JP2003048912A - Catalyst component for polymerizing vinyl compound, catalyst for polymerizing vinyl compound, method for producing vinyl compound polymer and use of transition metal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst component and a catalyst for polymerization capable of producing a copolymer of vinyl compounds having a bulky substituent with good copolymerizability, a method for producing the copolymer of the vinyl compounds having the bulky substituent and uses of a transition metal compound for producing the copolymer of the vinyl compounds having the bulky substituent with the good copolymerizability. SOLUTION: This catalyst component is used when the bulky vinyl compounds are subjected to addition polymerization. The catalyst component used for polymerizing the vinyl compounds comprises a transition metal compound represented by the following general formula [I] or [II]. The vinyl compound (1): a vinyl compound represented by CH2 =CH-R in which the steric parameter Es of the substituent R is <=-1.64 and the steric parameter B1 of the substituent R is >=1.53 and the vinyl compound (2): a vinyl compound represented by CH2 =CH-R' in which the substituent R' is a secondary alkyl group or a tertiary alkyl group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization catalyst component and a polymerization catalyst used in addition polymerization of a vinyl compound having a bulky substituent, and a method for producing a polymer of a vinyl compound having a bulky substituent. And the use of transition metal compounds in the addition polymerization of vinyl compounds having bulky substituents.

[0002]

2. Description of the Related Art In the field of polymerization of olefins such as ethylene and propylene, with the advent of single-site catalysts prepared by using transition metal compounds such as so-called metallocenes and nonmetallocenes, polymers with properties different from conventional ones are produced. The progress is being made that it is possible.

The application of such catalysts has also been proposed for the polymerization of vinyl compounds having bulky substituents such as vinylcyclohexane, for example Polymer Science USS.
R, Vol32.No.9,1868-1872 (1990), Polymer, Vol34 (9),
1941 (1993) discloses a method for producing a copolymer of ethylene and vinylcyclohexane.

[0004]

A polymer of a vinyl compound having such a bulky substituent has properties similar to polyvinyl chloride and is expected as a non-halogenated material.
However, the known method for producing the polymer as described above has low copolymerizability (that is, in comparison with the molar ratio of the vinyl compound having a bulky substituent in the monomer used for the polymerization,
The ratio of the repeating units derived from the vinyl compound contained in the obtained polymer (copolymerization composition) is considerably low),
It was difficult to obtain a copolymer having a high vinyl compound copolymerization composition. Under such circumstances, the problems to be solved by the present invention include a catalyst component and a polymerization catalyst capable of producing a copolymer of a vinyl compound having a bulky substituent with good copolymerizability, and a vinyl having a bulky substituent. It is to provide a method for producing a copolymer of a compound with good copolymerizability. Another object of the present invention is to provide a use of a transition metal compound for producing a copolymer of a vinyl compound having a bulky substituent with good copolymerizability.

[0005]

The present invention relates to a catalyst component used in the addition polymerization of the following vinyl compound (1) or the following vinyl compound (2), which is represented by the following general formula [I] or [II]: A catalyst component for polymerization of a vinyl compound comprising a transition metal compound represented by the following formula: a catalyst used when addition-polymerizing the following vinyl compound (1) or the following vinyl compound (2), wherein (A) the following general formula [I] or A vinyl compound polymerization catalyst obtained by contacting the transition metal compound represented by [II] with the following (B) and / or (C); using the vinyl compound polymerization catalyst, the following vinyl compound (1 ) Or a method for producing a vinyl compound polymer by addition-polymerizing the following vinyl compound (2); and; in addition polymerization of the following vinyl compound (1) or the following vinyl compound (2), the following general formula: The use of the transition metal compound represented by [I] or [II] as a catalyst component solves the above problems. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group. (In the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 24 carbon atoms or a substituted hydrocarbon group, a sulfonyloxy group having 1 to 24 carbon atoms,
Alternatively, it represents a disubstituted amino group having 2 to 24 carbon atoms. C
p represents a group having a cyclopentadiene type anion skeleton, and R represents an aryl group having 6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms. However, the general formula [I
Two Rs in I] may be the same or different. ) (B): One or more aluminum compounds (B1) selected from the following (B1) to (B3) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3 having the structure represented by _b) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
_A linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same) Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, c represents an integer of 1 or more.) (C): One or more boron compounds (C1) selected from the following (C1) to (C3): boron represented by the general formula BQ ¹ Q ² Q ^3. A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , and (C3) a general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, hydrocarbon Group, halogenated hydrocarbon group, substituted silyl group, an alkoxy group or a di-substituted amino group, they may be different even in the same .G ⁺ is an inorganic or organic cation, L is a neutral Lewis base and (L-H) ⁺ is Bronsted acid.).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula [I] or [II], M represents a transition metal atom of Group 4 of the periodic table of elements (IUPAC Inorganic Chemistry Nomenclature Revised Edition 1989), and preferably titanium. Atom, zirconium atom, or hafnium atom, more preferably titanium atom or zirconium atom, and particularly preferably titanium atom.

In the above general formula [I] or [II],
Cp represents a group having a cyclopentadiene type anion skeleton, for example, a η ^5- (substituted) cyclopentadienyl group,
η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -tert-butylcyclopentadienyl group,
η ⁵ -2,3-Dimethylcyclopentadienyl group, η ^5-
2,4-dimethylcyclopentadienyl group, η ⁵ -2-
Methyl, 3-tert-butylcyclopentadienyl group, eta ^5-2-methyl, 4-tert-butylcyclopentadienyl group, eta ^5-2-methyl, 3-isopropyl-cyclopentadienyl group, eta ⁵ - 2-methyl, 4-isopropylcyclopentadienyl group, η ⁵ -2,3,4-
Trimethylcyclopentadienyl group, η ⁵ -2,3,5
- trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, η ⁵ -4,
5,6,7-tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ⁵
4-methylindenyl group, eta ^{5-5-methylindenyl} group, eta ^{5-6-methylindenyl} group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert-butylindenyl group, η ⁵ -4
-Tert- butyl indenyl group, η ⁵ -5-tert
- butyl indenyl group, η ⁵ -6-tert- butyl indenyl group, η ⁵ -7-tert- butyl indenyl group, eta ^{5-2,3-dimethyl-indenyl} group, eta ^5-4,7
- dimethyl indenyl group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ^{5-4,5-benzindenyl} group, eta ⁵
-2-methyl-4,5-benzindenyl group, η ⁵ -4
- phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group, eta ⁵ - fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl-fluorenyl group, and substituted products thereof. C
More preferably, p is an η ^5- (substituted) cyclopentadienyl group or an η ^5- (substituted) indenyl group,
More preferably, it is an η ^5- (substituted) cyclopentadienyl group. In this specification, “η ⁵ −” may be omitted as the name of the transition metal compound.

In the above general formula [I], R represents an aryl group having 6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and O represents an oxygen atom. (RO-)
Specific examples of the aryloxy group, as a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group,
2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group Base, 2, 4,
6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,3-diethylphenoxy group, 2,4-diethylphenoxy group, Two
5-diethylphenoxy group, 2,6-diethylphenoxy group, 3,4-diethylphenoxy group, 3,5-diethylphenoxy group, 2,3,5-triethylphenoxy group, 2,3,6-triethylphenoxy group, 2, 4, 6
-Triethylphenoxy group, 3,4,5-triethylphenoxy group, 2-n-propylphenoxy group, 4-n-
Propylphenoxy group, 2,3-di-n-propylphenoxy group, 2,4-di-n-propylphenoxy group,
2,5-di-n-propylphenoxy group, 2,6-di-
n-propylphenoxy group, 3,4-di-n-propylphenoxy group, 3,5-di-n-propylphenoxy group, 2,3,5-tri-n-propylphenoxy group,
2,3,6-tri-n-propylphenoxy group, 2,
4,6-tri-n-propylphenoxy group, 3,4,5
-Tri-n-propylphenoxy group, 2-isopropylphenoxy group, 3-isopropylphenoxy group, 4-isopropylphenoxy group, 2,3-diisopropylphenoxy group, 2,4-diisopropylphenoxy group, 2,
5-diisopropylphenoxy group, 2,6-diisopropylphenoxy group, 3,4-diisopropylphenoxy group, 3,5-diisopropylphenoxy group, 2,3,5
-Triisopropylphenoxy group, 2,3,6-triisopropylphenoxy group, 2,4,6-triisopropylphenoxy group, 3,4,5-triisopropylphenoxy group, 2-sec-butylphenoxy group, 4-sec
-Butylphenoxy group, 2-tert-butylphenoxy group, 3-tert-butylphenoxy group, 4-ter
t-butylphenoxy group, 2,4-di-sec-butylphenoxy group, 2,6-di-sec-butylphenoxy group, 3,5-di-sec-butylphenoxy group, 2,4
-Di-tert-butylphenoxy group, 2,6-di-t
ert-butylphenoxy group, 3,5-di-tert-
Butylphenoxy group, 2-tert-butyl-4,6-
Dimethylphenoxy group,

2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group, 2-ethoxyphenoxy group, 4-ethoxyphenoxy group, 4-propoxyphenoxy group, 2-isopropyloxyphenoxy group, 4-butoxyphenoxy group. Group, 2,3-dimethoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,
4-dimethoxyphenoxy group, 3,5-dimethoxyphenoxy group, 3-ethoxy-4-methoxyphenoxy group,
2-bromophenoxy group, 3-bromophenoxy group, 4
-Bromophenoxy group, 2-chlorophenoxy group, 3-
Chlorophenoxy group, 4-chlorophenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-
Fluorophenoxy group, 2-iodophenoxy group, 3-
Iodophenoxy group, 4-iodophenoxy group, 4-nitrosophenoxy group, 2-nitrophenoxy group, 3-nitrophenoxy group, 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4- Aminophenoxy group, 2,4-dibromophenoxy group, 2,6
-Dibromophenoxy group, 2,3-dichlorophenoxy group, 2,4-dichlorophenoxy group, 2,5-dichlorophenoxy group, 2,6-dichlorophenoxy group, 3,4
-Dichlorophenoxy group, 3,5-dichlorophenoxy group, 2,3-difluorophenoxy group, 2,4-difluorophenoxy group, 2,5-difluorophenoxy group,
2,6-difluorophenoxy group, 3,4-difluorophenoxy group, 3,5-difluorophenoxy group, 2,
4-dinitrophenoxy group, 2,5-dinitrophenoxy group, 2,6-dinitrophenoxy group, 3,5-dinitrophenoxy group, 2,3-diaminophenoxy group,

2-bromo-4-chlorophenoxy group, 4
-Bromo-2-chlorophenoxy group, 2-bromo-4-
Fluorophenoxy group, 2-bromo-5-fluorophenoxy group, 4-bromo-2-fluorophenoxy group, 4
-Bromo-2-nitrophenoxy group, 2-chloro-4-
Fluorophenoxy group, 3-chloro-4-fluorophenoxy group, 4-chloro-2-fluorophenoxy group, 4
-Chloro-3-fluorophenoxy group, 2-chloro-4
-Nitrophenoxy group, 4-chloro-2-nitrophenoxy group, 4-chloro-3-nitrophenoxy group, 2-fluoro-4-nitrophenoxy group, 3-fluoro-4-
Nitrophenoxy group, 4-fluoro-2-nitrophenoxy group, 5-fluoro-2-nitrophenoxy group, 2,
4,6-tribromophenoxy group, 2,3,4-trichlorophenoxy group, 2,3,5-trichlorophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,5
-Trichlorophenoxy group, 2,4,6-trichlorophenoxy group, 2,3,4-trifluorophenoxy group,
2,3,5-trifluorophenoxy group, 2,3,6-
Trifluorophenoxy group, 2,4,6-trifluorophenoxy group, 2,4,6-triiodophenoxy group,
4-bromo-2-fluoro-6-nitrophenoxy group,
2-bromo-4,5-difluorophenoxy group, 2,6
-Dibromo-4-fluorophenoxy group, 2,6-dibromo-4-nitrophenoxy group, 2-chloro-3,5-
Difluorophenoxy group, 2,6-dichloro-4-fluorophenoxy group, 2,4-dichloro-6-nitrophenoxy group, 2,3-difluoro-6-nitrophenoxy group, 2,6-diiodo-4-nitrophenoxy group Base 2,
3,5,6-Tetrafluorophenoxy group, pentachlorophenoxy group, pentafluorophenoxy group, 2-chloro-4-methylphenoxy group, 2-chloro-5-methylphenoxy group, 4-chloro-2-methylphenoxy group , 4-chloro-3-methylphenoxy group, 4-chloro-3-ethylphenoxy group, 4-chloro-2-isopropyl-5-methylphenoxy group, 4-fluoro-2-methylphenoxy group, 4-fluoro-3 -Methylphenoxy group, 2-bromo-4-methylphenoxy group, 4-iodo-2-methylphenoxy group, 2-amino-3-methylphenoxy group, 2-amino-4-methylphenoxy group,
3-amino-2-methylphenoxy group, 4-amino-2
-Methylphenoxy group, 4-amino-3-methylphenoxy group, 2-amino-5-methylphenoxy group, 3-chloro-5-methoxyphenoxy group, 2-fluoro-6-
Examples thereof include a methoxyphenoxy group, a 5-amino-2-methoxyphenoxy group, a 2,4-dichloro-3-methylphenoxy group, and a 2,4-dibromo-4-methylphenoxy group.

Specific examples of (RO-) include aralkyloxy groups such as benzyloxy group and (2
-Methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group,
(2,3-Dimethylphenyl) methoxy group, (2,4-
Dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group,
(3,5-dimethylphenyl) methoxy group, (2,3,
4-trimethylphenyl) methoxy group, (2,3,5-
Trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4, 5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethyl (Phenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec
-Butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) A methoxy group, a naphthyl methoxy group, an anthracenyl methoxy group, etc. are mentioned, Preferably it is a benzyloxy group. Any of these aralkyloxyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group or the like.

In the transition metal compound represented by the above general formula [I] or [II], although the details of the mechanism are not known at present, since R is an aryl group or an aralkyl group, its steric structure is It is considered that due to such factors, the stability of the transition metal compound in the reaction system, and further the selectivity of the reaction as a ligand are improved, and therefore high activity is provided. Therefore, R is preferably an aryl group or an aralkyl group having at least one substituent on the aromatic ring. More preferably, R is an aryl group or aralkyl group having a hydrocarbon group or a substituted hydrocarbon group having 1 to 10 carbon atoms in at least the 2-position on the aromatic ring, and even more preferably, R is at least an aromatic ring. It is an aryl group or an aralkyl group having a hydrocarbon group or a substituted hydrocarbon group having 1 to 10 carbon atoms at the above 2- and 6-positions. Particularly preferably, R is an aryl group having a hydrocarbon group having 1 to 10 carbon atoms or a substituted hydrocarbon group at least at the 2- and 6-positions on the aromatic ring. In the general formula [II], two Rs may be the same or different.

In the above general formula [I] or [II],
X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 24 carbon atoms or a substituted hydrocarbon group, a sulfonyloxy group having 1 to 24 carbon atoms, or 2 having 2 to 24 carbon atoms. Represents a substituted amino group. Specific examples of the halogen atom include chlorine atom, bromine atom, iodine atom and the like.

Examples of the hydrocarbon group having 1 to 24 carbon atoms include an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and an aralkyl group having 7 to 24 carbon atoms. And, to give a specific example of the alkyl group,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neo-pentyl group, amyl group, n-hexyl group, n-octyl group Group, n-decyl, n
-Dodecyl group, n-pentadecyl group, n-eicosyl group and the like can be mentioned, and preferably methyl group, ethyl group, isopropyl group, tert-butyl group or amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and the like.

As the aryl group, for example, a phenyl group,
2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-
Xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5
-Xylyl group, 2,3,4-trimethylphenyl group,
2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4
5-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-
Butylphenyl group, tert-butylphenyl group, n-
Pentylphenyl group, neo-pentylphenyl group, n
-Hexylphenyl group, naphthyl group, anthracenyl group and the like can be mentioned, with preference given to phenyl group. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group or the like.

Examples of the aralkyl group include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group,
(2,3-Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (4,6
-Dimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group , (N-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl)
Methyl group, (n-pentylphenyl) methyl group, (ne
o-pentylphenyl) methyl group, naphthylmethyl group,
Anthracenylmethyl group and the like can be mentioned, and benzyl group is preferable. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group or the like.

The sulfonyloxy group having 1 to 24 carbon atoms refers to a compound represented by the general formula R "SO _3- , specifically, R" such as methanesulfonyloxy group, ethanesulfonyloxy group and dodecanesulfonyloxy group. Is an alkyl group, or is partially substituted with halogen such as a trifluoromethanesulfonyloxy group,
R ″ is an aryl group such as a p-toluenesulfonyloxy group.

The disubstituted amino group having 2 to 24 carbon atoms is an amino group substituted with two hydrocarbon groups or the like,
Here, as the hydrocarbon group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and other alkyl groups having 1 to 23 carbon atoms, and phenyl group and other aryl groups. . Examples of the disubstituted amino group having 2 to 24 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group. , Di-tert-butylamino group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino Group, a bis-tert-butyldimethylsilylamino group and the like, and preferably a dimethylamino group or a diethylamino group.

These X and Y may optionally combine to form a ring. X and Y in the general formula [I] or [II] are preferably each independently a halogen atom, an alkyl group, an aralkyl group, or a sulfonyloxy group, and more preferably, each independently a chlorine atom, a methyl group, It is a trifluoromethanesulfonyloxy group or a benzyl group.

The transition metal compound represented by the above general formula [I] or [II] is, for example, the following general formula [III]
It is easily synthesized by reacting the transition metal compound represented by the formula (I) with a compound represented by the following general formula [IV] or an alkali metal salt thereof. (In the above general formula [III] or [IV], Cp,
X, Y and R are each of the general formula [I] or [I
I], and Z is the same as X or Y in the general formula [I] or [II]. O represents an oxygen atom and H represents a hydrogen atom. )

The reaction conditions at this time are the same as those for the usual reaction using an organometallic compound. Specifically, the solvent is an ether solvent such as diethyl ether, or a halogenated hydrocarbon solvent such as dichloromethane. , And a hydrocarbon solvent such as toluene or hexane can be used, and the reaction temperature is usually from −50 ° C. to 110 ° C.

These transition metal compounds may be used alone or in combination of two or more. In the present invention, μ-oxo type or bisμ which is a reaction product of the transition metal compound represented by the above general formula [I] or [II] and 0.5 times or equimolar amount of water thereof.
-Oxo type transition metal compounds may be used.

The transition metal compound represented by the above general formula [I] or [II] is used as a catalyst component used in the addition polymerization of a vinyl compound having a bulky substituent. In the present invention, the catalyst used in the addition polymerization of the vinyl compound having a bulky substituent is obtained by bringing the transition metal compound represented by the general formula [I] or [II] into contact with the activation cocatalyst. The resulting vinyl compound polymerization catalyst is preferably obtained by contacting (A) a transition metal compound represented by the above general formula [I] or [II] with the following (B) and / or (C). The resulting vinyl compound polymerization catalyst. (B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O-} _b Cyclic aluminoxane (B3) having a structure represented by the general formula E ³ {-Al (E ³ ) -O-} _c AlE ³
_A linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same) Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, c represents an integer of 1 or more.) (C): One or more boron compounds (C1) selected from the following (C1) to (C3): boron represented by the general formula BQ ¹ Q ² Q ^3. A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , and (C3) a general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, hydrocarbon Group, halogenated hydrocarbon group, substituted silyl group, an alkoxy group or a di-substituted amino group, they may be different even in the same .G ⁺ is an inorganic or organic cation, L is a neutral Lewis base and (L-H) ⁺ is Bronsted acid.). The preferred vinyl compound polymerization catalyst will be further described below.

(B) Aluminum Compound In the above aluminum compound (B), E ¹ , E ²
As the hydrocarbon group for and E ^3, a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexyl aluminum chloride; alkyl aluminum dichlorides such as methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride and hexyl aluminum dichloride. Dimethylal Examples thereof include dialkyl aluminum hydrides such as minium hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride. It is preferably a trialkylaluminum, more preferably triethylaluminum or triisobutylaluminum.

[0026] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 Specific examples of E ² and E ^{3 in} the linear aluminoxane (B3) having the structure shown are a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and neopentyl. An alkyl group such as a group can be exemplified. b is 2
The above is an integer, and c is an integer of 1 or more. Preferably, E ² and E ³ are methyl groups or isobutyl groups, b is 2-40 and c is 1-40.

The above aluminoxanes can be made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, it is prepared by bringing a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) into contact with water. In addition, a method in which a trialkylaluminum (eg, trimethylaluminum) is brought into contact with a metal salt containing crystal water (eg, copper sulfate hydrate) can be exemplified. The aluminoxane thus obtained and the commercially available aluminoxane are usually (B
It is considered to be a mixture of 2) and (B3).

(C) Boron Compound A boron compound represented by the general formula BQ ¹ Q ² Q ³ (C
1), B is a boron atom in a trivalent valence state, Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, substituted silyl groups, alkoxy groups or disubstituted amino groups. , They may be the same or different. Q ^{1 to} Q ³ are preferably halogen atoms, 1
To a hydrocarbon group containing 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy containing 1 to 20 carbon atoms Group or an amino group containing 2 to 20 carbon atoms, more preferably Q ^{1 to} Q ³ are halogen atoms, 1
A hydrocarbon group containing -20 carbon atoms, or 1-20
It is a halogenated hydrocarbon group containing 4 carbon atoms. More preferably Q ¹ to Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, particularly preferably Q ¹ to Q ⁴ are each at least one fluorine It is a fluorinated aryl group having 6 to 20 carbon atoms including atoms.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane and tris (2,3,3).
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Examples thereof include phenylbis (pentafluorophenyl) borane, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. an atom, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

Specific examples of G ⁺ , which is an inorganic cation in the compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , include ferrocenium cations, alkyl-substituted ferrocenium cations, and silver. Examples of G ⁺ , which is an organic cation such as a cation, include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
Tetrakis (pentafluorophenyl) borate, Tetrakis (2,3,5,6-tetrafluorophenyl) borate, Tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluoro) Phenyl) borate, tetrakis (2,3,4-)
Trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5
-Bistrifluoromethylphenyl) borate and the like.

Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, but most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

Further, the general formula (L-H) ⁺ (BQ ¹ Q ² Q
^{In the} boron compound (C3) represented by ³ Q ⁴ ) ^- , L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, and B is a boron atom in a trivalent valence state. in and, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

General formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} Examples of Bronsted acid (L-H) ⁺ of the compound represented by trialkyl, N, N-dialkyl anilinium, dialkyl ammonium, triarylphosphonium and the like, ^{(BQ 1 Q 2 Q 3 Q} 4) - as include the same as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, but most preferably tri (n-butyl) ammonium tetrakis (pentafluoro). Phenyl) borate or N, N-
It is dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization] A preferable vinyl compound polymerization catalyst used in the present invention is (A) a transition metal compound represented by the above general formula [I] or [II], and (B) and / or ( It is a catalyst for vinyl compound polymerization obtained by contacting with C). The contact here may be any means as long as the above (A) and (B) and / or (C) come into contact with each other to form a catalyst, and they may be diluted or not diluted with a solvent in advance. To (A) above
And (B) and / or (C) are mixed and brought into contact with each other, or a method of supplying them separately to the polymerization tank and bringing them into contact with each other in the polymerization tank to form a catalyst can be employed. As a method of supplying each catalyst component to the polymerization tank, it is preferable to supply nitrogen, an inert gas such as argon in a water-free state,
In that case, two or three arbitrary members may be mixed in advance and brought into contact with each other, and then separately supplied to the polymerization tank.

As the polymerization catalyst (A) and (B)
When using a polymerization catalyst obtained by contacting (B)
As the above, the above-mentioned cyclic aluminoxane (B2) and / or linear aluminoxane (B3) are preferable. Another preferred embodiment of the polymerization catalyst is a polymerization catalyst obtained by bringing the above (A), (B) and (C) into contact with each other. ) Is easy to use.

The amount of each component used is usually such that the molar ratio [converted to Al atoms contained in (B)] / (A) is 0.1 to 10.
000, preferably 5-2000, and the molar ratio of (C) / (A) is 0.01-100, preferably 0.5-10.
It is desirable to use each component so as to be in the range.
The concentration when each component is used in a solution state or in a state of being suspended in a solvent is appropriately selected depending on the conditions such as the performance of the apparatus for supplying each component to the polymerization reactor, but generally,
(A) is usually 0.01 to 500 μmol / g, more preferably 0.05 to 100 μmol / g, further preferably 0.05 to 50 μmol / g, and (B) is A
Usually 0.01 to 10,000 μmol / g in terms of 1 atom
And more preferably 0.1 to 5000 μmol / g,
More preferably, 0.1-2000 μmol / g,
(C) is usually 0.01 to 500 μmol / g, preferably 0.05 to 200 μmol / g, and more preferably 0.05 to 100 μmol / g. desirable.

As the catalyst used in the present invention, a particulate carrier containing an inorganic carrier such as SiO ₂ or Al ₂ O _{3 and} an organic polymer carrier such as a polymer such as ethylene or styrene may be used in combination.

The polymerization method is not particularly limited, and any method such as a batch or continuous gas phase polymerization method, a bulk polymerization method, a solution polymerization method using a suitable solvent or a slurry polymerization method can be used. can do. When a solvent is used, various solvents can be used provided that they do not deactivate the catalyst. Examples of such a solvent include hydrocarbons such as benzene, toluene, pentane, hexane, heptane and cyclohexane; Examples thereof include halogenated hydrocarbon groups such as styrene chloride.

The polymerization temperature is not particularly limited, and generally -100 to 250 ° C, preferably -50 to 200 ° C is adopted. The pressure is not limited, but is generally 10 MPa or less, preferably 0.1 MPa to 5 MPa.
It is carried out in. Also, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

The vinyl compound targeted by the present invention is a vinyl compound having a bulky substituent, and the following vinyl compound (1) is targeted by the present invention. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more.

Solid parameters Es and B1 referred to here
Is a parameter (Es represents a three-dimensional spread and B1 represents a two-dimensional spread) representing the steric bulkiness of a substituent, and is a document (C. Hansch and A. Leo:
"Exploring QSAR Fundament
als and Applications in Ch
emissary and Biology "Chapt
er3 (ACS Professional Ref.
Rence Book, Washington, DC (1
995)).

The vinyl compound (1) is exemplified below.

For reference, the steric parameters of some vinyl compounds having non-bulky substituents are shown below.

The present invention is more preferably applied to vinyl compounds having a bulkier substituent. The steric parameter Es of the substituent R is preferably -3.10 to -1.70, more preferably -2.80 to -1.72,
Particularly preferred is -2.35 to -1.75, and most preferred is -2.10 to -1.75. The steric parameter B1 of the substituent R is preferably 1.53 to
It is 2.90, more preferably 1.70 to 2.70, and particularly preferably 1.91 to 2.60. Explaining the properties of the obtained copolymer, if the steric parameter Es is too large or the steric parameter B1 is too small, elastic recovery and delayed recovery are poor, which is not preferable. Further, the present invention is suitable for the vinyl compound (1) in which the substituent R is a hydrocarbon group, and more preferably for the vinyl compound (1) in which the substituent R is a saturated hydrocarbon group.

The vinyl compound having a bulky substituent, which is the object of the present invention, is the following vinyl compound (2) from another viewpoint. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group.

The secondary alkyl group or tertiary alkyl group referred to herein is preferably a secondary alkyl group having 3 to 20 carbon atoms or a tertiary alkyl group having 4 to 20 carbon atoms. R may be a cycloalkyl group, in which case it is preferably a cycloalkyl group having a 3 to 16 membered ring, and more preferably 3 to 20 carbon atoms in a 3 to 10 membered ring.
Is a cycloalkyl group. R ′ is preferably 3
It is a cycloalkyl group having 3 to 20 carbon atoms in a 10-membered ring or a tertiary alkyl group having 4 to 20 carbon atoms.

Specific examples of the vinyl compound (2) include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane and 3-methyl-1-.
Butene, 3-methyl-1-pentene, 3-methyl-1-
Hexene, 3-methyl-1-heptene, 3-methyl-1
-Octene, 3,3-dimethyl-1-butene, 3,3-
Dimethyl-1-pentene, 3,3-dimethyl-1-hexene, 3,3-dimethyl-1-heptene, 3,3-dimethyl-1-octene, 3,4-dimethyl-1-pentene, 3,4- Dimethyl-1-hexene, 3,4-dimethyl-1-heptene, 3,4-dimethyl-1-octene,
3,5-dimethyl-1-hexene, 3,5-dimethyl-
1-heptene, 3,5-dimethyl-1-octene, 3,
6-dimethyl-1-heptene, 3,6-dimethyl-1-
Octene, 3,7-dimethyl-1-octene, 3,3
4-trimethyl-1-pentene, 3,3,4-trimethyl-1-hexene, 3,3,4-trimethyl-1-heptene, 3,3,4-trimethyl-1-octene, 3,
4,4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,4,4-trimethyl-1-
Heptene, 3,4,4-trimethyl-1-octene, 5
-Vinyl-2-norbornene, 1-vinyl adamantane, 4-vinyl-1-cyclohexene and the like can be mentioned.

More preferred vinyl compounds (2) are vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane and 5-vinyl-2-.
Norbornene, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-methyl-1-hexene, 3,3-dimethyl-1-butene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 3,5-dimethyl-1- It is hexene, 3,3,4-trimethyl-1-pentene, or 3,4,4-trimethyl-1-pentene. More preferable vinyl compound (2) is vinylcyclohexane, vinylnorbornene or 3-methyl-1-.
Butene, 3-methyl-1-pentene, 3,3-dimethyl-1-butene, 3,4-dimethyl-1-pentene, or 3,3,4-trimethyl-1-pentene, and particularly preferred vinyl compound ( 2) is vinylcyclohexane or 3,3-dimethyl-1-butene.

In the present invention, the vinyl compound having a bulky substituent is homopolymerized or copolymerized. In the case of copolymerization, it is possible to copolymerize a plurality of kinds of vinyl compounds or to copolymerize the vinyl compound with another addition-polymerizable monomer that is copolymerizable. In the latter case, the invention shows high copolymerizability.

The other addition-polymerizable monomer is preferably an olefin, more preferably ethylene and / or
Alternatively, it is an α-olefin. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-
Non-linear olefins such as 1-decene and 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, branched olefins such as 5-methyl-1-hexene Etc. More preferred α-olefins are propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, or 4-
Methyl-1-pentene, particularly preferably propylene, 1-butene or 1-hexene.

In such a copolymer, the copolymer composition of the vinyl compound having a bulky substituent is 0.1 to 99 mol.
The present invention is applicable to a wide range of copolymers such as%. The present invention is particularly useful for producing a copolymer having a high copolymerization composition, and the copolymerization composition is preferably 5 to 99 mol.
%, More preferably 15 to 99 mol%, and particularly preferably 25 to 99 mol%. If the copolymer composition is too low, the copolymer may form crystals derived from a chain of olefin units in its skeleton, which is not preferable in terms of transparency. The copolymer composition is ¹ H-NM
It can be easily obtained by a conventional method using an R spectrum or a ¹³ C-NMR spectrum.

A secondary compound derived from a vinyl compound having a bulky substituent is present in the polymer skeleton of the polymer produced by the present invention (including a branched polymer chain in the polymer molecular chain). There are carbon atoms and tertiary carbon atoms. Further, in the case of a copolymer of ethylene and a vinyl compound having a bulky substituent, a secondary carbon atom derived from ethylene is also present, and in the case of a copolymer of α-olefin such as propylene, α-olefin. There are also secondary and tertiary carbon atoms of origin. Depending on the sequence in the polymer skeleton, a structure in which tertiary carbon atoms are separated by one methylene group, a structure in which two methylene groups are separated, a structure in which three methylene groups are separated, 4 There may be structures separated by more than one methylene group. The polymer structure is determined by ¹³ C-NMR spectrum. As the copolymer produced in the present invention, a vinyl compound having two or more bulky substituents is He.
Copolymers having chains linked in an ad-to-tail fashion are also obtained, in which case there is a structure in which the tertiary carbon atoms are separated by one methylene group.

Specific examples of the above addition-polymerizable monomers other than olefins include methyl vinyl ether, ethyl vinyl ether, acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate and the like, and one of them is used. Alternatively, two or more kinds may be used for copolymerization.

[0056]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples. The properties of the polymers in the examples were measured by the following methods.

The intrinsic viscosity [η] was measured at 135 ° C. with tetralin as a solvent using an Ubbelohde viscometer.

The glass transition point and the melting point were measured under the following conditions using DSC (SSC-5200 manufactured by Seiko Instruments Inc.). Temperature rise 20 ° C to 200 ° C (20 ° C / min) Hold for 10 minutes Cooling 200 ° C to -50 ° C (20 ° C / min) Hold for 10 minutes Measurement -50 ° C to 300 ° C (20 ° C / min)

The copolymerization composition of vinylcyclohexane units in the polymer and the structure of the polymer were determined by ¹³ C-NMR analysis. ¹³ C-NMR apparatus BRXER DRX600 measurement solvent 4: 1 (volume ratio) mixed solution of orthodichlorobenzene and orthodichlorobenzene-d4 Measurement temperature 135 ° C

[Example 1] 400 m purged with argon
27 m vinylcyclohexane in an autoclave
1, and 168 ml of dehydrated toluene were added. After heating to 30 ° C., 0.8 MPa of ethylene was charged. Toluene solution of methylalumoxane [MMA manufactured by Tosoh Akzo Co., Ltd.
O, Al atomic conversion concentration 6 wt%] 2.8 ml was charged, and then synthesized by the method described in JP-A No. 11-166010 (pentamethylcyclopentadienyl) (2.
A solution prepared by dissolving 2.1 mg of 6-diisopropylphenoxy) titanium dichloride in 2.1 ml of dehydrated toluene was charged. After stirring the reaction solution for 1 hour, the reaction solution was poured into 500 ml of ethanol, and the precipitated white solid was collected by filtration. The solid was washed with ethanol and dried under reduced pressure to give 16.19 g of a polymer. [Η] of the polymer
Was 1.43 dl / g, the glass transition point was -23 ° C, and the copolymerization composition of vinylcyclohexane was 20 mol%. The press sheet of the polymer had very high transparency and excellent flexibility and elastic recovery. The ¹³ C-NMR spectrum of the obtained polymer is shown in FIG. It was confirmed that the carbon atoms substituted with a cyclohexyl group have a structure separated by three methylene groups and a structure separated by one methylene group.

Example 2 27 ml of vinylcyclohexane used in Example 1 was replaced with 103 m of vinylcyclohexane.
1 liter of dehydrated toluene 168 ml was added to dehydrated toluene 44
ml, (pentamethylcyclopentadienyl) (2,
6-Diisopropylphenoxy) titanium dichloride 2.1 mg was dissolved in dehydrated toluene 2.1 ml, and 1.1 mg was replaced with dehydrated toluene 1.1 ml. Then, 13.77 g of a polymer was obtained. The [η] of the polymer was 0.91 dl / g, the glass transition point was 11 ° C., and the copolymer composition of vinylcyclohexane was 37 mol%. The press sheet of the polymer had very high transparency and excellent flexibility and elastic recovery. ^{13 of the} obtained polymer
The C-NMR spectrum is shown in FIG. It was confirmed that the carbon atoms substituted with a cyclohexyl group have a structure separated by three methylene groups and a structure separated by one methylene group.

Comparative Example 1 44 ml of dehydrated toluene in Example 2 was replaced with 40 ml of dehydrated toluene, and 1.1 mg of (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium dichloride was added to 1.1 ml of dehydrated toluene. After being dissolved, biscyclopentadienyl zirconium dichloride [Stre
m company] 2.2 mg was dissolved in 4.5 ml of dehydrated toluene, and the same procedure as in Example 1 was carried out to obtain 11.70 g of a polymer. The copolymer composition of vinylcyclohexane in the polymer was 0.31 mol%. The ¹³ C-NMR spectrum of the obtained polymer is shown in FIG.

[Embodiment 3] 300 m purged with argon
68m vinylcyclohexane in a glass reactor of 1
1, and 17 ml of dehydrated toluene were added. After heating to 50 ° C., 0.1 MPa of ethylene was charged. Toluene solution of methylalumoxane [MMA manufactured by Tosoh Akzo Co., Ltd.
O, Al atom conversion concentration 6 wt%] 5.9 ml was charged, followed by (pentamethylcyclopentadienyl)
A solution prepared by dissolving 4.3 mg of (2,6-diisopropylphenoxy) titanium dichloride in 8.6 ml of dehydrated toluene was charged. After stirring the reaction solution for 1 hour, the reaction solution was poured into 500 ml of ethanol, and the precipitated white solid was collected by filtration. The solid was washed with ethanol and dried under reduced pressure to obtain 1.11 g of a polymer. [Η] of the polymer was 0.18 dl / g, the glass transition point was 76 ° C,
The copolymerization composition of vinylcyclohexane was 75 mol%. The pressed sheet of the polymer was very transparent. The ¹³ C-NMR spectrum of the obtained polymer is shown in FIG. Carbon atoms substituted with cyclohexyl groups,
It was confirmed to have a structure separated by three methylene groups and a structure separated by one methylene group.

[0064]

As described above, according to the present invention,
A catalyst component and a polymerization catalyst capable of producing a copolymer of a vinyl compound having a bulky substituent with good copolymerizability, and
Provided is a method for producing a copolymer of a vinyl compound having a bulky substituent with good copolymerizability. Further, according to the present invention, there is provided a use of the transition metal compound for producing a copolymer of a vinyl compound having a bulky substituent with good copolymerizability.

[Brief description of drawings]

FIG. 1 is a diagram showing the ¹³ C-form of the copolymer obtained in Example 1.
It is an NMR spectrum.

FIG. 2 shows ¹³ C-of the copolymer obtained in Example 2.
It is an NMR spectrum.

FIG. 3 is a graph showing the ¹³ C-type of the copolymer obtained in Comparative Example 1.
It is an NMR spectrum.

FIG. 4 is a graph of ¹³ C-of the copolymer obtained in Example 3.
It is an NMR spectrum.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AB00A AB01A AC01A                       AC10A AC28A BA00A BA02B                       BB00A BB01B BC12B BC15B                       BC16B BC17B BC25B EA02                       EB02 EB04 EB05 EB07 EB10                       EB21 ED04 ED05 ED09

Claims (5)

[Claims] 1. A catalyst component used in the addition polymerization of the following vinyl compound (1) or the following vinyl compound (2), which comprises a transition metal compound represented by the following general formula [I] or [II]: Catalyst component for vinyl compound polymerization. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group. (In the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 24 carbon atoms or a substituted hydrocarbon group, a sulfonyloxy group having 1 to 24 carbon atoms,
Alternatively, it represents a disubstituted amino group having 2 to 24 carbon atoms. C
p represents a group having a cyclopentadiene type anion skeleton, and R represents an aryl group having 6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms. However, the general formula [I
Two Rs in I] may be the same or different. ) 2. A catalyst used in the addition polymerization of the following vinyl compound (1) or the following vinyl compound (2), which is (A) a transition metal compound represented by the following general formula [I] or [II]: And the following (B) and / or the following (C)
A catalyst for vinyl compound polymerization obtained by contacting with. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group. (In the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 24 carbon atoms or a substituted hydrocarbon group, a sulfonyloxy group having 1 to 24 carbon atoms,
Alternatively, it represents a disubstituted amino group having 2 to 24 carbon atoms. C
p represents a group having a cyclopentadiene type anion skeleton, and R represents an aryl group having 6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms. However, the general formula [I
Two Rs in I] may be the same or different. ) (B): One or more aluminum compounds (B1) selected from the following (B1) to (B3) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3 having the structure represented by _b) the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3
_A linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ are the same) Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. An integer, c represents an integer of 1 or more.) (C): One or more boron compounds (C1) selected from the following (C1) to (C3): boron represented by the general formula BQ ¹ Q ² Q ^3. A compound, (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , and (C3) a general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, hydrocarbon Group, halogenated hydrocarbon group, substituted silyl group, an alkoxy group or a di-substituted amino group, they may be different even in the same .G ⁺ is an inorganic or organic cation, L is a neutral Lewis base and (L-H) ⁺ is Bronsted acid.). 3. A method for producing a vinyl compound polymer, which comprises subjecting the following vinyl compound (1) or the following vinyl compound (2) to addition polymerization using the catalyst for vinyl compound polymerization according to claim 2. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group. 4. The method for producing a vinyl compound polymer according to claim 3, wherein the vinyl compound polymer is a copolymer of an olefin and the vinyl compound (1) or the vinyl compound (2). 5. When the following vinyl compound (1) or the following vinyl compound (2) is subjected to addition polymerization, the following general formula [I]
Alternatively, use of the transition metal compound represented by [II] as a catalyst component. Vinyl compound (1): A vinyl compound represented by CH ₂ ═CH—R, the steric parameter Es of the substituent R is −1.64 or less, and the steric parameter B1 of the substituent R is 1.53 or more. Vinyl compound (2): A vinyl compound represented by CH ₂ ═CH—R ′, in which the substituent R ′ is a secondary alkyl group or a tertiary alkyl group. (In the above general formula [I] or [II], M
Represents a transition metal atom of Group 4 of the periodic table, and O represents an oxygen atom. X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 24 carbon atoms or a substituted hydrocarbon group, a sulfonyloxy group having 1 to 24 carbon atoms,
Alternatively, it represents a disubstituted amino group having 2 to 24 carbon atoms. C
p represents a group having a cyclopentadiene type anion skeleton, and R represents an aryl group having 6 to 24 carbon atoms or an aralkyl group having 7 to 24 carbon atoms. However, the general formula [I
Two Rs in I] may be the same or different. )