyl group, Y
Represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an amide group or a trifluoromethanesulfonic acid group, and when Y is plural, they may be the same or different. , R ¹ represents an optionally substituted alkylene group or silylene group,
R ² represents a divalent covalent crosslinking group containing an element of Group 14 of the periodic table, n is 0 <n ≦ 2, m is 0 ≦ m <2, and 1
≦ m + n ≦ 2, and r represents 0 or 1, respectively), Component (A-2): Magnesium compound Component (B): Organoaluminum compound.