JP2006233117A - Olefin-terpenoid copolymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an olefin-terpenoid copolymer having a low gel content and to provide a method for producing the same. <P>SOLUTION: The olefin-terpenoid copolymer is obtained by copolymerizing an olefin with a terpenoid containing at least one unsaturated bond and has ≤10 wt% gel content contained in the polymer (the total of the copolymer is 100 wt%). The method for producing the olefin-terpenoid copolymer comprises using a polymerization catalyst obtained by bringing a specific transition metal compound represented by the general formula: L<SB>α</SB>MX<SB>β</SB>into contact with an organoaluminum compound and/or a boron compound and copolymerizing an olefin with a terpenoid containing at least one unsaturated bond. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an olefin-terpenoid copolymer having a low gel content, and further relates to a method for producing an olefin-terpenoid copolymer in which an olefin and a terpenoid are copolymerized using a transition metal compound as a polymerization catalyst.

For the purpose of improving the physical properties of olefin polymers such as polyethylene and polypropylene, various olefin copolymers have been developed in which a compound having a bulky structure such as a ring structure is copolymerized as a comonomer in the olefin polymer.
A terpenoid, which is one of compounds having a bulky structure, is generally a compound containing a hydrocarbon having a composition represented by (C ₅ H ₈ ) _n and oxygen derived therefrom. Terpenoids are also abundant in compounds contained in plant sap and seed essential oils, and can be obtained at low cost. Among these, there is a compound having an unsaturated bond, and attempts have been made to use it as a comonomer of an olefin copolymer.

  As a conventional olefin-terpenoid copolymer, for example, Non-Patent Document 1 describes an ethylene-propylene-terpenoid terpolymer copolymerized using a vanadium Ziegler-Natta catalyst, Non-Patent Document 2 describes an ethylene-terpenoid copolymer copolymerized by a high-pressure radical polymerization method.

“Journal of Polymer Science” (Part A, Volume 3, pages 3815-3823, 1965) “Australian Chemical Engineering” (page 3-12, April 1968)

However, since the ethylene-terpenoid copolymer produced by the production method described in Non-Patent Document 1 and Non-Patent Document 2 contains a gel content generated by homopolymerization of the terpenoid, However, there is a problem that it is difficult to apply to applications where transparency is important.
In such a situation, the problem to be solved by the present invention, that is, an object of the present invention is to provide an olefin-terpenoid copolymer having a low gel content and a method for producing the same.

  The first of the present invention is obtained by copolymerizing an olefin and a terpenoid having at least one unsaturated bond, and the gel content contained in the copolymer is 10% by weight or less (however, the total copolymer is Olefin-terpenoid copolymer).

The second of the present invention is the use of a polymerization catalyst obtained by contacting a transition metal compound represented by the following general formula [I], an organoaluminum compound and / or a boron compound, with an olefin and at least one unsaturated bond. The present invention relates to a method for producing an olefin-terpenoid copolymer in which a terpenoid having a terpolymer is copolymerized.
L _α MX _β [I]
(In the above general formula [I], M represents a group 4 to 10 or lanthanoid series transition metal atom of the periodic table. L represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. And when a plurality of L are present, the plurality of L may be the same or different, and the plurality of L may be directly or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or phosphorus X may represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of Xs are present, the plurality of Xs may be the same. In addition, the hydrocarbon group having 1 to 20 carbon atoms may contain a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and α satisfies 0 <α ≦ 8. Represents a satisfied number, β represents a number satisfying 0 <β ≦ 8.)

  According to the present invention, an olefin-terpenoid copolymer having a low gel content and a method for producing the same are provided.

The present invention will be described in detail below.
The olefin-terpenoid copolymer of the present invention is a copolymer obtained by copolymerizing an olefin and a terpenoid having at least one unsaturated bond.

  Examples of the olefin used in the present invention include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, Examples include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, vinylcyclohexane, and the like, and an olefin having 2 to 20 carbon atoms is preferable. The above olefins may be used alone or in combination.

  The terpenoid referred to in the present invention is any of terpene hydrocarbons and derivatives thereof, terpene alcohols and derivatives thereof, terpene aldehyde derivatives that do not contain heteroatoms, and terpene ketone derivatives that do not contain heteroatoms. Among these compounds, terpenoids having at least one unsaturated bond are used. The above terpenoids having at least one unsaturated bond may be used alone or in combination.

  Examples of the terpene hydrocarbon having the at least one unsaturated bond include monoterpene hydrocarbon, sesquiterpene hydrocarbon, and diterpene hydrocarbon. Monoterpene hydrocarbons include, for example, limonene, terpinolene, α-terpinene, γ-terpinene, β-ferrandrene, sabinene, 2-carene, 3-carene, himacarene, α-pinene, β-pinene, camphene, α- Myrcene, β-myrcene, and the like. Examples of the sesquiterpene hydrocarbon include bisabolen, kazinene, caryophyllene, cedrene, humulene, aristolene, elemorphylene, guaien, germane and the like. Examples of the diterpene hydrocarbon include kaurene.

  Examples of the terpenoid having at least one unsaturated bond include monoterpene alcohol, sesquiterpene alcohol, and diterpene alcohol. As monoterpene alcohol, terpineol etc. are mentioned, for example. Examples of sesquiterpene alcohol include eudesmol. Examples of the diterpene alcohol include hinokiol.

  As the terpenoid having at least one unsaturated bond, as a compound that is a terpene aldehyde derivative and does not contain a hetero atom, for example, a hetero atom in a terpenoid such as citronellal, citral, cyclocitral, safranal, ferrandral, perilaldehyde, etc. The compound of the structure which converted the carbonyl group into the carbon-carbon double bond by substituting for a carbon atom is mentioned.

  As the above-mentioned terpenoid having at least one unsaturated bond, as a compound that is a terpene ketone derivative and does not contain a heteroatom, for example, a carbonyl group can be obtained by substituting a carbon atom for a heteroatom in a terpenoid such as Santenone or camphor. The compound of the structure which converted into a carbon-carbon double bond is mentioned.

  The terpenoid having at least one unsaturated bond is preferably a monoterpene hydrocarbon and a derivative thereof, more preferably a monoterpene hydrocarbon, still more preferably a monocyclic or bicyclic monoterpene hydrocarbon. Particularly preferred are limonene, α-pinene and β-pinene.

  The gel content contained in the olefin-terpenoid copolymer of the present invention is, for example, an olefin or a terpenoid copolymer having a terpenoid having at least one unsaturated bond, a step of post-treating the polymer, or the like. Among the polymers in which the terpenoids are homopolymerized or copolymerized with each other, there may be mentioned, for example, components that have become superpolymerized or have a three-dimensional network structure and are insoluble in organic solvents.

  The molecular weight of the ethylene-terpenoid copolymer in the present invention is preferably 10,000 or more in terms of weight average molecular weight from the viewpoint of mechanical strength when formed into a molded body.

  In the olefin-terpenoid copolymer of the present invention, the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 or more and 3.0 or less. It is preferable. The molecular weight distribution is more preferably 1.0 or more and 2.5 or less.

  In the olefin-terpenoid copolymer of the present invention, the copolymerization composition (molar ratio) of the olefin and the terpenoid having at least one unsaturated bond is not particularly limited, and ranges from 99.999 to 1: 0.001 to 99. However, it is preferably 99 to 20: 1 to 80.

The method for producing an olefin-terpenoid copolymer of the present invention is obtained by contacting a transition metal compound (A) represented by the following general formula [I], an organoaluminum compound (B) and / or a boron compound (C). And a terpenoid having at least one unsaturated bond is copolymerized using the polymerization catalyst.
L _α MX _β [I]
(In the above general formula [I], M represents a group 4 to 10 or lanthanoid series transition metal atom of the periodic table. L represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. And when a plurality of L are present, the plurality of L may be the same or different, and the plurality of L may be directly or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or phosphorus X may represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of Xs are present, the plurality of Xs may be the same. In addition, the hydrocarbon group having 1 to 20 carbon atoms may contain a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and α satisfies 0 <α ≦ 8. Represents a satisfied number, β represents a number satisfying 0 <β ≦ 8.)

  The transition metal compound (A) includes a transition metal compound represented by the above general formula [I] and a μ-oxo type transition obtained by combining a plurality of transition metal compounds represented by the general formula [I]. A metal compound etc. are mentioned.

  In the above general formula [I], M is a transition metal atom of Group 4 to 10 of the Periodic Table of Elements (IUPAC 1985) or a lanthanoid series. Specific examples of the group 4-10 or lanthanoid series transition metal atoms include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, palladium, samarium, ytterbium and the like. It is done.

  In the above general formula [I], L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and when a plurality of L are present, the plurality of L may be the same or different. . Moreover, several L may be connected directly or through the residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom.

  Examples of the group having a cyclopentadiene-type anion skeleton of L in the general formula [I] include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, and a substituted fluorenyl group. It is done. Examples of the group having a cyclopentadiene-type anion skeleton include a (substituted) cyclopentadienyl group, a (substituted) indenyl group, and a (substituted) fluorenyl group. Specifically, for example, cyclopentadienyl group, methylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group 1-tert-butyl-2-methylcyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3- Isopropylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl Group, 4,5,6,7-tetrahydroindenyl group, 2-methylindenyl group, 3-methyli Denyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group, 2-tert-butylindenyl group, 3-tert-butylindenyl group, 4 -Tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert-butylindenyl group, 2,3-dimethylindenyl group, 4,7-dimethylindene Nyl group, 2,4,7-trimethylindenyl group, 2-methyl-4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl-4-phenylindenyl group, 2-methyl-4-naphthylindenyl group, fluorescein Group, 2,7-dimethyl fluorenyl group, 2,7-di -tert- butyl-fluorenyl group, and substituted versions thereof, and the like.

  The polydentate η of the group having a cyclopentadiene type anion skeleton is not particularly limited, and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

  Examples of the hetero atom in the group containing a hetero atom of L in the general formula [I] include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of the group containing a hetero atom include an alkoxy group, Aryloxy group, thioalkoxy group, thioaryloxy group, alkylamino group, arylamino group, alkylphosphino group, arylphosphino group, or oxygen, sulfur, nitrogen and / or phosphorus atoms in the ring structure And aromatic or aliphatic heterocyclic groups, chelating ligands and the like.

  Specific examples of the group containing a hetero atom include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 2-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy. Group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6- Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5- Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitropheno group Si group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, Diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4- Isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-hyphenyldiol group, 1,1′-bi-2-naphthol group, 2,2 ′ -Dihydroxy-6,6'-dimethylbiphenyl group, 4,4 ', 6,6'-teto -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.

  The chelating ligand here refers to a ligand having a plurality of coordination sites, specifically, for example, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, Examples include triethylenetetramine, porphyrin, crown ether, and cryptate.

  Groups having a cyclopentadiene-type anion skeleton, groups having a cyclopentadiene-type anion skeleton and a group containing a heteroatom, or groups containing a heteroatom may be directly connected to each other, a carbon atom, It may be linked via a residue containing a silicon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Examples of such residues include alkylene groups such as ethylene groups and propylene groups, substituted alkylene groups such as dimethylmethylene groups and diphenylmethylene groups, or silylene groups, dimethylsilylene groups, diphenylsilylene groups, and tetramethyldisilylene groups. A substituted silylene group or a heteroatom such as nitrogen, oxygen, sulfur, phosphorus atom and the like can be mentioned.

  X in the general formula [I] is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom, and a methyl group, ethyl group, n-propyl group, isopropyl group, n as a hydrocarbon group having 1 to 20 carbon atoms. -A butyl group, a phenyl group, a benzyl group, etc. are mentioned.

  Among the transition metal compounds, specific examples of compounds in which the transition metal atom is a titanium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, and bis (n-butylcyclopentadidi). Enyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride Bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride Id, bis (2-phenylindenyl) titanium dichloride, bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride Bis [2- (4-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, Bis [2- (pentafluorophenyl) indenyl] titanium dichloride, cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) tita Dichloride, indenyl (fluorenyl) titanium dichloride, pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclo Pentadienyl (2-phenylindenyl) titanium dichloride, ethylenebis (cyclopentadienyl) titanium dichloride, ethylenebis (2-methylcyclopentadienyl) titanium dichloride, ethylenebis (3-methylcyclopentadienyl) titanium Dichloride, ethylenebis (2-n-butylcyclopentadienyl) titanium dichloride,

Ethylene bis (3-n-butylcyclopentadienyl) titanium dichloride, ethylene bis (2,3-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,4-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,5-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (3,4-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis ( 2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, ethyl Bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylene bis (tetramethylcyclopentadienyl) titanium dichloride, ethylene bis (Indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-phenylindenyl) titanium dichloride, ethylenebis (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) ) (Pentamethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentadienyl) (indenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (indenyl) titanium dichlora , Ethylene (n-butylcyclopentadienyl) (indenyl) dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (methylcyclopenta Dienyl) (fluorenyl) titanium dichloride, ethylene (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (tetramethylpentadienyl) (fluorenyl) ) Titanium dichloride, ethylene (indenyl) (fluorenyl) titanium dichloride, isopropylidenebis (cyclopentadienyl) titanium dichloride,

Isopropylidenebis (2-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene Bis (2,5-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-ethylmethyl) Clopentadienyl) titanium dichloride, isopropylidenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3 5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, Isopropylidenebis (tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride Rholide, isopropylidenebis (2-phenylindenyl) titanium dichloride, isopropylidenebis (fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) ) (Indenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (indenyl) dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (indenyl) dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (n-butyl) Cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (cyclopentadienyl) titanium dichloride, Dimethylsilylenebis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) ) Titanium dichloride, dimethylsilylene bis (2-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3-dimethylcyclopentadiene) Enyl) titanium dichloride, dimethylsilylene bis (2,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3,4-dimethylcyclopenta Dienyl) titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride Dimethylsilylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,4-trimethylcyclopentadiene) Enyl) titanium dichloride, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (indenyl) titanium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadiene) Nyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n- Butylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (indenyl) (fluorenyl) titanium dichloride, cyclopentadienyl titanium trichloride, pentamethylcyclo Pentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) ) Titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) Titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert- Butylphenyl) titanium dichloride, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride, methylene (cyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl- 2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride,

Methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene ( Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopenta Dienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) ) (3-Feni -2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5 -Methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl -5-chloro-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert -Bu Ru-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3- Phenyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) ( 3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylsuccinate) Lopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Chloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride , Methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (Trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenyl) Noxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-) Phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3 -Tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, Methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methyl (Fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadi) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyldimethylsilyl) 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3,5 -Dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5 -Methyl-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2- Enoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5- Methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (Tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2- Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium Dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2) -Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadiene) ) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) thio Dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluoro Lenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (cyclohexane) Pentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3- ert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadi) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) ) Titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro) -2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclo) Pentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene ( tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-meth) Ci-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3 , 5-Dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclope) Tantadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2- Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) ( 3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert- Til-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride Diphenylmethylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride dimethylsilylene (cyclopentadienyl) ( 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl- -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2) − Enoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclope Tantadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5 − Toxi-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5- Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride , Dimethylsilylene (n-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichlora Dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert -Butyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert -Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclo Pentadienyl (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2 -Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) ) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl) Ru-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium Dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylsilane) Lopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenyl) Noxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( Indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3- tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5 -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl) 3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl- 2-Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichlora (Tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dimethyl, (tert-butyramide) ) Tetramethylcyclopentadienyl-1,2-ethanediyltitanium dibenzyl,

(Methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethyl Silane titanium dichloride, (tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dimethyl, (tert-Butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl, (Benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium Dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl, (tert-butylamido) indenyl-1, -Ethanediyl titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyltitanium dimethyl, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroindenyl-1 , 2-ethanediyl titanium dimethyl, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dimethyl, (tert-butylamido) indenyldimethylsilane titanium Dichloride, (tert-butylamido) indenyldimethylsilanetitanium dimethyl, (tert-butylamido) tetrahydroindenyldimethylsilanetitanium dichloride, (te t-Butylamide) tetrahydroindenyldimethylsilanetitanium dimethyl, (tert-butylamido) fluorenyldimethylsilanetitanium dichloride, (tert-butylamido) fluorenyldimethylsilanetitanium dimethyl, (dimethylaminomethyl) tetramethylcyclopentadienyltitanium (III) Dichloride, (Dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (Dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride, (N-pyrrolidinylethyl) tetramethylcyclo Pentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienylzirconium dichloride, cyclopentadienyl (9-mesitylbora Anthracenyl) zirconium dichloride, 2,2'-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride,

2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′-thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2′-thiobis (4- Methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-methylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-ethylenebis (4-methyl-6-tert-butyl) Phenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2 '-(4,4', 6,6'-tetra-tert-butyl-1 , 1′biphenoxy) titanium dichloride 2,2′-thiobis (4-methyl-6-tert-butylphenoxy) ) Titanium diisopropoxide, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) Titanium diisopropoxide, 2,2′-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, (di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl) -1,3-propanediamide) titanium dichloride, [bis (trimethylsilyl) -1,3-propanedidiamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3 Propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] titanium Dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride,

[Bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dibromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium triiodide, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium tribromide, [hydrotris ( 3,5-diethylpyrazolyl) borate] titanium triiodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert- Tilpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium triiodide, [tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3 , 5-Dimethylpyrazolyl) methyl] titanium tribromide, [Tris (3,5-dimethylpyrazolyl) methyl] titanium triiodide, [Tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [Tris (3 5-diethylpyrazolyl) methyl] titanium tribromide, [tris (3,5-diethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-bu Rupyrazolyl) methyl] titanium tribromide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium triiodide, μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium Chloride], μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2 -Phenoxy) titanium chloride] μ- Okisobisu [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide],

μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert- Butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadiene) Enyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene] Redene (Tetramethylsik Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene ( Cyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [ Dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (medium Le cyclopentadienyl) (2-phenoxy) titanium methoxide], .mu. Okisobisu [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride],

μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2- Phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl -5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], di-μ -Oxobis [isopropylidene (cycl Lopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di-μ-oxobis [isopropylidene (Methylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di- μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium], di-μ-oxobis [dimethylsilylene (cyclope Tadienyl) (2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (Methylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di- μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2 -Phenoxy) titanium] and the like, and (2-phenoxy) of these compounds (3-phenoxy) -2-phenoxy), (3-trimethylsilyl-2-phenoxy),

Alternatively, a compound in which (3-tert-butyldimethylsilyl-2-phenoxy) is replaced, or a compound in which dimethylsilylene is replaced with diethylsilylene, diphenylsilylene, or dimethoxysilylene. And compounds in which the dichlorides of these compounds are replaced with difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, bis (dimethylamide), bis (diethylamide), dimethoxide, diethoxide, di-n-butoxide, diisopropoxide In addition, in the above titanium compound, a compound in which the titanium atom is replaced with a zirconium atom or a hafnium atom can be exemplified as well.

  Among the transition metal compounds, specific examples of compounds in which the transition metal atom is a nickel atom include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, Nickel cyanide, nickel oxalate, nickel acetylacetonate, bis (allyl) nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (Benzonitrile) nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichroic [1,2-bis (diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1 , 3-bis (diphenylphosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, nickel phthalocyanine, 2,2′-methylenebis [(4R) -4-phenyl-5,5 ′ -Dimethyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5 , 5'-diethyloxazoline] nickel dichlorai 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-di- n-propyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-di-n-propyloxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5′-diisopropyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diisopropyloxazoline] nickel Dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dicyclohexyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dicyclohexyl Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethoxyoxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5 '-Dimethoxyoxazoline] nickel dibromide, 2,2'-methylenebis (4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-phenyl-5,5'-diphenyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diphenyloxazoline] nickel dibromide Methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3-methylphenyl) ) Oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4-methyl) Enyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5- Di- (3-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [spiro {(4R)- 4-methyloxazoline-5,1′-cyclobutane}], methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclopentane}] nickel dibromide, methylenebis [spiro {(4R) -4- Methyloxazoline-5,1'-cyclohexane}] nickel dibromide, me Tylene bis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline] nickel di Bromide, 2,2'-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl- 5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazoline ] Nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Ckell dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl- 5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2, 2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxa Phosphorus] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) — 4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {( 4R) -4-isobutyloxazoline-5,1'-cyclopentane}] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5, 1'-cycloheptane}] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-tert-butyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazo Nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] Nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl -5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5 , 5-Di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- -Tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methoxy) Phenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-tert-butyloxazoline-5,1'-cyclobutane}] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert- Butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2, 2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] ni Keldibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5 -Dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5 , 5-Di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylpheni) oxazoline] nickel dibromide, 2, , 2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline Nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel Dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline -5,1'-cyclopentane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-fe Nyloxazoline-5,1'-cyclohexane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzene Dil-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Id, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline- 5,1′-cyclopentane}] nickel dibromide,

（式中、Ｒ⁷とＲ⁸はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｘ、Ｒ⁹、およびＲ¹⁰は下記の表１に表される置換基である。） 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5, 1′-cycloheptane}] nickel dibromide, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-dimethylpyrazolyl) ) Borate] nickel iodide, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickelethyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel Allyl, [ Hydrotris (3,5-dimethylpyrazolyl) borate] nickel methallyl [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5 -Diethylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-diethylpyrazolyl) borate] nickelmethyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickelethyl, [hydrotris (3,5-diethylpyrazolyl) Borate] nickel allyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickel methallyl [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride, [hydro Lis (3,5-di-tert-butylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-di-tert-butyl) Pyrazolyl) borate] nickel methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickelethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel allyl, [hydrotris (3 5-di-tert-butylpyrazolyl) borate] nickel methallyl, and compounds in which (4R) in each of the above compounds corresponds to (4S). As the meso-type isomer, for example, (4R) in each compound described above as an optically active bisoxazoline is a compound in which one oxazoline skeleton is (4R) and the other oxazoline skeleton is (4S) And compounds in which bromide is substituted with chloride, methyl, methoxy, acetoxy and the like, and compounds represented by the following structural formulas.

(In the formula, R ⁷ and R ⁸ are each 2,6-diisopropylphenyl groups, and X, R ⁹ , and R ¹⁰ are substituents shown in Table 1 below.)

  In addition, in the above nickel compound, compounds in which nickel atoms are replaced with palladium atoms, cobalt atoms, rhodium atoms, iron atoms, or ruthenium atoms can be exemplified as well.

Among the transition metal compounds, specific examples of compounds in which the transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, [hydrotris (3,5- [Dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-dimethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-dimethylpyrazolyl) borate ] Iron Methyl, [Hydrotris ( , 5-dimethylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron methallyl, [hydrotris (3,5-diethyl) [Pyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-diethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-diethylpyrazolyl) borate] Ironmethyl, [hydrotris (3,5-diethylpyrazolyl) borate] ethylethyl, [hydrotris (3,5-diethylpyrazolyl) borate] ironallyl, [hydrotris (3,5-diethylpyra) Ril) borate] iron methallyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3 , 5-Di-tert-butylpyrazolyl) borate] iron iodide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] ironmethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate Ironethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] ironallyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methallyl, and the like.
In addition, in the above iron compound, a compound in which an iron atom is replaced with a cobalt atom or a nickel atom can be exemplified similarly.

  Among the transition metal compounds, specific examples of compounds in which the transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride and the like.

  Among the transition metal compounds, specific examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.

  Among the transition metal compounds, specific examples of compounds in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

（上記一般式［ＩＩ］において、Ｍ¹は元素周期律表の第４族の遷移金属原子を表し、Ａは元素周期律表の第１６族の原子を表し、Ｊは元素周期律表の第１４族の原子を表す。Ｃｐ¹はシクロペンタジエン形アニオン骨格を有する基を表す。Ｘ¹、Ｘ²、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ任意に結合して単環構造または多環構造を形成していてもよい。該単環構造または多環構造は、芳香族環構造であっても、非芳香族環構造であってもよい。） In the method for producing such an olefin-terpenoid copolymer, it is preferable to use a transition metal compound represented by the following general formula [II] as the transition metal compound (A).

(In the above general formula [II], M ¹ represents a group 4 transition metal atom in the periodic table, A represents a group 16 atom in the periodic table, and J represents the number in the periodic table) Represents a group 14 atom, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, and X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen R ¹ , R represents an atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally bonded to each other to form a monocyclic structure or polycyclic structure, which is an aromatic ring structure. Or a non-aromatic ring structure.

In the general formula [II], M ¹ represents a transition metal atom of Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), preferably a titanium atom, a zirconium atom or a hafnium atom, more preferably Is a titanium atom.

  In general formula [II], A is an atom of group 16 of the periodic table. Examples of the group 16 atom of the periodic table include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.

  In the general formula [II], J is an atom of Group 14 of the periodic table. Examples of Group 14 atoms in the Periodic Table of Elements include a carbon atom, a silicon atom, a germanium atom, and the like, preferably a carbon atom or a silicon atom.

In the general formula [II], Cp ¹ is a group having a cyclopentadiene type anion skeleton. Examples of the group having a cyclopentadiene-type anion skeleton include a (substituted) cyclopentadienyl group, a (substituted) indenyl group, and a (substituted) fluorenyl group. Specifically, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclo Pentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, n-pentylcyclopentadienyl group, neopentylcyclopentadienyl Group, n-hexylcyclopentadienyl group, n-octylcyclopentadienyl group, phenylcyclopentadienyl group, naphthylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, triethylsilylcyclopenta An enyl group, a tert-butyldimethylsilylcyclopentadienyl group, an indenyl group, a methylindenyl group, a dimethylindenyl group, an ethylindenyl group, an n-propylindenyl group, an isopropylindenyl group, an n-butylindenyl group, sec-butyl indenyl group, tert-butyl indenyl group, n-pentyl indenyl group, neopentyl indenyl group, n-hexyl indenyl group, n-octyl indenyl group, n-decyl indenyl group, phenyl indenyl group Methylphenylindenyl group, naphthylindenyl group, trimethylsilylindenyl group, triethylsilylindenyl group, tert-butyldimethylsilylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl Base Ethyl fluorenyl group, diethyl fluorenyl group, n-propyl fluorenyl group, di-n-propyl fluorenyl group, isopropyl fluorenyl group, diisopropyl fluorenyl group, n-butyl fluorenyl group, sec-butyl fluorenyl group, tert-butyl fluorenyl group, di-n-butyl fluorenyl group, di-sec-butyl fluorenyl group, di-tert-butyl fluorenyl group, n-pentyl fluor Olenyl group, neopentylfluorenyl group, n-hexylfluorenyl group, n-octylfluorenyl group, n-decylfluorenyl group, n-dodecylfluorenyl group, phenylfluorenyl group, di- -Phenylfluorenyl group, methylphenylfluorenyl group, naphthylfluorenyl group, trimethylsilylfluorenyl group, bis-tri Examples include methylsilylfluorenyl group, triethylsilylfluorenyl group, tert-butyldimethylsilylfluorenyl group, etc., preferably cyclopentadienyl group, methylcyclopentadienyl group, tert-butylcyclopentadienyl. Group, a tetramethylcyclopentadienyl group, an indenyl group, or a fluorenyl group.

In the general formula [II], X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, A substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably they are a chlorine atom or a bromine atom, More preferably, it is a chlorine atom.

The alkyl group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n- A dodecyl group, n-pentadecyl group, n-eicosyl group etc. are mentioned, More preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert- butyl group, or an 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 or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl. Group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl Group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group Perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

As the aralkyl group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, an aralkyl group having 7 to 20 carbon atoms is preferable, and examples thereof include a benzyl group, (2-methyl Phenyl) 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-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl Group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethyl) Phenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) 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, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decyl) Phenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, Torasenirumechiru group and the like, more preferably a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

The aryl group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group or a 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-trimethyl Phenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group N-propylphenyl group, isopropyl Ruphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, An n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and the like can be mentioned, and a phenyl group is more preferable.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

The substituted silyl group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a silyl group substituted with a hydrocarbon group. For example, carbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of such substituted silyl groups include 1- to 20-carbon monosubstituted silyl groups such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, 2 to 2 carbon atoms such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group. 20 disubstituted silyl groups, trimethylsilyl groups, triethylsilyl groups, tri-n-propylsilyl groups, triisopropylsilyl groups, tri-n-butylsilyl groups, tri-sec-butylsilyl groups, tri-tert-butylsilyl groups, tri- Trisubstituted silyl groups having 3 to 20 carbon atoms such as isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, etc. Preferably trimethylsilyl group, tert-butyldi A Chirushiriru group or triphenylsilyl group.
All of these substituted silyl groups have a hydrocarbon group such as 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 a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The alkoxy group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy group, n -Propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group , N-icosoxy group, and the like, more preferably a methoxy group, an ethoxy group, or a tert-butoxy group.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aralkyloxy group for X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aralkyloxy group having 7 to 20 carbon atoms is preferable. 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-trimethyl) Phenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) Enyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, 3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) 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-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, Chirumetokishi group, anthracenylmethoxy methoxy group and the like, more preferably a benzyloxy group.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

As the aryloxy group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryloxy group having 6 to 20 carbon atoms is preferable, and examples thereof include 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, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5- Trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2, 3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec -Butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

The disubstituted amino group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, wherein the hydrocarbon group As, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. And an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms such as a phenyl group, and an aralkyl group having 7 to 10 carbon atoms. Examples of the disubstituted amino group substituted with the hydrocarbon group having 1 to 10 carbon atoms include, for example, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-amino group. 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, bistrimethylsilyl An amino group, a bis-tert-butyldimethylsilylamino group, etc. are mentioned, Preferably they are a dimethylamino group or a diethylamino group.
These disubstituted amino groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyl such as benzyloxy group. A part thereof may be substituted with an oxy group or the like.

Examples of the hydrocarbon thio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include an alkylthio group, an aralkylthio group, and an arylthio group.

Examples of the alkylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, and sec-butylthio group, tert-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group, and the like. .
These alkylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

The alkylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an alkylthio group having 1 to 20 carbon atoms, more preferably a methylthio group, an ethylthio group, An isopropylthio group or a tert-butylthio group.

Examples of the aralkylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a benzylthio group, a (2-methylphenyl) methylthio group, and (3-methylphenyl) Methylthio group, (4-methylphenyl) methylthio group, (2,3-dimethylphenyl) methylthio group, (2,4-dimethylphenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6- (Dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, (2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) ) Methylthio group, (2,3,6-trimethylphenyl) methylthio group, (2,4,5-trimethylphenyl) methylthio group, (2,4 , 6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) methylthio group, (2,3,4,6-tetramethylphenyl) ) Methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group , (N-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group, (n-octylphenyl) methylthio group, (n-decyl) Phenyl) methylthio group, naphthylmethylthio group, anthracenylmethyl Thio group, and the like.
All of these aralkylthio groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkylthio group having 7 to 20 carbon atoms, more preferably a benzylthio group. .

Examples of the arylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, 4- Methylphenylthio group, 2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4-methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2- tert-butyl-6-methylphenylthio, 2,3,4-trimethylphenylthio, 2,3,5-trimethylphenylthio, 2,3,6-trimethyl Enylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethylphenylthio group, 2-tert-butyl-3,5- Dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4,5-dimethylphenylthio Group, 2,6-di-tert-butyl-4-methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4,5-tetramethylphenylthio group, 2-tert-butyl- 3,4,5-trimethylphenylthio group, 2,3,4,6-tetramethylphenylthio group, 2-tert-butyl-3,4,6-trimethylphenylthio group, 2 6-di-tert-butyl-3,4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2-tert-butyl-3,5,6-trimethylphenylthio group, 2, 6-di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio group, isopropylphenylthio group, n-butylphenylthio group, sec-butyl Phenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n-tetradecylphenylthio group, naphthylthio group, anthracenylthio group, etc. It is done.
These arylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be substituted.

The arylthio group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an arylthio group having 6 to 20 carbon atoms.

Examples of the hydrocarbon seleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include an alkylseleno group, an aralkylseleno group, an arylseleno group and the like. .

Examples of the alkyl seleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include, for example, methyl seleno group, ethyl seleno group, n-propyl seleno group, isopropyl seleno group, n- Butylseleno group, sec-butylseleno group, tert-butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group, n-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n -Eicosylseleno group etc. are mentioned.
These alkylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As the alkylseleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ , an alkylseleno group having 1 to 20 carbon atoms is preferable, and a methylseleno group or ethylseleno group is more preferable. Group, isopropylseleno group or tert-butylseleno group.

Examples of the aralkylseleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) ) Methylseleno group, (4-methylphenyl) methylseleno group, (2,3-dimethylphenyl) methylseleno group, (2,4-dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6 -Dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethyl) Phenyl) methylseleno group, (2,3,6-trimethylphenyl) methylseleno group, (2,4,5-trimethylphene) Nyl) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4,5-trimethylphenyl) methylseleno group, (2,3,4,5-tetramethylphenyl) methylseleno group, (2, 3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (ethylphenyl) methylseleno group, (n-propylphenyl) Methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (n-hexylphenyl) methylseleno group, (n-octyl) Phenyl) methylseleno group, (n-decylpheny) ) Methylseleno group, naphthylmethyl seleno group, anthracenylmethyl seleno group and the like.
These aralkylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkylseleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an aralkylseleno group having 7 to 20 carbon atoms, more preferably a benzylseleno group. is there.

Examples of the arylseleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a phenylseleno group, a 2-methylphenylseleno group, a 3-methylphenylseleno group, 4-methylphenylseleno group, 2,3-dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 2,5-dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group Group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2,3,4-trimethylphenylseleno group, 2,3,5-trimethylphenyl Seleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2-tert-butyl-3,4-dimethylphenylseleno group 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di-tert-butyl-3-methylphenylseleno group, 2- tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethylphenylseleno group, 2,3,4,5-tetra Methylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group, 2,3,4,6-tetramethylphenylseleno group, 2 tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group, 2,3,5,6-tetramethylphenylseleno group, 2- tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno Group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno group, n-octylphenylseleno group, n-decylphenylseleno group, n -Tetradecylphenylseleno group, naphthylseleno group, anthracenylseleno group And the like.
These arylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The arylseleno group in X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is preferably an arylseleno group having 6 to 20 carbon atoms, more preferably a phenylseleno group. is there.

R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ may be optionally combined to form a monocyclic structure or a polycyclic structure. The monocyclic structure or polycyclic structure may be an aromatic ring structure or a non-aromatic ring structure.

R ¹ is preferably an alkyl group, an aralkyl group, an aryl group, or a substituted silyl group.
X ¹ and X ² are preferably each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, more preferably a halogen atom or an alkoxy group.

  Examples of the transition metal compound (A) represented by the general formula [II] include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3 -Tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2) -Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2) -Phenoxy) titanium dic , Methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium Dichloride,

Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert -Butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) tita Um dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5 -Chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, iso Ropyridene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride ,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen Xyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-to Methylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl) 5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Id, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) ) Titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert- Tilcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethyl) Rylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenyl Methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3- ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium or hafnium of these compounds. As well as compounds in which dichloride is replaced with dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxide, (cyclopentadienyl) with (dimethylcyclohexane) A compound substituted with (pentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), or (indenyl), (3,5- Methyl-2-phenoxy) to (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-) A transition metal complex in which J in the general formula [II] is a carbon atom, such as a compound substituted with (phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or (3-trimethylsilyl-2-phenoxy);

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3- Enyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl- 3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert- Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2- Phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert -Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylene) Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2 Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-) - phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Rushiriren (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2 Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5- Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro- - phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (I Denyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil) -2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like (cyclopent Dienyl) to (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclo) Compound substituted with (pentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl), A compound in which (2-phenoxy) is replaced by (3-phenyl 2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), and dimethylsilylene is converted to diethyl Silylene, diphenylsilylene, Or a compound in which dimethoxysilylene is replaced, a compound in which titanium is replaced with zirconium or hafnium, a dichloride is dibromide, diiodide, dimethyl, diethyl, diisopropyl, bis (dimethylamide), bis (diethylamide), dimethoxide, diethoxide, di-n- Examples thereof include transition metal complexes in which J in General Formula [II] is an atom belonging to Group 14 of the periodic table of elements other than carbon atoms, such as butoxide or a compound substituted with diisopropoxide.

  The transition metal compound (A) represented by the above general formula [II] can be produced, for example, by the method described in International Publication No. 97/03992.

These transition metal compounds (A) may be used alone or in combination of two or more.

Examples of the aluminum compound used in the method for producing the olefin-terpenoid copolymer include one or more organic aluminum compounds selected from the group consisting of the following (B1) to (B3).
(B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane (B3) having a structure represented by general formula {—Al (E ² ) —O—} _b A linear aluminoxane having a structure represented by the formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, E ¹ , a plurality of E ^{2 s,} and a plurality of E ^{3 s} may be the same or different from each other, Z represents a hydrogen atom or a halogen atom, and when a plurality of Z are present, the plurality of Z are the same A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)

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, trihexylaluminum; dimethylaluminum Dialkylaluminum chloride such as chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethyl Aluminum high You can ride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

Cyclic aluminoxane (B2) having a structure represented by the general formula {—Al (E ² ) —O—} a, represented by the general formula E ³ {—Al (E ³ ) —O—} _b AlE ³ ₂ Specific examples of E ² and E ³ in the linear aluminoxane (B3) having the structure: methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, neopentyl group An alkyl group such as can be exemplified. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

Examples of the boron compound used in the method for producing the olefin-terpenoid copolymer include one or more boron compounds selected from the following (C1) to (C3).
(C1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (C3) General formula (L ¹ − H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B represents a trivalent boron atom, Q ^{1 to} Q ⁴ are each independently a halogen atom, It represents a substituent selected from the group consisting of a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group, and a 2-substituted amino group, and Q ^{1 to} Q ⁴ may be the same or different. ⁺ Represents an inorganic or organic cation, L ¹ represents a neutral Lewis base, and (L ¹ -H) ⁺ represents a Bronsted acid.)

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups, halogenated hydrocarbons. A group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or the number of carbon atoms An alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having a substituent having 2 to 20 carbon atoms, and Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or It is a halogenated hydrocarbon group having 1 to 20 carbon atoms. Q ^{1 to} Q ⁴ are more preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and Q ^{1 to} Q ⁴ are particularly preferably at least one fluorine atom. It is a fluorinated aryl group having 6 to 20 carbon atoms.

Specific examples of the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2 , 3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. 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 a trivalent valence state boron atom. , Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

Specific examples of G ⁺ which is an inorganic cation in the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium cation, alkyl-substituted ferrocenium cation, A silver cation etc. are mentioned, A triphenylmethyl cation etc. are mentioned as G ^<+> which is an organic cation in this boron compound (C2). G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.

  Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (Pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

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

Formula ^{(L 1 -H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by the (L ¹ -H) ⁺ Specific examples of the trialkyl-substituted ammonium, N , N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like, and (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes 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 (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, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) Borate.

  In the method for producing such an olefin-terpenoid copolymer, only the transition metal compound (A) may be used. Preferably, the transition metal compound (A), the organoaluminum compound (B) and / or the boron compound ( An olefin polymerization catalyst obtained by contacting C) is used. As the organoaluminum compound (B) in this case, the above (B1) is easy to use. Further, an olefin polymerization catalyst obtained by contacting two compounds of the transition metal compound (A) and the organoaluminum compound (B) may be used. In this case, the organoaluminum compound (B) is as described above. Cyclic aluminoxane (B2) and / or linear aluminoxane (B3) are preferred.

In the method for producing such an olefin-terpenoid copolymer, the amount of each compound used is usually (B) / (A) molar ratio in the range of 0.1 to 10,000, preferably in the range of 5 to 2,000. Yes, each compound is used so that the molar ratio of (C) / (A) is in the range of 0.01 to 100, and preferably in the range of 0.5 to 10.
The concentration when each compound is used in a solution state or in a suspended state in a solvent is appropriately selected according to conditions such as the performance of an apparatus for supplying each component to the polymerization reactor, but in general, the compound (A) is usually used. The range is 0.01 to 500 μmol / g, more preferably the range is 0.05 to 100 μmol / g, still more preferably the range is 0.05 to 50 μmol / g, and the compound (B) is an aluminum atom. In terms of conversion, it is usually in the range of 0.01 to 10000 μmol / g, more preferably in the range of 0.1 to 5000 μmol / g, still more preferably in the range of 0.1 to 2000 μmol / g, and the compound (C) Is usually in the range of 0.01 to 500 μmol / g, more preferably in the range of 0.05 to 200 μmol / g, still more preferably 0.05 to 100 μmol / g. It is desirable to use the compound to be in the range of.

  In such a method for producing an olefin-terpenoid copolymer, the polymerization temperature can be usually carried out over a range of −30 to 300 ° C., preferably 0 to 280 ° C., more preferably 20 to 250 ° C. It is a range.

  Further, the polymerization pressure is not particularly limited, but is preferably about normal pressure to about 15 MPa from an industrially economical viewpoint. In general, the polymerization time is appropriately determined depending on the type of the target copolymer and the reaction apparatus, but may range from 30 seconds to 40 hours, for example.

  In such a method for producing an olefin-terpenoid copolymer, the polymerization process can be employed either continuously or batchwise. Further, for example, slurry polymerization with an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization without solvent, or gas phase polymerization may be employed.

  In order to adjust the molecular weight of the olefin-terpenoid copolymer of the present invention, a chain transfer agent such as hydrogen can be added during the polymerization.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited only to an Example.
In addition, the measured value of each item in an Example was measured with the following method.

(1) Intrinsic viscosity ([η], unit: dl / g)
It measured at 135 degreeC in the tetralin solvent using the Ubbelohde viscometer.

(2) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)
It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene.
Measuring machine Made by Millipore Outers 150CV type column Shodex M / S 80
Measurement temperature 145 ° C, solvent: orthodichlorobenzene,
Sample concentration 5mg / 8ml

(3) Differential scanning calorimetry (DSC) measurement It measured on condition of the following using DSC-VII by Perkin-Elmer.
Temperature rise: 20 ° C to 200 ° C (20 ° C / min) Hold for 10 minutes Cooling: 200 ° C to -100 ° C (20 ° C / min) Hold for 10 minutes Measurement: -100 ° C to 300 ° C (temperature rise at 20 ° C / min) )
(4) ¹³ C Nuclear Magnetic Resonance Spectra (NMR) Measurement The measurement was performed at 135 ° C. in an orthodichlorobenzene / orthodichlorobenzene-d ₂ mixed solvent using an Excubiber / 400 MHz manufactured by JEOL.
(5) Content of gel content in copolymer The copolymer was wrapped in a double-folded 1000-mesh wire mesh and dissolved in orthodichlorobenzene at 140 ° C. Thereafter, the wire mesh was dried, and the residue remaining inside the wire mesh was weighed as a gel content to obtain the gel content (% by weight) when the weight of the copolymer was 100% by weight.

Example 1
After the fully dried 100 mL stainless steel autoclave was purged with nitrogen, 10 mL of limonene as a terpenoid and 10 mL of toluene as a polymerization solvent were charged using a syringe, respectively, followed by triisobryl aluminum (B) as an organoaluminum compound (B). 2 mL of Tosoh Finechem 1 mol / L toluene solution) was added. On the other hand, 10 μmol of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a transition metal compound (A) was added to 5 mL of purified toluene in a nitrogen-substituted eggplant type flask. The total amount of the dissolved product was put into an autoclave, and further 3 mL of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate previously dissolved in toluene and adjusted to a concentration of 10 mmol / L as a boron compound (C). After charging, ethylene was pressurized to 0.5 MPa as olefin, and polymerization was performed at room temperature for 1 hour. After completion of the reaction, unreacted ethylene was purged, the autoclave content was put into about 200 mL of acidic ethanol, the precipitated polymer was filtered, and dried at 80 ° C. for about 2 hours. As a result, 1.60 g of a polymer was obtained. As a result of analyzing the obtained polymer, [η] = 0.5 (dl / g), polystyrene-equivalent weight average molecular weight Mw = 70,000, Mw / Mn = 2.2, melting point 114 ° C., glass transition point -31 ° C. ^From the results of ¹³ C-NMR analysis, the polymer was an ethylene-limonene copolymer having a limonene content of 0.7 mol%. No gel content was observed.

Example 2
The 100 mL eggplant-shaped flask which had been sufficiently dried was purged with nitrogen, and then 20 mL of limonene was charged as a terpenoid using a syringe, followed by triisobryl aluminum (1 mol / L toluene manufactured by Tosoh Finechem Co., Ltd.) as the organoaluminum compound (B). Solution) 2 mL was added. On the other hand, 10 μmol of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a transition metal compound (A) was added to 5 mL of purified toluene in a nitrogen-substituted eggplant type flask. The total amount of the dissolved product was put into an autoclave, and further 3 mL of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate previously dissolved in toluene and adjusted to a concentration of 10 mmol / L as a boron compound (C). After charging, polymerization was performed at room temperature for 1 hour while bubbling ethylene as an olefin. After completion of the reaction, unreacted ethylene was purged, the contents of the flask were put into about 200 mL of acidic ethanol, the precipitated polymer was filtered, and dried at 80 ° C. for about 2 hours. As a result, 0.37 g of a polymer was obtained. As a result of analyzing the obtained polymer, the polystyrene-reduced weight average molecular weight Mw = 19000, Mw / Mn = 1.8, the melting point was 65.5 ° C., and the glass transition point was −10.1 ° C. ^From the results of ¹³ C-NMR analysis, the polymer was an ethylene-limonene copolymer having a limonene content of 15 mol%. No gel content was observed.

Example 3
After the fully dried 100 mL stainless steel autoclave was purged with nitrogen, 20 mL of α-pinene was charged as a terpenoid using a syringe, followed by triisobryl aluminum (1 mol, manufactured by Tosoh Finechem) as the organoaluminum compound (B). 2 mL of / L toluene solution) was added. On the other hand, 10 μmol of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a transition metal compound (A) was added to 5 mL of purified toluene in a nitrogen-substituted eggplant type flask. The total amount of the dissolved product was put into an autoclave, and further 3 mL of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate previously dissolved in toluene and adjusted to a concentration of 10 mmol / L as a boron compound (C). After charging, ethylene was pressurized to 0.3 MPa as an olefin, and polymerization was performed at room temperature for 1 hour. After completion of the reaction, unreacted ethylene was purged, the autoclave content was put into about 200 mL of acidic ethanol, the precipitated polymer was filtered, and dried at 80 ° C. for about 2 hours. As a result, 0.2 g of a polymer was obtained. As a result of analyzing the obtained polymer, [η] = 0.4 (dl / g), polystyrene-equivalent weight average molecular weight Mw = 26,000, Mw / Mn = 2.4, and melting point was 127 ° C. . As a result of ¹³ C-NMR analysis, the polymer was an ethylene-α-pinene copolymer. No gel content was observed.

Example 4
After the inside of a fully dried 100 mL stainless steel autoclave was purged with nitrogen, 20 mL of β-pinene was charged as a terpenoid using a syringe, followed by triisobryl aluminum (1 mol, manufactured by Tosoh Finechem Co., Ltd.) as the organoaluminum compound (B). 1 mL of / L toluene solution) was added. On the other hand, 5 μmol of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a transition metal compound (A) was added to 5 mL of purified toluene in a nitrogen-substituted eggplant type flask. The total amount of the dissolved product is put into an autoclave. Further, as a boron compound (C), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate previously dissolved in toluene and adjusted to a concentration of 10 mmol / L is 1 After charging 5 mL, ethylene as an olefin was pressurized to 0.5 MPa and polymerized at room temperature for 1 hour. After completion of the reaction, unreacted ethylene was purged, the autoclave content was put into about 200 mL of acidic ethanol, the precipitated polymer was filtered, and dried at 80 ° C. for about 2 hours. As a result, 7.1 g of a polymer was obtained. As a result of analyzing the obtained polymer, [η] = 0.1 (dl / g) and the glass transition point was 3.6 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer having a β-pinene content of 33 mol%. No gel content was observed.

Example 5
After the inside of a fully dried 100 mL stainless steel autoclave was purged with nitrogen, 20 mL of β-pinene was charged as a terpenoid using a syringe, followed by triisobryl aluminum (1 mol, manufactured by Tosoh Finechem Co., Ltd.) as the organoaluminum compound (B). 2 mL of / L toluene solution) was added. On the other hand, 10 μmol of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a transition metal compound (A) was added to 5 mL of purified toluene in a nitrogen-substituted eggplant type flask. The total amount of the dissolved product is put into an autoclave, and 30 mL of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate previously dissolved in toluene and adjusted to a concentration of 10 mmol / L is added as a boron compound (C). After charging, ethylene was pressurized to 0.3 MPa as an olefin, and polymerization was performed at room temperature for 1 hour. After completion of the reaction, unreacted ethylene was purged, the autoclave content was put into about 200 mL of acidic ethanol, the precipitated polymer was filtered, and dried at 80 ° C. for about 2 hours. As a result, 1.3 g of a polymer was obtained. As a result of analyzing the obtained polymer, [η] = 0.1 (dl / g) and the glass transition point was 15.4 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer having a β-pinene content of 79 mol%. No gel content was observed.

Example 6
Into a 5 mL glass reaction vessel installed in a nitrogen-substituted glove box, 0.5 mL of α-pinene as a terpenoid, and purified toluene in an amount such that the total volume of the reaction solution is 2 mL are charged using a syringe, respectively. Subsequently, 40 μL of triisobutylaluminum (1M toluene solution manufactured by Tosoh Finechem) was added as the organoaluminum compound (B). Meanwhile, 5 mmol / m of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride prepared in advance in a sample tube under a nitrogen atmosphere as the transition metal compound (A). 60 μL of the L toluene solution was charged into the reaction vessel, and then 60 μL of a 10 mmol / L toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate prepared in advance was added as the boron compound (C). Then, ethylene was pressurized to 0.1 MPa as an olefin, and polymerization was performed at 70 ° C. for 10 minutes. After completion of the reaction, unreacted ethylene was purged, the solvent of the reaction solution was distilled off under reduced pressure, and the resulting polymer was dried at 80 ° C. overnight. As a result, 113 mg of polymer was obtained. As a result of analyzing the obtained polymer, the polystyrene-reduced weight average molecular weight Mw = 104,000, Mw / Mn = 1.6, and the melting point was 124 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer. No gel content was observed.

Example 7
Into a 5 mL glass reaction vessel installed in a nitrogen-substituted glove box, 0.5 mL of β-pinene as a terpenoid, and purified toluene in an amount such that the total volume of the reaction solution is 2 mL are charged using a syringe, respectively. Subsequently, 40 μL of triisobutylaluminum (1 mol / L toluene solution manufactured by Tosoh Finechem) was added as the organoaluminum compound (B). Meanwhile, 5 mmol / m of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride prepared in advance in a sample tube under a nitrogen atmosphere as the transition metal compound (A). 60 μL of the L toluene solution was charged into the reaction vessel, and then 60 μL of a 10 mmol / L toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate prepared in advance was added as the boron compound (C). Then, ethylene as an olefin was pressurized to 0.1 MPa and polymerized at 70 ° C. for 10 minutes. After completion of the reaction, unreacted ethylene was purged, the solvent of the reaction solution was distilled off under reduced pressure, and the resulting polymer was dried at 80 ° C. overnight. As a result, 223 mg of polymer was obtained. As a result of analyzing the obtained copolymer, the polystyrene-reduced weight average molecular weight Mw = 11,000, Mw / Mn = 2.0, and the melting point was 117 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer. No gel content was observed.

Example 8
Into a 5 mL glass reaction vessel installed in a nitrogen-substituted glove box, 1.0 mL of β-pinene as a terpenoid, and purified toluene in an amount such that the total volume of the reaction solution is 2 mL are charged using a syringe, Subsequently, 40 μL of triisobutylaluminum (1 mol / L toluene solution manufactured by Tosoh Finechem) was added as the organoaluminum compound (B). Meanwhile, 5 mmol / m of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride prepared in advance in a sample tube under a nitrogen atmosphere as the transition metal compound (A). 60 μL of the L toluene solution was charged into the reaction vessel, and then 60 μL of a 10 mmol / L toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate prepared in advance was added as the boron compound (C). Then, ethylene as an olefin was pressurized to 0.1 MPa and polymerized at 70 ° C. for 10 minutes. After completion of the reaction, unreacted ethylene was purged, the solvent of the reaction solution was distilled off under reduced pressure, and the resulting polymer was dried at 80 ° C. overnight. As a result, 283 mg of a polymer was obtained. As a result of analyzing the obtained polymer, polystyrene-equivalent weight average molecular weight Mw = 10,000, Mn = 4300, Mw / Mn = 2.3, melting point 115 ° C., crystallization temperature 101 ° C., glass transition temperature It was 4 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer. No gel content was observed.

Example 9
Into a 5 mL glass reaction vessel installed in a nitrogen-substituted glove box, 1.0 mL of limonene as a terpenoid and 2 mL of purified toluene with a total reaction solution volume of 2 mL were charged using a syringe, respectively. Then, 40 μL of triisobutylaluminum (1 mol / L toluene solution manufactured by Tosoh Finechem Co., Ltd.) was added as the organoaluminum compound (B). Meanwhile, 5 mmol / m of methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride prepared in advance in a sample tube under a nitrogen atmosphere as the transition metal compound (A). 60 μL of the L toluene solution was charged into the reaction vessel, and then 60 μL of a 10 mmol / L toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate prepared in advance was added as the boron compound (C). Then, ethylene as an olefin was pressurized to 0.1 MPa and polymerized at 70 ° C. for 10 minutes. After completion of the reaction, unreacted ethylene was purged, the solvent of the reaction solution was distilled off under reduced pressure, and the resulting polymer was dried at 80 ° C. overnight. As a result, 204 mg of polymer was obtained. As a result of analyzing the obtained polymer, the polystyrene-reduced weight average molecular weight Mw = 36,000, Mw / Mn = 1.6, the melting point was 120 ° C., and the crystallization temperature was 109 ° C. As a result of ¹³ C-NMR analysis, the polymer was an ethylene-β-pinene copolymer. No gel content was observed.

Claims (10)

  It is obtained by copolymerizing an olefin and a terpenoid having at least one unsaturated bond, and the gel content contained in the copolymer is 10% by weight or less (provided that the entire copolymer is 100% by weight). An olefin-terpenoid copolymer.   The olefin-terpenoid copolymer according to claim 1, wherein the terpenoid is a monoterpene hydrocarbon or a derivative thereof.   The olefin-terpenoid copolymer according to claim 1 or 2, wherein the olefin is selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms.   The olefin-terpenoid copolymer according to claim 1 or 2, wherein the olefin is ethylene.   The olefin-terpenoid copolymer according to any one of claims 1 to 4, which has a weight average molecular weight (Mw) of 10,000 or more.   The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.0 or more and 3.0 or less. Olefin-terpenoid copolymer. Using a polymerization catalyst obtained by contacting a transition metal compound (A), an organoaluminum compound (B) and / or a boron compound (C) represented by the following general formula [I], an olefin and at least one non-reactive compound are used. The method for producing an olefin-terpenoid copolymer according to any one of claims 1 to 6, wherein a terpenoid having a saturated bond is copolymerized.
L _α MX _β [I]
(In the above general formula [I], M represents a group 4 to 10 or lanthanoid series transition metal atom of the periodic table. L represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. And when a plurality of L are present, the plurality of L may be the same or different, and the plurality of L may be directly or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or phosphorus X may represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of Xs are present, the plurality of Xs may be the same. In addition, the hydrocarbon group having 1 to 20 carbon atoms may contain a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and α satisfies 0 <α ≦ 8. Represents a satisfied number, β represents a number satisfying 0 <β ≦ 8.) Using a polymerization catalyst obtained by contacting a transition metal compound (A), an organoaluminum compound (B) and / or a boron compound (C) represented by the following general formula [II], an olefin and at least one non-reactive compound are used. The method for producing an olefin-terpenoid copolymer according to any one of claims 1 to 6, wherein a terpenoid having a saturated bond is copolymerized.

(In the above general formula [II], M ¹ represents a group 4 transition metal atom in the periodic table, A represents a group 16 atom in the periodic table, and J represents the number in the periodic table) Represents a group 14 atom, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, and X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen R ¹ , R represents an atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally bonded to each other to form a monocyclic structure or polycyclic structure, which is an aromatic ring structure. Or a non-aromatic ring structure. The method for producing an olefin-terpenoid copolymer according to claim 7 or 8, wherein the organoaluminum compound (B) is at least one organoaluminum compound selected from the group consisting of the following (B1) to (B3).
(B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane (B3) having a structure represented by general formula {—Al (E ² ) —O—} _b A linear aluminoxane having a structure represented by the formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ (where E ¹ , E ² and E ³ are each a hydrocarbon group, E ¹ , a plurality of E ^{2 s,} and a plurality of E ^{3 s} may be the same or different from each other, Z represents a hydrogen atom or a halogen atom, and when a plurality of Z are present, the plurality of Z are the same A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.) The method for producing an olefin-terpenoid copolymer according to claim 7 or 8, wherein the boron compound (C) is at least one boron compound selected from the following (C1) to (C3).
(C1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (C3) General formula (L ¹ − H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B represents a trivalent boron atom, Q ^{1 to} Q ⁴ are each independently a halogen atom, It represents a substituent selected from the group consisting of a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group, and a 2-substituted amino group, and Q ^{1 to} Q ⁴ may be the same or different. ⁺ Represents an inorganic or organic cation, L ¹ represents a neutral Lewis base, and (L ¹ -H) ⁺ represents a Bronsted acid.)