JPH09165411A - Polymerization catalyst and production of polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerization catalyst which can efficiently give syndiotactic styrene polymers, polyolefins, etc., by mixing a specified transition metal compound with a specified oxygenic compound or the like and an alkylating agent. SOLUTION: This polymerization catalyst comprises a transition metal compound (a) containing at least one bond represented by M-X<1> in the molecule and containing no bond represented by M-Y<1> , a compound (i) which reacts with component (a) to form an ionic complex or oxygenic compounds (ii) (b) represented by formulas I and/or II and an alkylating agent. In the formulas, M is a metallic element of group 3-6 or in the lanthanoid series in the periodic table; X<1> is an element of group 15 in the periodic table; R<11> to R<15> are each a 1-8C alkyl; Y<2> to Y<4> are each an element of group 13 in the periodic table; (f) and (g) are each 10-50; f+g>=1; Y<5> and Y<6> are each an element of group 13 in the periodic table; (h) and (i) are each 0-50; and h+i>=1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerization catalyst and a method for producing a polymer, and more specifically, a styrene polymer having a syndiotactic structure, a polyolefin or the like which can be produced efficiently and inexpensively. The present invention relates to a catalyst and a method for producing the polymer.

[0002]

2. Description of the Related Art In recent years,
A method has been proposed in which a polymer having a syndiotactic structure is obtained by polymerizing a monomer using a catalyst mainly composed of a transition metal compound, particularly a titanium compound and methylaluminoxane (JP-A-62-187708). ). Further, in the production of the polymer as described above, in order to efficiently produce a polymer having a syndiotactic structure without using an expensive and often used aluminoxane,
A method using a coordination complex compound composed of an anion in which a plurality of groups are bound to a metal and a cation has also been proposed (JP-A-2-415573, JP-A-415574, etc.). Furthermore, when the monomer is polymerized using the above catalyst, a compound capable of reacting with a transition metal compound to form an ionic complex, or a reaction product of an organoaluminum compound and water and a transition metal compound are used. A method for synthesizing a high-performance polymer in a high yield by using a catalyst that has been allowed to act has already been disclosed.

However, these catalyst systems cannot always exhibit sufficient activity, so that a large amount of metal remains in the produced polymer, which adversely affects the physical properties of the polymer. Further, the polymer obtained using the above catalyst, mainly due to the halogen atoms contained in the transition metal compound, adversely affects the physical properties and the like, and as a countermeasure, complicated post-treatment facilities and the like are required. It was Therefore, the residual metal in the obtained polymer is reduced,
It has been desired to develop a polymerization catalyst that can simplify the polymer production process and reduce the production cost. Also,
As a result of the polymerization using the above catalyst, the halogen atoms remaining in the obtained polymer are reduced, the influence on the physical properties of the polymer is small, and the development of a polymerization catalyst that does not require complicated post-treatment equipment is desired. Was there. As a result of earnest research under such circumstances, the present inventors have found that when mainly polymerizing a monomer such as styrene, a transition metal compound having a specific substituent,
It has been found that a polymerization catalyst containing an alkylating agent and a compound capable of reacting with a specific oxygen-containing compound or a transition metal compound to form an ionic complex solves the above problems.

[0004]

The present invention has been completed based on the above findings. That is, the present invention is, (a) in one molecule, the following general formula ^{(1) M-X 1 ···} (1) wherein, M is the Periodic Table 3-6 Group or lanthanide series metal element, X ¹ represents an element belonging to Group 15 of the periodic table. ] At least one bond represented by the following general formula (2) MY ¹ ... (2) [In the formula, M is a metal element of the periodic table 3 to 6 group or lanthanoid series, Y ¹ represents an element belonging to Group 17 of the periodic table. ] A transition metal compound having no bond represented by the above, preferably the above transition metal compound having at least one Cp group in the above transition metal compound, (b) (a) reacting with the transition metal compound of the component (a) Or a compound capable of forming an ionic complex, or (b) the general formula (3)

[0005]

Embedded image [In the formula, R ^{11 to} R ¹⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and Y ^{2 to} Y ⁴ each represent an element of Group 13 of the periodic table,
They may be the same or different, and f and g each represent a number of 0 to 50, and f + g is 1 or more. ] And / or general formula (4)

[0006]

Embedded image [In the formula, R ¹⁶ and R ¹⁷ each represent an alkyl group having 1 to 8 carbon atoms, and they may be the same or different; Y ⁵ and Y ⁶ each represent an element of Group 13 of the periodic table; They may be the same or different, h
And i each represent a number of 0 to 50, and h + i is 1 or more. ] The oxygen-containing compound represented by these, and (c) alkylating agent are provided, The catalyst for polymerization characterized by the above-mentioned is provided. The present invention also provides a method for producing a styrene-based polymer, which comprises polymerizing a styrene-based monomer in the presence of the above-mentioned polymerization catalyst, and a method for producing a styrene-olefin-based copolymer. It is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, the transition metal compound used as the component (a) has, in one molecule, the following general formula (1) M-X ¹ ... (1) [In the formula, M is a group 3 to 6 of the periodic table. Alternatively, a lanthanoid series metal element, X ¹ represents an element of Group 15 of the periodic table. ] At least one bond represented by, and the following general formula (2) MY ¹ ... (2) [In the formula, M is a metal element of Group 3 to 6 of the periodic table or a lanthanoid series, Y ¹ represents an element belonging to Group 17 of the periodic table. ] It is a transition metal compound which does not contain the bond represented by these. In the above general formulas (1) and (2), M represents a metal element of Group 3 to 6 of the periodic table or a lanthanoid series, preferably 4
A metal element of the group, specifically titanium, zirconium or hafnium can be mentioned. X ¹ represents an element belonging to Group 15 of the periodic table, specifically, N,
P, As, Sb or Bi can be mentioned, but among these, N or P is preferable. In addition, Y ¹ represents an element of Group 17 of the periodic table, and specifically, by an element symbol,
F, Cl, Br, I or At may be mentioned.

In the present invention, the transition metal compound (a) which is more preferably used is represented by the following general formula (5) or (6) M (R ¹ R ² -A) _a X _b Y _c Z _{4- (a + b + c) ··· (5)} M ( in _{^{R 1 R 2 -A) d X}} e Y 3- (d + e) ··· (6) [wherein, M is the periodic table 3-6 or group A metal element of the lanthanoid series is shown, preferably a metal element of Group 4 and specifically titanium, zirconium or hafnium. A is a nitrogen atom or a phosphorus atom, R ¹ and R ² are each a hydrogen atom, an alkyl group, preferably 1 to 20 carbon atoms.
Alkyl group (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, etc.), aryl group, alkylaryl group, arylalkyl group, preferably having 6 carbon atoms. To 20 aryl group, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.), silyl group, preferably alkylsilyl group having 1 to 20 carbon atoms, aryl Silyl group (specifically, bistrimethylsilyl group, etc.), vinyl group, allyl group, preferably vinyl group having 1 to 20 carbon atoms, allyl group (specifically, vinyl group, propenylene group, allyl group, 2-butenyl group, etc.) ), An ethynyl group, preferably an ethynyl group having 1 to 20 carbon atoms (specifically, an ethynyl group, a phenylethynyl group, etc.),
Acyl group Preferably, an acyl group having 1 to 20 carbon atoms (specifically, formyl group, acetyl group, etc.) is shown, and these may be the same or different from each other. R ¹ and R ² may be bonded to each other. X, Y and Z are each independently a hydrogen atom, an alkyl group, preferably 1 to 20 carbon atoms.
An alkyl group (specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, an isoamyl group, an isobutyl group, an octyl group, etc.), an alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms (specifically, Specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, etc.), an aryl group, an alkylaryl group, an arylalkyl group, an aryloxy group, preferably a carbon number of 6 ~ 20
Aryl group, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group,
Benzyl group), acyloxyl group, preferably having 1 carbon atom
To 50 acyloxyl groups (specifically, acetoxyl group, benzoyloxyl group, trimethylacetoxyl group, triphenylacetoxyl group, etc.), vinyl group, allyl group, preferably vinyl group having 1 to 20 carbon atoms, allyl group (Specifically, vinyl group, propenylene group, allyl group,
2-butenyl group, etc.), ethynyl group, preferably 1 to 1 carbon atoms
20 ethynyl group (specifically, ethynyl group, phenylethynyl group, etc.), alkylthio group, arylthio group, preferably alkylthio group having 1 to 20 carbon atoms, arylthio group (specifically, methylthio group, ethylthio group, butylthio group) Group, amylthio group, phenylthio group, p-methylphenylthio group, etc.), or Cp group (cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, substituted fluorenyl group)
And is not an element of Group 17 of the periodic table. a is 1
An integer of 4, b and c are integers of 0 to 3, and d is 1 to 3
And an e is an integer of 0 to 2. (R ¹ R ² -A),
Any two of X, Y or Z may be crosslinked. ] Is represented.

Among the transition metal compounds represented by the above general formula (5) or (6), specific examples of the transition metal compound containing no Cp group include, for example, tetrakis (dimethylamido) titanium and tetrakis (diethylamido). Titanium, tetrakis (dibutylamido) titanium, tetrakis (diphenylamido) titanium, tetrakis (methylphenylamido) titanium, tetrakis (bistrimethylsilylamido) titanium, tris (dimethylamido) titaniummethyl, tris (diethylamido) titaniummethyl, tris (dibutyl) Amido) titanium methyl, tris (diphenylamido) titanium methyl, tris (methylphenylamido) titanium methyl, tris (bistrimethylsilylamido) titanium methyl, tris Dimethylamido) titanium phenyl, tris (diethylamido) titanium phenyl, tris (dibutylamido) titanium phenyl, tris (diphenylamido) titanium phenyl, tris (methylphenylamido) titanium phenyl, tris (bistrimethylsilylamido) titanium phenyl, tris (dimethyl) Amido) titanium methoxide, tris (diethylamido) titanium methoxide, tris (dibutylamide) titanium methoxide, tris (diphenylamide) titanium methoxide, tris (methylphenylamido) titanium methoxide, tris (bistrimethylsilylamide) titanium methoxide Side, tris (dimethylamido) phenoxy titanium, tris (diethylamido) phenoxy Taniumu,
Tris (dibutylamido) phenoxytitanium, tris (diphenylamido) phenoxytitanium, tris (methylphenylamido) phenoxytitanium, tris (bistrimethylsilylamido) phenoxytitanium, tris (dimethylamido) (acetoxy) titanium, tris (diethylamido) (acetoxy) ) Titanium, tris (dibutylamide) (acetoxy) titanium, tris (diphenylamide) (acetoxy) titanium, tris (methylphenylamide) (acetoxy)
Titanium, Tris (bistrimethylsilylamide)
(Acetoxy) titanium, tris (dimethylamide)
(Trimethylacetoxy) titanium, tris (diethylamide) (trimethylacetoxy) titanium, tris (dibutylamide) (trimethylacetoxy) titanium, tris (diphenylamide) (trimethylacetoxy) titanium, tris (methylphenylamide)
(Trimethylacetoxy) titanium, tris (bistrimethylsilylamide) (trimethylacetoxy) titanium,

Bis (dimethylamido) titanium dimethyl, bis (diethylamido) titanium dimethyl, bis (dibutylamido) titanium dimethyl, bis (diphenylamido) titanium dimethyl, bis (methylphenylamido) titanium dimethyl, bis (bistrimethylsilylamido) titanium Dimethyl, bis (dimethylamido) titanium diphenyl, bis (diethylamido)
Titanium diphenyl, bis (dibutylamide) titanium diphenyl, bis (diphenylamide) titanium diphenyl, bis (methylphenylamide) titanium diphenyl, bis (bistrimethylsilylamide) titanium diphenyl, bis (dimethylamide) titanium dimethoxide, bis (diethylamide) ) Titanium dimethoxide, bis (dibutylamide) titanium dimethoxide, bis (diphenylamide) titanium dimethoxide, bis (methylphenylamide) titanium dimethoxide, bis (bistrimethylsilylamide)
Titanium dimethoxide, bis (dimethylamide) diphenoxytitanium, bis (diethylamido) diphenoxytitanium, bis (dibutylamido) diphenoxytitanium, bis (diphenylamido) diphenoxytitanium, bis (methylphenylamido) diphenoxytitanium, Bis (bistrimethylsilylamido) diphenoxytitanium, bis (dimethylamido) di (acetoxy) titanium, bis (diethylamido) di (acetoxy) titanium, bis (dibutylamido) di (acetoxy) titanium, bis (diphenylamido) di (acetoxy) ) Titanium, bis (methylphenylamido) di (acetoxy) titanium, bis (bistrimethylsilylamido) di (acetoxy) titanium, bis (dimethylamido) di Trimethylacetoxy) titanium, bis (diethylamide) di (trimethylacetoxy) titanium, bis (dibutylamide) di (trimethylacetoxy) titanium, bis (diphenyl amide)
Di (trimethylacetoxy) titanium, bis (methylphenylamido) di (trimethylacetoxy) titanium, bis (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(Dimethylamido) titanium trimethyl, (diethylamido) titanium trimethyl, (dibutylamido) titanium trimethyl, (diphenylamido) titanium trimethyl, (methylphenylamido)
Titanium trimethyl, (bistrimethylsilylamido) titanium trimethyl, (dimethylamido) titanium triphenyl, (diethylamido) titanium triphenyl, (dibutylamido) titanium triphenyl, (diphenylamido) titanium triphenyl,
(Methylphenylamide) titanium triphenyl,
(Bistrimethylsilylamido) titanium triphenyl, (dimethylamido) titanium trimethoxide,
(Diethylamido) titanium trimethoxide, (dibutylamido) titanium trimethoxide, (diphenylamido) titanium trimethoxide, (methylphenylamido) titanium trimethoxide, (bistrimethylsilylamide) titanium trimethoxide,
(Dimethylamido) triphenoxytitanium, (Diethylamido) triphenoxytitanium, (Dibutylamido) triphenoxytitanium, (Diphenylamido) triphenoxytitanium, (Methylphenylamido) triphenoxytitanium, (Bistrimethylsilylamido) triphenoxytitanium, ( (Dimethylamido) tri (acetoxy) titanium, (diethylamido) tri (acetoxy) titanium, (dibutylamido) tri (acetoxy) titanium, (diphenylamido) tri (acetoxy) titanium, (methylphenylamido) tri (acetoxy) titanium, ( Bistrimethylsilylamido) tri (acetoxy) titanium,
(Dimethylamido) tri (trimethylacetoxy) titanium, (Diethylamido) tri (trimethylacetoxy) titanium, (Dibutylamido) tri (trimethylacetoxy) titanium, (Diphenylamido) tri (trimethylacetoxy) titanium, (Methylphenylamido) tri ( Trimethylacetoxy) titanium,
(Bistrimethylsilylamido) tri (trimethylacetoxy) titanium and the like.

Further, there can be mentioned similar compounds in which each amide group in these compounds is substituted with a corresponding phosphide group. Furthermore, zirconium or hafnium may be substituted for titanium in these compounds, or compounds similar to transition metal elements of other group or lanthanoid series may be mentioned, but the compounds are not limited thereto. Of these, titanium compounds are preferable from the viewpoint of catalytic activity. Moreover, you may use the mixture which combined these compounds arbitrarily.

In the transition metal compound represented by the general formula (5) or the general formula (6), there are various compounds as the compound in which M in the formula is Ti. For example, the following general formula ( At least one compound selected from the titanium compounds represented by 7) or (8) is preferably used. ^{Ti (R 1 R 2 -A)} a X b Y c Z 4- (a + b + c) ··· (7) Ti (R 1 R 2 -A) d X e Y 3- (d + e) (8) [wherein R ¹ , R ² , A, X, Y, Z, a, b, c, d
And e are the same as described above, and R ¹ , R ² , X, Y and Z
May be the same or different. The Ti compound is a compound having no Ti-halogen atom bond, and a titanium compound having at least one π-electron ligand is particularly preferable.

Further, in these transition metal compounds, at least one Cp group, preferably 1
Examples thereof include transition metal compounds having one or two Cp groups, and more preferably one Cp group, and include the following general formula (9) or (10) M (R ¹ R ² -A) _a (Cp) _b Y _c Z _{4- (a + b + c)} (9) M (R ¹ R ² -A) _d (Cp) _e Y _{3- (d + e)} (10) [wherein R ¹ , R ² , A, M, Cp, Y and Z are the same as above, and R ¹ , R ² , Cp, Y and Z may be the same or different. a, b, c, d and e are 1 ≦ a ≦ 3, 1 ≦ b ≦ 3, 0 ≦ c ≦ 2, 1 ≦ d ≦ 2, respectively.
It is an integer in the range of 1 ≦ e ≦ 2. ] The compound represented by the general formula (9) or (10) is M-
It is a compound having no halogen atom bond. Also, Cp
The group is a cyclopentadienyl group or a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group,
Dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc.), indenyl group, substituted indenyl group (specifically, methylindenyl group, dimethyl group Indenyl group, trimethylindenyl group, tetramethylindenyl group, hexamethylindenyl group, 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyl group, 1,2-dimethyl-4, 5,
6,7-tetrahydroindenyl group, 1,3-dimethyl-4,5,6,7-tetrahydroindenyl group, etc.), fluorenyl group, substituted fluorenyl group (specifically, methylfluorenyl group, dimethylfluorenyl group) Oleenyl group, tetramethylfluorenyl group, octamethylfluorenyl group,
1,2,3,4,5,6,7,8-octahydrofluorenyl group, 9-methyl-1,2,3,4,5,6,7,
8-octahydrofluorenyl group, etc.)
p is mutually, or the above (R ¹ R ² -A) group and one Cp group are alkylene groups having 1 to 5 carbon atoms and 1 to 1 carbon atoms.
8 alkylidene group (specifically, ethylidene group, propylidene group, etc.) or alkylsilylene group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, dimethylsilylene group, diethylsilylene group, diphenylsilylene group) Etc.) may be crosslinked.

Further, the transition metal compound represented by the general formula (9) or (10) contains one Cp, and Y
And Z are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkylaryl group, an arylalkyl group, an aryloxy group, an acyloxyl group, a vinyl group, an allyl group, an ethynyl group, an alkylthio group or an arylthio group. the following general formula (9 ') or ^{(10') M (R 1} R 2 -A) w CpR '3-w ··· (9') M (R 1 R 2 -A) x CpR '2-x · .. (10 ') ^{wherein, R 1, R 2, a} , M and Cp are as defined above, w is an integer of 1 to 3, x is 1 or 2. R'is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, a butyl group,
Amyl group, isoamyl group, isobutyl group, octyl group, etc.), alkoxy group, preferably alkoxy group having 1 to 20 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group) , 2-ethylhexyloxy group, etc.), aryl group, alkylaryl group, arylalkyl group, preferably aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group). Basis,
Xylyl group, benzyl group, etc.), aryloxy group, preferably aryloxy group having 6 to 20 carbon atoms (specifically, phenoxy group, etc.), acyloxyl group, preferably 1 carbon atom.
To 50 acyloxyl groups (specifically, acetoxyl group, benzoyloxyl group, trimethylacetoxyl group, triphenylacetoxyl group, etc.), vinyl group, allyl group, preferably vinyl group having 1 to 20 carbon atoms, allyl Group (specifically, vinyl group, propenylene group, allyl group, 2
-Butenyl group), ethynyl group, preferably having 1 to 2 carbon atoms
0 ethynyl group (specifically ethynyl group, phenylethynyl group, etc.), or alkylthio group, arylthio group, preferably alkylthio group having 1 to 20 carbon atoms, arylthio group (specifically, methylthio group, ethylthio group, Butylthio group, amylthio group, phenylthio group, p-methylphenylthio group and the like). ] The transition metal compound represented by these can be mentioned as a suitable compound. Further, in the general formula (9 ′) or (10 ′), a compound in which M is titanium is preferable.

Specific examples of the transition metal compound containing one Cp group represented by the general formula (9) or (10) are:
(Cyclopentadienyl) tris (dimethylamido) titanium, (Cyclopentadienyl) tris (diethylamido) titanium, (Cyclopentadienyl) tris (dibutylamido) titanium, (Cyclopentadienyl) tris (diphenylamido) titanium , (Cyclopentadienyl) tris (methylphenylamido) titanium, (Cyclopentadienyl) tris (bistrimethylsilylamido) titanium, (Cyclopentadienyl) bis (dimethylamido) titaniummethyl, (Cyclopentadienyl) bis (Diethylamido) titanium methyl, (cyclopentadienyl) bis (dibutylamido) titanium methyl, (cyclopentadienyl) bis (diphenylamido) titanium methyl, (cyclopentadienyl) bis Methylphenyl amides) titanium methyl, (cyclopentadienyl) bis (bistrimethylsilylamide) titanium methyl, (cyclopentadienyl) bis (dimethylamide) titanium phenyl,
(Cyclopentadienyl) bis (diethylamido) titanium phenyl, (cyclopentadienyl) bis (dibutylamido) titanium phenyl, (cyclopentadienyl) bis (diphenylamido) titanium phenyl,
(Cyclopentadienyl) bis (methylphenylamido) titaniumphenyl, (Cyclopentadienyl) bis (bistrimethylsilylamido) titaniumphenyl, (Cyclopentadienyl) bis (dimethylamido)
Titanium methoxide, (cyclopentadienyl) bis (diethylamido) titanium methoxide, (cyclopentadienyl) bis (dibutylamido) titanium methoxide, (cyclopentadienyl) bis (diphenylamido) titanium methoxide, (cyclo Pentadienyl) bis (methylphenylamido) titanium methoxide, (Cyclopentadienyl) bis (bistrimethylsilylamido) titanium methoxide, (Cyclopentadienyl) bis (dimethylamido) phenoxytitanium, (Cyclopentadienyl) Bis (diethylamido) phenoxytitanium, (cyclopentadienyl) bis (dibutylamido) phenoxytitanium,
(Cyclopentadienyl) bis (diphenylamido) phenoxytitanium, (Cyclopentadienyl) bis (methylphenylamido) phenoxytitanium, (Cyclopentadienyl) bis (bistrimethylsilylamido) phenoxytitanium, (Cyclopentadienyl)
Bis (dimethylamido) (acetoxy) titanium,
(Cyclopentadienyl) bis (diethylamido) (acetoxy) titanium, (Cyclopentadienyl) bis (dibutylamido) (acetoxy) titanium, (Cyclopentadienyl) bis (diphenylamide) (acetoxy) titanium, (Cyclopenta Dienyl) bis (methylphenylamido) (acetoxy) titanium, (Cyclopentadienyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (Cyclopentadienyl) bis (dimethylamido) (trimethylacetoxy)
Titanium, (cyclopentadienyl) bis (diethylamido) (trimethylacetoxy) titanium, (cyclopentadienyl) bis (dibutylamido) (trimethylacetoxy) titanium, (cyclopentadienyl)
Bis (diphenylamido) (trimethylacetoxy) titanium, (cyclopentadienyl) bis (methylphenylamido) (trimethylacetoxy) titanium,
(Cyclopentadienyl) bis (bistrimethylsilylamide) (trimethylacetoxy) titanium, (cyclopentadienyl) (dimethylamido) titanium dimethyl, (cyclopentadienyl) (diethylamido) titanium dimethyl, (cyclopentadienyl) ( Dibutylamido) titanium dimethyl, (cyclopentadienyl) (diphenylamido) titanium dimethyl, (cyclopentadienyl) (methylphenylamido) titanium dimethyl, (cyclopentadienyl) (bistrimethylsilylamido) titanium dimethyl, (cyclopentadiene) Dienyl) (dimethylamido) titanium diphenyl,
(Cyclopentadienyl) (diethylamido) titanium diphenyl, (cyclopentadienyl) (dibutylamido) titanium diphenyl, (cyclopentadienyl) (diphenylamido) titanium diphenyl, (cyclopentadienyl) (methylphenylamido) titanium Diphenyl, (cyclopentadienyl) (bistrimethylsilylamido) titanium diphenyl, (cyclopentadienyl) (dimethylamido) titanium dimethoxide, (cyclopentadienyl) (diethylamido) titanium dimethoxide, (cyclopentadienyl) ) (Dibutylamide) titanium dimethoxide,
(Cyclopentadienyl) (diphenylamido) titanium dimethoxide, (Cyclopentadienyl) (methylphenylamido) titanium dimethoxide, (Cyclopentadienyl) (bistrimethylsilylamido) titanium dimethoxide, (Cyclopentadienyl) (Dienyl)
(Dimethylamido) diphenoxytitanium, (Cyclopentadienyl) (diethylamido) diphenoxytitanium, (Cyclopentadienyl) (dibutylamide)
Diphenoxytitanium, (cyclopentadienyl)
(Diphenylamido) diphenoxytitanium, (cyclopentadienyl) (methylphenylamido) diphenoxytitanium, (cyclopentadienyl) (bistrimethylsilylamido) diphenoxytitanium, (cyclopentadienyl) (dimethylamido) di ( (Acetoxy) titanium, (cyclopentadienyl) (diethylamido) di (acetoxy) titanium, (cyclopentadienyl) (dibutylamido) di (acetoxy) titanium, (cyclopentadienyl) (diphenylamide)
Di (acetoxy) titanium, (cyclopentadienyl) (methylphenylamido) di (acetoxy) titanium, (cyclopentadienyl) (bistrimethylsilylamido) di (acetoxy) titanium, (cyclopentadienyl) (dimethylamide) Di (trimethylacetoxy) titanium, (cyclopentadienyl) (diethylamido) di (trimethylacetoxy) titanium,
(Cyclopentadienyl) (dibutylamido) di (trimethylacetoxy) titanium, (Cyclopentadienyl) (diphenylamido) di (trimethylacetoxy)
Titanium, (cyclopentadienyl) (methylphenylamido) di (trimethylacetoxy) titanium,
(Cyclopentadienyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(Tetramethylcyclopentadienyl) tris (dimethylamido) titanium, (Tetramethylcyclopentadienyl) tris (diethylamido) titanium, (Tetramethylcyclopentadienyl) tris (dibutylamido) titanium, (Tetramethyl Cyclopentadienyl) tris (diphenylamido) titanium, (Tetramethylcyclopentadienyl) tris (methylphenylamido) titanium, (Tetramethylcyclopentadienyl) tris (bistrimethylsilylamido) titanium, (Tetramethylcyclopentadienyl) (Ethyl) bis (dimethylamido) titanium methyl, (Tetramethylcyclopentadienyl) bis (diethylamido) titaniummethyl, (Tetramethylcyclopentadienyl) bis (dibutyl) Bromide) titanium methyl,
(Tetramethylcyclopentadienyl) bis (diphenylamido) titanium methyl, (Tetramethylcyclopentadienyl) bis (methylphenylamido) titanium methyl, (Tetramethylcyclopentadienyl) bis (bistrimethylsilylamido) titanium methyl,
(Tetramethylcyclopentadienyl) bis (dimethylamido) titaniumphenyl, (Tetramethylcyclopentadienyl) bis (diethylamido) titaniumphenyl, (Tetramethylcyclopentadienyl) bis (dibutylamido) titaniumphenyl, (Tetramethyl Cyclopentadienyl) bis (diphenylamido) titaniumphenyl, (tetramethylcyclopentadienyl)
Bis (methylphenylamido) titanium phenyl,
(Tetramethylcyclopentadienyl) bis (bistrimethylsilylamido) titanium phenyl, (Tetramethylcyclopentadienyl) bis (dimethylamido) titanium methoxide, (Tetramethylcyclopentadienyl) bis (diethylamido) titanium methoxide, (Tetramethylcyclopentadienyl) bis (dibutylamido) titanium methoxide, (Tetramethylcyclopentadienyl) bis (diphenylamido) titanium methoxide, (Tetramethylcyclopentadienyl) bis (methylphenylamido) titanium methoxide Side, (tetramethylcyclopentadienyl) bis (bistrimethylsilylamido) titanium methoxide, (tetramethylcyclopentadienyl) bis (dimethylamido) pheno Shi titanium, (tetramethylcyclopentadienyl) bis (diethylamide) phenoxy titanium, (tetramethylcyclopentadienyl)
Bis (dibutylamido) phenoxytitanium, (tetramethylcyclopentadienyl) bis (diphenylamido) phenoxytitanium, (tetramethylcyclopentadienyl) bis (methylphenylamido) phenoxytitanium, (tetramethylcyclopentadienyl) bis (Bistrimethylsilylamido) phenoxytitanium, (tetramethylcyclopentadienyl) bis (dimethylamido) (acetoxy) titanium, (tetramethylcyclopentadienyl) bis (diethylamido) (acetoxy) titanium, (tetramethylcyclopentadienyl) ) Bis (dibutylamido) (acetoxy) titanium, (tetramethylcyclopentadienyl) bis (diphenylamido) (acetoxy) titanium, (tetramethylcyclopentene Dienyl) bis (methylphenylamido) (acetoxy) titanium, (Tetramethylcyclopentadienyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (Tetramethylcyclopentadienyl) bis (dimethylamido) (trimethylacetoxy) titanium , (Tetramethylcyclopentadienyl) bis (diethylamido) (trimethylacetoxy) titanium, (Tetramethylcyclopentadienyl) bis (dibutylamido) (trimethylacetoxy)
Titanium, (tetramethylcyclopentadienyl) bis (diphenylamide) (trimethylacetoxy) titanium (tetramethylcyclopentadienyl) bis (methylphenylamide) (trimethylacetoxy) titanium, (tetramethylcyclopentadienyl) bis ( Bistrimethylsilylamide) (trimethylacetoxy)
Titanium, (tetramethylcyclopentadienyl)
(Dimethylamido) titanium dimethyl, (tetramethylcyclopentadienyl) (diethylamido) titanium dimethyl, (tetramethylcyclopentadienyl)
(Dibutylamido) titanium dimethyl, (tetramethylcyclopentadienyl) (diphenylamido) titanium dimethyl, (tetramethylcyclopentadienyl)
(Methylphenylamido) titanium dimethyl, (tetramethylcyclopentadienyl) (bistrimethylsilylamido) titanium dimethyl, (tetramethylcyclopentadienyl) (dimethylamido) titanium diphenyl, (tetramethylcyclopentadienyl) (diethylamide) Titaniumdiphenyl, (tetramethylcyclopentadienyl) (dibutylamido) titaniumdiphenyl, (tetramethylcyclopentadienyl) (diphenylamido) titaniumdiphenyl, (tetramethylcyclopentadienyl) (methylphenylamido) titaniumdiphenyl, ( Tetramethylcyclopentadienyl) (bistrimethylsilylamido) titanium diphenyl, (tetramethylcyclopentadienyl) (dimethylamido) titani Muzi methoxide, (tetramethylcyclopentadienyl) (diethylamido) titanium di methoxide, (tetramethylcyclopentadienyl) (dibutylamide) titanium di methoxide,
(Tetramethylcyclopentadienyl) (diphenylamido) titanium dimethoxide, (Tetramethylcyclopentadienyl) (methylphenylamido) titanium dimethoxide, (Tetramethylcyclopentadienyl) (bistrimethylsilylamido) titaniumdimethoxide Methoxide, (tetramethylcyclopentadienyl) (dimethylamido) diphenoxytitanium, (tetramethylcyclopentadienyl) (diethylamido) diphenoxytitanium, (tetramethylcyclopentadienyl) (dibutylamido) diphenoxytitanium, (Tetramethylcyclopentadienyl) (diphenylamido) diphenoxytitanium, (Tetramethylcyclopentadienyl) (methylphenylamido) diphenoxytitanium, (tetra Chill cyclopentadienyl)
(Bistrimethylsilylamido) diphenoxytitanium, (tetramethylcyclopentadienyl) (dimethylamido) di (acetoxy) titanium, (tetramethylcyclopentadienyl) (diethylamido) di (acetoxy) titanium, (tetramethylcyclopentadienyl) Enyl) (dibutylamido) di (acetoxy) titanium,
(Tetramethylcyclopentadienyl) (diphenylamido) di (acetoxy) titanium, (Tetramethylcyclopentadienyl) (methylphenylamido) di (acetoxy) titanium, (Tetramethylcyclopentadienyl) (bistrimethylsilylamide) Di (acetoxy) titanium, (tetramethylcyclopentadienyl) (dimethylamido) di (trimethylacetoxy) titanium, (tetramethylcyclopentadienyl) (diethylamido) di (trimethylacetoxy) titanium, (tetramethylcyclopentadienyl) ) (Dibutylamido) di (trimethylacetoxy) titanium, (Tetramethylcyclopentadienyl) (diphenylamido) di (trimethylacetoxy) titanium, (Tetramethylcyclopentadiene) Le) (methylphenyl amides) di (trimethylacetoxy) titanium, (tetramethylcyclopentadienyl) (bistrimethylsilylamide) di (trimethylacetoxy) titanium,

(Pentamethylcyclopentadienyl) tris (dimethylamido) titanium, (pentamethylcyclopentadienyl) tris (diethylamido) titanium, (pentamethylcyclopentadienyl) tris (dibutylamido) titanium, (pentamethyl Cyclopentadienyl) tris (diphenylamido) titanium, (pentamethylcyclopentadienyl) tris (methylphenylamido) titanium, (pentamethylcyclopentadienyl) tris (bistrimethylsilylamido) titanium, (pentamethylcyclopentadienyl) (Ethyl) bis (dimethylamido) titanium methyl, (pentamethylcyclopentadienyl) bis (diethylamido) titanium methyl, (pentamethylcyclopentadienyl) bis (dibutyl) Bromide) titanium methyl,
(Pentamethylcyclopentadienyl) bis (diphenylamido) titaniummethyl, (pentamethylcyclopentadienyl) bis (methylphenylamido) titaniummethyl, (pentamethylcyclopentadienyl) bis (bistrimethylsilylamido) titaniummethyl,
(Pentamethylcyclopentadienyl) bis (dimethylamido) titaniumphenyl, (pentamethylcyclopentadienyl) bis (diethylamido) titaniumphenyl, (pentamethylcyclopentadienyl) bis (dibutylamido) titaniumphenyl, (pentamethyl Cyclopentadienyl) bis (diphenylamido) titaniumphenyl, (pentamethylcyclopentadienyl)
Bis (methylphenylamido) titanium phenyl,
(Pentamethylcyclopentadienyl) bis (bistrimethylsilylamido) titaniumphenyl, (pentamethylcyclopentadienyl) bis (dimethylamido) titanium methoxide, (pentamethylcyclopentadienyl) bis (diethylamido) titanium methoxide, (Pentamethylcyclopentadienyl) bis (dibutylamido) titanium methoxide, (pentamethylcyclopentadienyl) bis (diphenylamido) titanium methoxide, (pentamethylcyclopentadienyl) bis (methylphenylamido) titanium methoxide Side, (pentamethylcyclopentadienyl) bis (bistrimethylsilylamido) titanium methoxide, (pentamethylcyclopentadienyl) bis (dimethylamido) pheno Shi titanium, (pentamethylcyclopentadienyl) bis (diethylamide) phenoxy titanium, (pentamethylcyclopentadienyl)
Bis (dibutylamido) phenoxytitanium, (pentamethylcyclopentadienyl) bis (diphenylamido) phenoxytitanium, (pentamethylcyclopentadienyl) bis (methylphenylamido) phenoxytitanium, (pentamethylcyclopentadienyl) bis (Bistrimethylsilylamido) phenoxytitanium, (pentamethylcyclopentadienyl) bis (dimethylamido) (acetoxy) titanium, (pentamethylcyclopentadienyl) bis (diethylamido) (acetoxy) titanium, (pentamethylcyclopentadienyl) ) Bis (dibutylamido) (acetoxy) titanium, (pentamethylcyclopentadienyl) bis (diphenylamido) (acetoxy) titanium, (pentamethylcyclopen Dienyl) bis (methylphenylamido) (acetoxy) titanium, (pentamethylcyclopentadienyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (pentamethylcyclopentadienyl) bis (dimethylamido) (trimethylacetoxy) titanium , (Pentamethylcyclopentadienyl) bis (diethylamido) (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) bis (dibutylamido) (trimethylacetoxy)
Titanium, (pentamethylcyclopentadienyl) bis (diphenylamide) (trimethylacetoxy) titanium (pentamethylcyclopentadienyl) bis (methylphenylamide) (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) bis ( Bistrimethylsilylamide) (trimethylacetoxy)
Titanium, (pentamethylcyclopentadienyl)
(Dimethylamido) titanium dimethyl, (pentamethylcyclopentadienyl) (diethylamido) titanium dimethyl, (pentamethylcyclopentadienyl)
(Dibutylamido) titanium dimethyl, (pentamethylcyclopentadienyl) (diphenylamido) titanium dimethyl, (pentamethylcyclopentadienyl)
(Methylphenylamido) titanium dimethyl, (pentamethylcyclopentadienyl) (bistrimethylsilylamido) titanium dimethyl, (pentamethylcyclopentadienyl) (dimethylamido) titanium diphenyl, (pentamethylcyclopentadienyl) (diethylamide) Titanium diphenyl, (pentamethylcyclopentadienyl) (dibutylamido) titanium diphenyl, (pentamethylcyclopentadienyl) (diphenylamido) titanium diphenyl, (pentamethylcyclopentadienyl) (methylphenylamido) titanium diphenyl, ( Pentamethylcyclopentadienyl) (bistrimethylsilylamido) titanium diphenyl, (pentamethylcyclopentadienyl) (dimethylamido) titani Muzi methoxide, (pentamethylcyclopentadienyl) (diethylamido) titanium di methoxide, (pentamethylcyclopentadienyl) (dibutylamide) titanium di methoxide,
(Pentamethylcyclopentadienyl) (diphenylamido) titanium dimethoxide, (pentamethylcyclopentadienyl) (methylphenylamido) titanium dimethoxide, (pentamethylcyclopentadienyl) (bistrimethylsilylamido) titaniumdimethoxide Methoxide, (pentamethylcyclopentadienyl) (dimethylamido) diphenoxytitanium, (pentamethylcyclopentadienyl) (diethylamido) diphenoxytitanium, (pentamethylcyclopentadienyl) (dibutylamido) diphenoxytitanium, (Pentamethylcyclopentadienyl) (diphenylamido) diphenoxytitanium, (Pentamethylcyclopentadienyl) (methylphenylamido) diphenoxytitanium, (Penta Chill cyclopentadienyl)
(Bistrimethylsilylamido) diphenoxytitanium, (pentamethylcyclopentadienyl) (dimethylamido) di (acetoxy) titanium, (pentamethylcyclopentadienyl) (diethylamido) di (acetoxy) titanium, (pentamethylcyclopentadienyl) Enyl) (dibutylamido) di (acetoxy) titanium,
(Pentamethylcyclopentadienyl) (diphenylamido) di (acetoxy) titanium, (pentamethylcyclopentadienyl) (methylphenylamido) di (acetoxy) titanium, (pentamethylcyclopentadienyl) (bistrimethylsilylamide) Di (acetoxy) titanium, (pentamethylcyclopentadienyl) (dimethylamido) di (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) (diethylamido) di (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) ) (Dibutylamido) di (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) (diphenylamido) di (trimethylacetoxy) titanium, (pentamethylcyclopentadiene) Le) (methylphenyl amides) di (trimethylacetoxy) titanium, (pentamethylcyclopentadienyl) (bis trimethylsilyl amide) di (trimethylacetoxy) titanium,

(Indenyl) tris (dimethylamide)
Titanium, (indenyl) tris (diethylamide)
Titanium, (indenyl) tris (dibutylamide)
Titanium, (indenyl) tris (diphenylamido) titanium, (indenyl) tris (methylphenylamido) titanium, (indenyl) tris (bistrimethylsilylamido) titanium, (indenyl) bis (dimethylamido) titaniummethyl, (indenyl) bis ( Diethylamido) titaniummethyl, (indenyl) bis (dibutylamido) titaniummethyl,
(Indenyl) bis (diphenylamido) titanium methyl, (indenyl) bis (methylphenylamido) titanium methyl, (indenyl) bis (bistrimethylsilylamido) titanium methyl, (indenyl) bis (dimethylamido) titaniumphenyl, (indenyl) bis (Diethylamido) titaniumphenyl, (indenyl) bis (dibutylamido) titaniumphenyl, (indenyl) bis (diphenylamido) titaniumphenyl, (indenyl) bis (methylphenylamido) titaniumphenyl, (indenyl) bis (bistrimethylsilylamido) titanium Phenyl, (indenyl) bis (dimethylamido) titanium methoxide, (indenyl) bis (diethylamido) titanium methoxide, (indene Le) bis (dibutyl)
Titanium methoxide, (indenyl) bis (diphenylamido) titanium methoxide, (indenyl)
Bis (methylphenylamido) titanium methoxide, (indenyl) bis (bistrimethylsilylamido) titanium methoxide, (indenyl) bis (dimethylamido) phenoxytitanium, (indenyl)
Bis (diethylamido) phenoxytitanium, (indenyl) bis (dibutylamido) phenoxytitanium, (indenyl) bis (diphenylamido) phenoxytitanium, (indenyl) bis (methylphenylamido) phenoxytitanium, (indenyl) bis (bistrimethylsilylamide) Phenoxytitanium,
(Indenyl) bis (dimethylamide) (acetoxy)
Titanium, (indenyl) bis (diethylamide)
(Acetoxy) titanium, (indenyl) bis (dibutylamido) (acetoxy) titanium, (indenyl) bis (diphenylamido) (acetoxy) titanium, (indenyl) bis (methylphenylamido) (acetoxy) titanium, (indenyl) bis ( (Bistrimethylsilylamido) (acetoxy) titanium, (indenyl) bis (dimethylamido) (trimethylacetoxy) titanium, (indenyl) bis (diethylamido) (trimethylacetoxy) titanium, (indenyl) bis (dibutylamido) (trimethylacetoxy)
Titanium, (indenyl) bis (diphenylamide)
(Trimethylacetoxy) titanium, (indenyl)
Bis (methylphenylamide) (trimethylacetoxy) titanium, (indenyl) bis (bistrimethylsilylamide) (trimethylacetoxy) titanium,
(Indenyl) (dimethylamido) titanium dimethyl, (indenyl) (diethylamido) titanium dimethyl, (indenyl) (dibutylamido) titanium dimethyl, (indenyl) (diphenylamido) titanium dimethyl, (indenyl) (methylphenylamide)
Titanium dimethyl, (indenyl) (bistrimethylsilylamido) titanium dimethyl, (indenyl)
(Dimethylamido) titanium diphenyl, (indenyl) (diethylamido) titanium diphenyl, (indenyl) (dibutylamido) titanium diphenyl,
(Indenyl) (diphenylamido) titanium diphenyl, (indenyl) (methylphenylamido) titanium diphenyl, (indenyl) (bistrimethylsilylamido) titanium diphenyl, (indenyl) (dimethylamido) titanium dimethoxide, (indenyl) (diethylamide) Titanium dimethoxide,
(Indenyl) (dibutylamido) titanium dimethoxide, (indenyl) (diphenylamido) titanium dimethoxide, (indenyl) (methylphenylamido) titanium dimethoxide, (indenyl) (bistrimethylsilylamido) titanium dimethoxide, (Indenyl) (dimethylamido) diphenoxytitanium, (indenyl) (diethylamido) diphenoxytitanium, (indenyl) (dibutylamido) diphenoxytitanium, (indenyl) (diphenylamido) diphenoxytitanium, (indenyl) (methylphenylamide) ) Diphenoxytitanium, (indenyl) (bistrimethylsilylamido) diphenoxytitanium, (indenyl) (dimethylamido) di (acetoxy) titanium (Indenyl) (diethylamido) di (acetoxy) titanium, (indenyl) (dibutylamido) di (acetoxy) titanium, (indenyl) (diphenylamido) di (acetoxy) titanium, (indenyl) (methylphenylamido) di (acetoxy) Titanium, (indenyl) (bistrimethylsilylamido) di (acetoxy) titanium, (indenyl) (dimethylamido) di (trimethylacetoxy)
Titanium, (indenyl) (diethylamido) di (trimethylacetoxy) titanium, (indenyl) (dibutylamido) di (trimethylacetoxy) titanium, (indenyl) (diphenylamido) di (trimethylacetoxy) titanium, (indenyl) (methylphenylamide) ) Di (trimethylacetoxy) titanium, (indenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(Heptamethylindenyl) tris (dimethylamido) titanium, (heptamethylindenyl)
Tris (diethylamido) titanium, (heptamethylindenyl) tris (dibutylamido) titanium,
(Heptamethylindenyl) tris (diphenylamido) titanium, (heptamethylindenyl) tris (methylphenylamido) titanium, (heptamethylindenyl) tris (bistrimethylsilylamido) titanium, (heptamethylindenyl) bis (dimethyl) Amido) titanium methyl, (heptamethylindenyl) bis (diethylamido) titaniummethyl, (heptamethylindenyl) bis (dibutylamido) titaniummethyl, (heptamethylindenyl) bis (diphenylamido) titaniummethyl, (heptamethylindene) Nyl) bis (methylphenylamido) titanium methyl,
(Heptamethylindenyl) bis (bistrimethylsilylamido) titanium methyl, (heptamethylindenyl) bis (dimethylamido) titaniumphenyl, (heptamethylindenyl) bis (diethylamido) titaniumphenyl, (heptamethylindenyl) bis ( Dibutylamido) titaniumphenyl, (heptamethylindenyl) bis (diphenylamido) titaniumphenyl, (heptamethylindenyl) bis (methylphenylamido) titaniumphenyl, (heptamethylindenyl) bis (bistrimethylsilylamido) titaniumphenyl, (Heptamethylindenyl) bis (dimethylamido) titanium methoxide, (Heptamethylindenyl) bis (diethylamido) titanium methoxide, Denyl) bis (dibutylamido) titanium methoxide, (heptamethylindenyl) bis (diphenylamido) titanium methoxide, (heptamethylindenyl) bis (methylphenylamido) titanium methoxide, (heptamethylindenyl) bis ( (Bistrimethylsilylamido) titanium methoxide, (heptamethylindenyl) bis (dimethylamido) phenoxytitanium, (heptamethylindenyl) bis (diethylamido) phenoxytitanium, (heptamethylindenyl) bis (dibutylamido) phenoxytitanium, ( Heptamethylindenyl) bis (diphenylamido) phenoxytitanium,
(Heptamethylindenyl) bis (methylphenylamido) phenoxytitanium, (heptamethylindenyl) bis (bistrimethylsilylamido) phenoxytitanium, (heptamethylindenyl) bis (dimethylamido) (acetoxy) titanium, (heptamethylindene) Nyl) bis (diethylamido) (acetoxy) titanium, (heptamethylindenyl) bis (dibutylamido) (acetoxy) titanium, (heptamethylindenyl) bis (diphenylamido) (acetoxy) titanium, (heptamethylindenyl) bis (Methylphenylamide) (acetoxy) titanium, (heptamethylindenyl) bis (bistrimethylsilylamide)
(Acetoxy) titanium, (heptamethylindenyl) bis (dimethylamide) (trimethylacetoxy)
Titanium, (heptamethylindenyl) bis (diethylamide) (trimethylacetoxy) titanium, (heptamethylindenyl) bis (dibutylamide) (trimethylacetoxy) titanium, (heptamethylindenyl) bis (diphenylamide) (trimethylacetoxy) Titanium, (heptamethylindenyl) bis (methylphenylamide) (trimethylacetoxy) titanium, (heptamethylindenyl) bis (bistrimethylsilylamide) (trimethylacetoxy) titanium, (heptamethylindenyl) (dimethylamido) titanium dimethyl , (Heptamethylindenyl) (diethylamido) titanium dimethyl, (heptamethylindenyl) (dibutylamido) titanium dimethyl, (heptamethylindeni) ) (Diphenylamido) titanium dimethyl, (heptamethylindenyl) (methylphenylamido) titanium dimethyl, (heptamethylindenyl) (bistrimethylsilylamido) titanium dimethyl, (heptamethylindenyl) (dimethylamido) titanium diphenyl, ( Heptamethylindenyl) (diethylamido) titanium diphenyl, (heptamethylindenyl) (dibutylamido) titanium diphenyl, (heptamethylindenyl) (diphenylamido) titanium diphenyl, (heptamethylindenyl) (methylphenylamido) titanium diphenyl ,
(Heptamethylindenyl) (bistrimethylsilylamido) titanium diphenyl, (heptamethylindenyl) (dimethylamido) titanium dimethoxide,
(Heptamethylindenyl) (diethylamido) titanium dimethoxide, (heptamethylindenyl) (dibutylamido) titanium dimethoxide, (heptamethylindenyl) (diphenylamido) titanium dimethoxide, (heptamethylindenyl) (Methylphenylamido) titanium dimethoxide, (heptamethylindenyl) (bistrimethylsilylamido) titanium dimethoxide, (heptamethylindenyl) (dimethylamido) diphenoxytitanium, (heptamethylindenyl) (diethylamido) di Phenoxytitanium, (heptamethylindenyl) (dibutylamide)
Diphenoxytitanium, (heptamethylindenyl)
(Diphenylamido) diphenoxytitanium, (heptamethylindenyl) (methylphenylamido) diphenoxytitanium, (heptamethylindenyl) (bistrimethylsilylamido) diphenoxytitanium,
(Heptamethylindenyl) (dimethylamido) di (acetoxy) titanium, (heptamethylindenyl)
(Diethylamido) di (acetoxy) titanium, (heptamethylindenyl) (dibutylamido) di (acetoxy) titanium, (heptamethylindenyl) (diphenylamido) di (acetoxy) titanium, (heptamethylindenyl) (methylphenyl Amido) di (acetoxy) titanium, (heptamethylindenyl) (bistrimethylsilylamide) di (acetoxy) titanium, (heptamethylindenyl) (dimethylamido) di (trimethylacetoxy) titanium, (heptamethylindenyl) (diethylamide) ) Di (trimethylacetoxy) titanium, (heptamethylindenyl) (dibutylamido) di (trimethylacetoxy) titanium,
(Heptamethylindenyl) (diphenylamido) di (trimethylacetoxy) titanium, (heptamethylindenyl) (methylphenylamido) di (trimethylacetoxy) titanium, (heptamethylindenyl)
(Bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(Fluorenyl) tris (dimethylamido) titanium, (fluorenyl) tris (diethylamido) titanium, (fluorenyl) tris (dibutylamido) titanium, (fluorenyl) tris (diphenylamido) titanium, (fluorenyl) tris (methylphenylamide) ) Titanium, (fluorenyl) tris (bistrimethylsilylamido) titanium, (fluorenyl) bis (dimethylamido) titaniummethyl, (fluorenyl) bis (diethylamido) titaniummethyl, (fluorenyl) bis (dibutylamido) titaniummethyl, (fluorenyl) bis (Diphenylamido) titanium methyl, (fluorenyl) bis (methylphenylamido) titanium methyl, (fluorenyl) bis (bistrimethyi) (Silylamido) titaniummethyl, (fluorenyl) bis (dimethylamido) titaniumphenyl, (fluorenyl) bis (diethylamido) titaniumphenyl, (fluorenyl) bis (dibutylamido) titaniumphenyl, (fluorenyl) bis (diphenylamido) titaniumphenyl, (fluorenyl) ) Bis (methylphenylamido) titanium phenyl, (fluorenyl) bis (bistrimethylsilylamido) titanium phenyl, (fluorenyl) bis (dimethylamido) titanium methoxide, (fluorenyl) bis (diethylamido) titanium methoxide,
(Fluorenyl) bis (dibutylamido) titanium methoxide, (fluorenyl) bis (diphenylamido) titanium methoxide, (fluorenyl) bis (methylphenylamido) titanium methoxide,
(Fluorenyl) bis (bistrimethylsilylamide)
Titanium methoxide, (fluorenyl) bis (dimethylamido) phenoxytitanium, (fluorenyl)
Bis (diethylamido) phenoxytitanium, (fluorenyl) bis (dibutylamido) phenoxytitanium, (fluorenyl) bis (diphenylamido) phenoxytitanium, (fluorenyl) bis (methylphenylamido) phenoxytitanium, (fluorenyl) bis (bistrimethylsilylamide) Phenoxytitanium, (fluorenyl) bis (dimethylamido) (acetoxy) titanium, (fluorenyl) bis (diethylamido) (acetoxy) titanium, (fluorenyl) bis (dibutylamido) (acetoxy) titanium, (fluorenyl) bis (diphenylamide) ( Acetoxy)
Titanium, (fluorenyl) bis (methylphenylamide) (acetoxy) titanium, (fluorenyl) bis (bistrimethylsilylamide) (acetoxy) titanium, (fluorenyl) bis (dimethylamide) (trimethylacetoxy) titanium, (fluorenyl) bis (diethylamide) ) (Trimethylacetoxy) titanium, (Fluorenyl) bis (dibutylamide) (trimethylacetoxy) titanium, (Fluorenyl) bis (diphenylamide) (trimethylacetoxy) titanium, (Fluorenyl) bis (methylphenylamide)
(Trimethylacetoxy) titanim, (fluorenyl)
Bis (bistrimethylsilylamide) (trimethylacetoxy) titanium,

(Fluorenyl) (dimethylamido) titanium dimethyl, (fluorenyl) (diethylamido)
Titanium dimethyl, (fluorenyl) (dibutylamido) titanium dimethyl, (fluorenyl) (diphenylamido) titanium dimethyl, (fluorenyl) (methylphenylamido) titanium dimethyl, (fluorenyl) (bistrimethylsilylamide) titanium dimethyl, (fluorenyl) (dimethyl) Amido) titanium diphenyl, (fluorenyl) (diethylamido) titanium diphenyl, (fluorenyl) (dibutylamido) titanium diphenyl, (fluorenyl) (diphenylamido) titanium diphenyl, (fluorenyl)
(Methylphenylamido) titanium diphenyl, (fluorenyl) (bistrimethylsilylamido) titanium diphenyl, (fluorenyl) (dimethylamido) titanium dimethoxide, (fluorenyl) (diethylamido) titanium dimethoxide, (fluorenyl)
(Dibutylamide) titanium dimethoxide, (fluorenyl) (diphenylamide) titanium dimethoxide, (fluorenyl) (methylphenylamide) titanium dimethoxide, (fluorenyl) (bistrimethylsilylamide) titanium dimethoxide, (fluorenyl) (Dimethylamido) diphenoxytitanium, (fluorenyl) (diethylamido) diphenoxytitanium, (fluorenyl) (dibutylamido) diphenoxytitanium, (fluorenyl) (diphenylamido) diphenoxytitanium, (fluorenyl) (methylphenylamido) diphenoxy Titanium, (fluorenyl) (bistrimethylsilylamido) diphenoxytitanium, (fluorenyl) (dimethylamido) di (acetoxy) tita Umm, (fluorenyl) (diethylamide) di (acetoxy) titanium, (fluorenyl) (dibutyl) di (acetoxy) titanium,
(Fluorenyl) (diphenylamido) di (acetoxy) titanium, (fluorenyl) (methylphenylamido) di (acetoxy) titanium, (fluorenyl)
(Bistrimethylsilylamido) di (acetoxy) titanium, (fluorenyl) (dimethylamido) di (trimethylacetoxy) titanium, (fluorenyl) (diethylamido) di (trimethylacetoxy) titanium, (fluorenyl) (dibutylamido) di (trimethylacetoxy) Titanium, (fluorenyl) (diphenylamido) di (trimethylacetoxy) titanium,
(Fluorenyl) (methylphenylamido) di (trimethylacetoxy) titanium, (Fluorenyl) (bistrimethylsilylamido) di (trimethylacetoxy)
Examples include titanium.

Further, specific examples of the compound in which the Cp group and the amide group are crosslinked include (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dimethyl, (t-butylamido) dimethyl (tetramethylcyclopentadiene). (Enyl) silane titanium diphenyl, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dimethoxide, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane diphenoxy titanium, (t-butylamide) Examples thereof include dimethyl (tetramethylcyclopentadienyl) silanedi (acetoxy) titanium and (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanedi (trimethylacetoxy) titanium.

Further, there can be mentioned similar compounds in which each amide group in these compounds is substituted with a corresponding phosphide group. Furthermore, zirconium or hafnium may be substituted for titanium in these compounds, or compounds similar to transition metal elements of other group or lanthanoid series may be mentioned, but the compounds are not limited thereto. Of these, titanium compounds are preferable from the viewpoint of catalytic activity. Moreover, you may use the mixture which combined these compounds arbitrarily.

The transition metal compound as the component (a) is a transition metal compound having two Cp groups, for example, the following general formula (11) or general formula (12) M (R ¹ R ² -A) _{a ^{Cp 1 Cp 2 Z 2-a}} ··· (11) M (R 1 R 2 -A) Cp 1 Cp 2 ··· (12) [respectively wherein, Cp ¹ and Cp ² are cyclopentadienyl groups, Substituted cyclopentadienyl group, indenyl group,
A substituted indenyl group, a fluorenyl group or a substituted fluorenyl group is shown, R ¹ , R ² , M, A and Z are the same as defined above, and a is 1 or 2. ] It is also possible to use at least one compound selected from the group consisting of transition metal compounds represented by The general formula (11) or (12)
Cp ¹ and Cp ² therein are independently the same as Cp in the general formula (9) or (10), and may be the same or different. Z is the same as Z in the general formula (9) or (10).

Specific examples of the transition metal compound containing two Cp groups represented by the general formula (11) or (12) include bis (cyclopentadienyl) bis (dimethylamido) titanium and bis (cyclopentadiene). Bis (cyclopentadienyl) bis (dibutylamido) titanium, bis (cyclopentadienyl) bis (diphenylamido) titanium, bis (cyclopentadienyl) bis (methylphenylamido) titanium , Bis (cyclopentadienyl) bis (bistrimethylsilylamido) titanium,
Bis (cyclopentadienyl) (dimethylamido) titanium, bis (cyclopentadienyl) (diethylamido) titanium methyl, bis (cyclopentadienyl)
(Dibutylamido) titanium methyl, bis (cyclopentadienyl) (diphenylamido) titanium methyl, bis (cyclopentadienyl) (methylphenylamido) titanium methyl, bis (cyclopentadienyl) (bistrimethylsilylamido) titanium methyl , Bis (cyclopentadienyl) (dimethylamide)
Titanium phenyl, bis (cyclopentadienyl)
(Diethylamido) titaniumphenyl, bis (cyclopentadienyl) (dibutylamido) titaniumphenyl, bis (cyclopentadienyl) (diphenylamido) titaniumphenyl, bis (cyclopentadienyl) (methylphenylamido) titaniumphenyl, bis (Cyclopentadienyl) (bistrimethylsilylamido) titanium phenyl, bis (cyclopentadienyl) (dimethylamido) titanium methoxide, bis (cyclopentadienyl) (diethylamido) titanium methoxide, bis (cyclopentadienyl) (Dibutylamido) titanium methoxide, bis (cyclopentadienyl) (diphenylamido) titanium methoxide, bis (cyclopentadienyl) (methylphenylamido) titanium Toxide, bis (cyclopentadienyl) (bistrimethylsilylamido) titanium methoxide, bis (cyclopentadienyl) (dimethylamido) phenoxytitanium, bis (cyclopentadienyl) (diethylamido) phenoxytitanium, bis (cyclopentadienyl) (Enyl) (dibutylamide)
Phenoxytitanium, bis (cyclopentadienyl)
(Diphenylamide) phenoxytitanium, bis (cyclopentadienyl) (methylphenylamido) phenoxytitanium, bis (cyclopentadienyl) (bistrimethylsilylamido) phenoxytitanium, bis (cyclopentadienyl) (dimethylamide) (acetoxy ) Titanium, bis (cyclopentadienyl) (diethylamido) (acetoxy) titanium, bis (cyclopentadienyl) (dibutylamido) (acetoxy)
Titanium, bis (cyclopentadienyl) (diphenylamide) (acetoxy) titanium, bis (cyclopentadienyl) (methylphenylamide) (acetoxy) titanium, bis (cyclopentadienyl) (bistrimethylsilylamide) (acetoxy) Titanium,
Bis (cyclopentadienyl) (dimethylamido) (trimethylacetoxy) titanium, bis (cyclopentadienyl) (diethylamido) (trimethylacetoxy) titanium, bis (cyclopentadienyl) (dibutylamido) (trimethylacetoxy) titanium, Bis (cyclopentadienyl) (diphenylamide) (trimethylacetoxy) titanium, bis (cyclopentadienyl) (methylphenylamide) (trimethylacetoxy) titanium, bis (cyclopentadienyl)
(Bistrimethylsilylamide) (trimethylacetoxy) titanium,

Bis (pentamethylcyclopentadienyl) bis (dimethylamido) titanium, bis (pentamethylcyclopentadienyl) bis (diethylamide)
Titanium, bis (pentamethylcyclopentadienyl) bis (dibutylamido) titanium, bis (pentamethylcyclopentadienyl) bis (diphenylamido) titanium, bis (pentamethylcyclopentadienyl) bis (methylphenylamido) titanium , Bis (pentamethylcyclopentadienyl) bis (bistrimethylsilylamido) titanium, bis (pentamethylcyclopentadienyl) (dimethylamido) titanium, bis (pentamethylcyclopentadienyl) (diethylamido) titaniummethyl, bis ( Pentamethylcyclopentadienyl) (dibutylamido) titanium methyl, bis (pentamethylcyclopentadienyl) (diphenylamido) titanium methyl, bis (pentamethylcyclopentadienyl) (Methylphenylamido) titanium methyl, bis (pentamethylcyclopentadienyl) (bistrimethylsilylamido) titaniummethyl, bis (pentamethylcyclopentadienyl) (dimethylamido) titaniumphenyl, bis (pentamethylcyclopentadienyl) (Diethylamido) titanium phenyl, bis (pentamethylcyclopentadienyl)
(Dibutylamido) titaniumphenyl, bis (pentamethylcyclopentadienyl) (diphenylamido) titaniumphenyl, bis (pentamethylcyclopentadienyl) (methylphenylamido) titaniumphenyl, bis (pentamethylcyclopentadienyl) ( Bis (trimethylsilylamido) titaniumphenyl, bis (pentamethylcyclopentadienyl) (dimethylamido) titanium methoxide, bis (pentamethylcyclopentadienyl) (diethylamido) titanium methoxide, bis (pentamethylcyclopentadienyl)
(Dibutylamido) titanium methoxide, bis (pentamethylcyclopentadienyl) (diphenylamido) titanium methoxide, bis (pentamethylcyclopentadienyl) (methylphenylamido) titanium methoxide, bis (pentamethylcyclopentadiene) (Enyl) (bistrimethylsilylamido) titanium methoxide, bis (pentamethylcyclopentadienyl)
(Dimethylamido) phenoxytitanium, bis (pentamethylcyclopentadienyl) (diethylamido) phenoxytitanium, bis (pentamethylcyclopentadienyl) (dibutylamido) phenoxytitanium,
Bis (pentamethylcyclopentadienyl) (diphenylamido) phenoxytitanium, bis (pentamethylcyclopentadienyl) (methylphenylamido) phenoxytitanium, bis (pentamethylcyclopentadienyl) (bistrimethylsilylamido) phenoxytitanium, Bis (pentamethylcyclopentadienyl)
(Dimethylamido) (acetoxy) titanium, bis (pentamethylcyclopentadienyl) (diethylamido) (acetoxy) titanium, bis (pentamethylcyclopentadienyl) (dibutylamido) (acetoxy) titanium, bis (pentamethylcyclopenta) Dienyl) (diphenylamido) (acetoxy) titanium, bis (pentamethylcyclopentadienyl) (methylphenylamido) (acetoxy) titanium, bis (pentamethylcyclopentadienyl) (bistrimethylsilylamido) (acetoxy) titanium, Bis (pentamethylcyclopentadienyl) (dimethylamide)
(Trimethylacetoxy) titanium, bis (pentamethylcyclopentadienyl) (diethylamido) (trimethylacetoxy) titanium, bis (pentamethylcyclopentadienyl) (dibutylamido) (trimethylacetoxy) titanium, bis (pentamethylcyclopentadiene) (Phenyl) (diphenylamido) (trimethylacetoxy) titanium, bis (pentamethylcyclopentadienyl) (methylphenylamido) (trimethylacetoxy) titanium, bis (pentamethylcyclopentadienyl) (bistrimethylsilylamide) (trimethylacetoxy) Titanium,

Bis (indenyl) bis (dimethylamido) titanium, bis (indenyl) bis (diethylamido) titanium, bis (indenyl) bis (dibutylamido) titanium, bis (indenyl) bis (diphenylamido) titanium, bis (indenyl) Bis (methylphenylamido) titanium, bis (indenyl)
Bis (bistrimethylsilylamido) titanium, bis (indenyl) (dimethylamido) titanium, bis (indenyl) (diethylamido) titaniummethyl,
Bis (indenyl) (dibutylamido) titanium methyl, bis (indenyl) (diphenylamido) titanium methyl, bis (indenyl) (methylphenylamido) titanium methyl, bis (indenyl) (bistrimethylsilylamido) titanium methyl, bis (indenyl) (Dimethylamido) titaniumphenyl, bis (indenyl) (diethylamido) titaniumphenyl, bis (indenyl) (dibutylamido) titaniumphenyl, bis (indenyl) (diphenylamido) titaniumphenyl, bis (indenyl) (methylphenylamido) titaniumphenyl , Bis (indenyl)
(Bistrimethylsilylamide) titanium phenyl,
Bis (indenyl) (dimethylamido) titanium methoxide, bis (indenyl) (diethylamido) titanium methoxide, bis (indenyl) (dibutylamido) titanium methoxide, bis (indenyl)
(Diphenylamido) titanium methoxide, bis (indenyl) (methylphenylamido) titanium methoxide, bis (indenyl) (bistrimethylsilylamido) titanium methoxide, bis (indenyl) (dimethylamido) phenoxytitanium, bis (indenyl) ( Diethylamido) phenoxytitanium, bis (indenyl) (dibutylamido) phenoxytitanium, bis (indenyl) (diphenylamide)
Phenoxytitanium, bis (indenyl) (methylphenylamido) phenoxytitanium, bis (indenyl) (bistrimethylsilylamido) phenoxytitanium, bis (indenyl) (dimethylamido) (acetoxy) titanium, bis (indenyl) (diethylamido) (acetoxy) Titanium, bis (indenyl)
(Dibutylamide) (acetoxy) titanium, bis (indenyl) (diphenylamide) (acetoxy) titanium, bis (indenyl) (methylphenylamide) (acetoxy) titanium, bis (indenyl)
(Bistrimethylsilylamido) (acetoxy) titanium, bis (indenyl) (dimethylamido) (trimethylacetoxy) titanium, bis (indenyl) (diethylamido) (trimethylacetoxy) titanium,
Bis (indenyl) (dibutylamide) (trimethylacetoxy) titanium, bis (indenyl) (diphenylamido) (trimethylacetoxy) titanium, bis (indenyl) (methylphenylamide) (trimethylacetoxy) titanium, bis (indenyl) (bistrimethylsilyl) Amide) (trimethylacetoxy) titanium and the like.

Further, similar compounds in which each amide group in these compounds is substituted with a corresponding phosphide group can be mentioned. Furthermore, zirconium or hafnium may be substituted for titanium in these compounds, or compounds similar to transition metal elements of other group or lanthanoid series may be mentioned, but the compounds are not limited thereto. Of these, titanium compounds are preferable from the viewpoint of catalytic activity. Moreover, you may use the mixture which combined these compounds arbitrarily.

In the above general formula (11) or (12), Cp ¹ and Cp ² are alkylene groups having 1 to 5 carbon atoms,
Alkylidene group having 1 to 8 carbon atoms (specifically, ethylidene group, propylidene group, dimethylcarbyl group, etc.) or alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, dimethylsilyl group) Group, a diethylsilyl group, a dibenzylsilyl group, etc.). Specifically, for example, the following general formula (13)

[0031]

Embedded image [Wherein R ¹ , R ² , A, Cp, M and Z are the same as defined above, Q is a methylene group, an ethylene group, a dimethylsilylene group, a diethylsilylene group or a phenylene group, and
Is 1 or 2. And the like.

Specific examples of the transition metal compound containing two Cp groups represented by the above general formula (13) and bridging these are dimethylsilylbis (cyclopentadienyl) bis (dimethylamido) titanium and dimethyl. Silylbis (cyclopentadienyl) bis (diethylamido) titanium, dimethylsilylbis (cyclopentadienyl) bis (dibutylamido) titanium, dimethylsilylbis (cyclopentadienyl) bis (diphenylamido) titanium, dimethylsilylbis ( Cyclopentadienyl) bis (methylphenylamido) titanium, dimethylsilylbis (cyclopentadienyl) bis (bistrimethylsilylamido) titanium, dimethylsilylbis (cyclopentadienyl) (dimethylamido) titanium, dimethyl Rylbis (cyclopentadienyl) (diethylamido) titaniummethyl, dimethylsilylbis (cyclopentadienyl) (dibutylamido) titaniummethyl, dimethylsilylbis (cyclopentadienyl) (diphenylamido) titaniummethyl, dimethylsilylbis (cyclo Pentadienyl) (methylphenylamido) titaniummethyl, dimethylsilylbis (cyclopentadienyl) (bistrimethylsilylamido) titaniummethyl, dimethylsilylbis (cyclopentadienyl) (dimethylamido) titaniumphenyl, dimethylsilylbis (cyclo) Pentadienyl)
(Diethylamido) titaniumphenyl, dimethylsilylbis (cyclopentadienyl) (dibutylamido) titaniumphenyl, dimethylsilylbis (cyclopentadienyl) (diphenylamido) titaniumphenyl,
Dimethylsilylbis (cyclopentadienyl) (methylphenylamido) titaniumphenyl, dimethylsilylbis (cyclopentadienyl) (bistrimethylsilylamido) titaniumphenyl, dimethylsilylbis (cyclopentadienyl) (dimethylamido) titanium methoxide , Dimethylsilylbis (cyclopentadienyl) (diethylamido) titanium methoxide, dimethylsilylbis (cyclopentadienyl) (dibutylamido) titanium methoxide, dimethylsilylbis (cyclopentadienyl) (diphenylamido) titanium methoxide , Dimethylsilylbis (cyclopentadienyl) (methylphenylamido) titanium methoxide, dimethylsilylbis (cyclopentadienyl)
(Bistrimethylsilylamido) titanium methoxide, dimethylsilylbis (cyclopentadienyl) (dimethylamido) phenoxytitanium, dimethylsilylbis (cyclopentadienyl) (diethylamido) phenoxytitanium, dimethylsilylbis (cyclopentadienyl) ( Dibutylamide) phenoxytitanium,
Dimethylsilylbis (cyclopentadienyl) (diphenylamide) phenoxytitanium, dimethylsilylbis (cyclopentadienyl) (methylphenylamide)
Phenoxytitanium, dimethylsilylbis (cyclopentadienyl) (bistrimethylsilylamide) phenoxytitanium, dimethylsilylbis (cyclopentadienyl) (dimethylamide) (acetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (diethylamide) (Acetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (dibutylamide)
(Acetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (diphenylamide) (acetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (methylphenylamide) (acetoxy) titanium, dimethylsilylbis (cyclopentadienyl) )
(Bistrimethylsilylamide) (acetoxy) titanium, dimethylsilylbis (cyclopentadienyl)
(Dimethylamido) (trimethylacetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (diethylamido) (trimethylacetoxy) titanium,
Dimethylsilylbis (cyclopentadienyl) (dibutylamide) (trimethylacetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (diphenylamide) (trimethylacetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (methylphenyl Amido) (trimethylacetoxy) titanium, dimethylsilylbis (cyclopentadienyl) (bistrimethylsilylamido) (trimethylacetoxy) titanium,

Dimethylsilylbis (indenyl) bis (dimethylamido) titanium, dimethylsilylbis (indenyl) bis (diethylamido) titanium, dimethylsilylbis (indenyl) bis (dibutylamido) titanium, dimethylsilylbis (indenyl) bis (diphenyl) Amido) titanium, dimethylsilylbis (indenyl) bis (methylphenylamido) titanium, dimethylsilylbis (indenyl) bis (bistrimethylsilylamido) titanium, dimethylsilylbis (indenyl) (dimethylamido) titanium, dimethylsilylbis (indenyl) (Diethylamido) titanium methyl, dimethylsilylbis (indenyl) (dibutylamido) titanium methyl, dimethylsilylbis (indenyl) (dife (Lamido) titanium methyl, dimethylsilylbis (indenyl) (methylphenylamido) titaniummethyl, dimethylsilylbis (indenyl) (bistrimethylsilylamido) titaniummethyl, dimethylsilylbis (indenyl) (dimethylamido) titaniumphenyl, dimethylsilylbis ( Indenyl) (diethylamido) titaniumphenyl, dimethylsilylbis (indenyl) (dibutylamido) titaniumphenyl, dimethylsilylbis (indenyl)
(Diphenylamide) titanium phenyl, dimethylsilylbis (indenyl) (methylphenylamido) titanium phenyl, dimethylsilylbis (indenyl)
(Bistrimethylsilylamide) titanium phenyl,
Dimethylsilylbis (indenyl) (dimethylamide)
Titanium methoxide, dimethylsilylbis (indenyl) (diethylamido) titanium methoxide, dimethylsilylbis (indenyl) (dibutylamido) titanium methoxide, dimethylsilylbis (indenyl) (diphenylamido) titanium methoxide, dimethylsilylbis (indenyl) ) (Methylphenylamido) titanium methoxide, dimethylsilylbis (indenyl) (bistrimethylsilylamido) titanium methoxide, dimethylsilylbis (indenyl) (dimethylamido) phenoxytitanium, dimethylsilylbis (indenyl) (diethylamido) phenoxytitanium, Dimethylsilylbis (indenyl) (dibutylamido) phenoxytitanium, dimethylsilylbis (indenyl) (di Eniruamido) phenoxy titanium, dimethylsilyl bis (indenyl) (methyl phenyl amide) phenoxy titanium, dimethylsilyl bis (indenyl) (bistrimethylsilylamide) phenoxy titanium, dimethylsilyl bis (indenyl)
(Dimethylamide) (acetoxy) titanium, dimethylsilylbis (indenyl) (diethylamide) (acetoxy) titanium, dimethylsilylbis (indenyl) (dibutylamide) (acetoxy) titanium, dimethylsilylbis (indenyl) (diphenylamide)
(Acetoxy) titanium, dimethylsilylbis (indenyl) (methylphenylamide) (acetoxy) titanium, dimethylsilylbis (indenyl) (bistrimethylsilylamide) (acetoxy) titanium, dimethylsilylbis (indenyl) (dimethylamide) (trimethylacetoxy) ) Titanium, dimethylsilylbis (indenyl) (diethylamido) (trimethylacetoxy) titanium, dimethylsilylbis (indenyl)
(Dibutylamide) (trimethylacetoxy) titanium, dimethylsilylbis (indenyl) (diphenylamide) (trimethylacetoxy) titanium, dimethylsilylbis (indenyl) (methylphenylamide)
(Trimethylacetoxy) titanium, dimethylsilylbis (indenyl) (bistrimethylsilylamide)
(Trimethylacetoxy) titanium and the like can be mentioned.

Further, there can be mentioned similar compounds in which each amide group in these compounds is substituted with a corresponding phosphide group. Furthermore, zirconium or hafnium may be substituted for titanium in these compounds, or compounds similar to transition metal elements of other group or lanthanoid series may be mentioned, but the compounds are not limited thereto. Of these, titanium compounds are preferable from the viewpoint of catalytic activity. Moreover, you may use the mixture which combined these compounds arbitrarily.

Further, as the transition metal compound of the component (a), in the above general formula (9) or (10), especially Cp
There is at least one compound selected from the group consisting of transition metal compounds in which the group is a fused polycyclic cyclopentadienyl group in which at least one of the fused multi-membered rings is a saturated ring. Examples of such fused polycyclic cyclopentadienyl groups include those represented by the general formulas (14) to (16)

[0036]

[Chemical 6]

[In the formula, R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon number. 1
Alkoxy group having 20 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, carbon group having 6 to 2 carbon atoms
0 represents a thioaryloxy group, an amino group, an amido group, a carboxyl group or an alkylsilyl group, each R ⁷ , each R ⁸
And each R ⁹ may be the same as or different from each other, and r, s, t and u represent an integer of 1 or more. ] The thing selected from the condensed polycyclic cyclopentadienyl group represented by these can be mentioned. Specific examples of the condensed polycyclic cyclopentadienyl group include 4,5,6,7
-Tetrahydroindenyl group; 1-methyl-4,5,
6,7-tetrahydroindenyl group; 2-methyl-4,
5,6,7-tetrahydroindenyl group; 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group;
1,3-dimethyl-4,5,6,7-tetrahydroindenyl group; 1,2,3-trimethyl-4,5,6,7-
Tetrahydroindenyl group; 1,2,3,4,5,6
7-heptamethyl-4,5,6,7-tetrahydroindenyl group; 1,2,4,5,6,7-hexamethyl-
4,5,6,7-tetrahydroindenyl group;
4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl group; octahydrofluorenyl group;
1,2,3,4-tetrahydrofluorenyl group; 9-methyl-1,2,3,4-tetrahydrofluorenyl group;
1,2,3,4,5,6,7,8-octahydrofluorenyl group; 9-methyl-octahydrofluorenyl group and the like.

Examples of the transition metal compound having such a fused polycyclic cyclopentadienyl group include (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) tris (dimethylamido) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) tris (diethylamido) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) tris (dibutylamido) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) tris (diphenylamido) titanium,
(1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) tris (methylphenylamido) titanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) tris ( Bistrimethylsilylamido) titanium, (1,2,3trimethyl-4,5,5
6,7-Tetrahydroindenyl) bis (dimethylamido) titaniummethyl, (1,2,3trimethyl-4,
5,6,7-Tetrahydroindenyl) bis (diethylamido) titanium methyl, (1,2,3 trimethyl-
4,5,6,7-Tetrahydroindenyl) bis (dibutylamido) titaniummethyl, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titaniummethyl, (1 , 2, 3
Trimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) titanium methyl,
(1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methyl, (1,2,3 trimethyl-4,5,5
6,7-Tetrahydroindenyl) bis (dimethylamido) titaniumphenyl, (1,2,3trimethyl-
4,5,6,7-Tetrahydroindenyl) bis (diethylamido) titaniumphenyl, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titaniumphenyl, (1, A few
Trimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titaniumphenyl,
(1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) titanium phenyl, (1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium phenyl,

(1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) bis (dimethylamido) titanium methoxide, (1,2,3 trimethyl-4,
5,6,7-Tetrahydroindenyl) bis (diethylamido) titanium methoxide, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titanium methoxide, (1,2
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titanium methoxide, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenyl Amido) titanium methoxide, (1,2,3 trimethyl-4,
5,6,7-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methoxide, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) phenoxytitanium, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) phenoxy Titanium, (1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) bis (dibutylamido) phenoxytitanium, (1,2,3trimethyl-4,
5,6,7-tetrahydroindenyl) bis (diphenylamido) phenoxytitanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) phenoxytitanium,
(1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) bis (bistrimethylsilylamido) phenoxytitanium, (1,2,3trimethyl-4,
5,6,7-tetrahydroindenyl) bis (dimethylamido) (acetoxy) titanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) (acetoxy) titanium,
(1,2,3 Trimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamide) (acetoxy)
Titanium, (1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) bis (diphenylamide)
(Acetoxy) titanium, (1,2,3 trimethyl-
4,5,6,7-Tetrahydroindenyl) bis (methylphenylamido) (acetoxy) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (1,2,3 trimethyl-4,
5,6,7-Tetrahydroindenyl) bis (dimethylamido) (trimethylacetoxy) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) (trimethylacetoxy) titanium, (1,2,3 trimethyl-4,5,5
6,7-Tetrahydroindenyl) bis (dibutylamido) (trimethylacetoxy) titanium, (1,2,
3 trimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) (trimethylacetoxy) titanium, (1,2,3 trimethyl-4,5,5
6,7-tetrahydroindenyl) bis (methylphenylamide) (trimethylacetoxy) titanium,
(1,2,3 Trimethyl-4,5,6,7-tetrahydroindenyl) bis (bistrimethylsilylamide)
(Trimethylacetoxy) titanium,

(1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) (dimethylamido) titanium dimethyl, (1,2,3 trimethyl-4,5,6,6)
7-Tetrahydroindenyl) (diethylamido) titanium dimethyl, (1,2,3 trimethyl-4,5,5
6,7-Tetrahydroindenyl) (dibutylamide)
Titanium dimethyl, (1,2,3 trimethyl-4,
5,6,7-Tetrahydroindenyl) (diphenylamido) titanium dimethyl, (1,2,3 trimethyl-
4,5,6,7-Tetrahydroindenyl) (methylphenylamido) titanium dimethyl, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl)
(Bistrimethylsilylamide) titanium dimethyl,
(1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) titanium diphenyl, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) Titanium diphenyl, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamido) titanium diphenyl, (1,2,3 trimethyl-4,5,6,7)
-Tetrahydroindenyl) (diphenylamido) titanium diphenyl, (1,2,3 trimethyl-4,5,5
6,7-Tetrahydroindenyl) (methylphenylamido) titanium diphenyl, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium diphenyl, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) titanium dimethoxide, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) titanium Dimethoxide, (1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) (dibutylamido) titanium dimethoxide, (1,2,3 trimethyl-4,
5,6,7-tetrahydroindenyl) (diphenylamido) titanium dimethoxide, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamido) titanium dimethoxide,
(1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium dimethoxide, (1,2,3 trimethyl-4,
5,6,7-Tetrahydroindenyl) (dimethylamido) diphenoxytitanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) diphenoxytitanium, (1,2,3) 3 trimethyl-4,5,6,7-tetrahydroindenyl)
(Dibutylamide) diphenoxytitanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) diphenoxytitanium, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamide) Diphenoxytitanium, (1,2,3 trimethyl-4,5,
6,7-tetrahydroindenyl) (bistrimethylsilylamido) diphenoxytitanium,

(1,2,3 trimethyl-4,5,6,7
-Tetrahydroindenyl) (dimethylamido) di (acetoxy) titanium, (1,2,3trimethyl-4,
5,6,7-Tetrahydroindenyl) (diethylamido) di (acetoxy) titanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamido) di (acetoxy) titanium, ( 1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) di (acetoxy) titanium, (1,2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (methylphenyl Amido) di (acetoxy) titanium, (1,2,3trimethyl-4,
5,6,7-Tetrahydroindenyl) (bistrimethylsilylamido) di (acetoxy) titanium, (1,
2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) di (trimethylacetoxy) titanium, (1,2,3 trimethyl-4,5,5
6,7-Tetrahydroindenyl) (diethylamide)
Di (trimethylacetoxy) titanium, (1,2,3
Trimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamido) di (trimethylacetoxy) titanium, (1,2,3 trimethyl-4,5,6,7-
Tetrahydroindenyl) (diphenylamido) di (trimethylacetoxy) titanium, (1,2,3trimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamido) di (trimethylacetoxy) titanium, (1, 2,3 trimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) tris (dimethylamido) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) tris ( Diethylamido) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) tris (dibutylamido) titanium,
(1,2-dimethyl-4,5,6,7-tetrahydroindenyl) tris (diphenylamido) titanium,
(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) tris (methylphenylamido) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) tris (bistrimethylsilyl) Amide)
Titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) titanium methyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis ( Diethylamido) titanium methyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titanium methyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) ) Bis (diphenylamido) titanium methyl, (1,2-dimethyl-4,5,6,7-
Tetrahydroindenyl) bis (methylphenylamido) titanium methyl, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) titaniumphenyl, (1,2-dimethyl) -4,5,6,7-Tetrahydroindenyl) bis (diethylamido) titaniumphenyl, (1,2-
Dimethyl-4,5,6,7-tetrahydroindenyl)
Bis (dibutylamido) titaniumphenyl, (1,2
-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titaniumphenyl,
(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) titaniumphenyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (bis Trimethylsilylamido) titanium phenyl, (1,2-dimethyl-4,
5,6,7-Tetrahydroindenyl) bis (dimethylamido) titanium methoxide, (1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) titanium methoxide, (1,2 -Dimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titanium methoxide, (1,
2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titanium methoxide, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamide) Titanium methoxide, (1,2-dimethyl-4,5,6,7
-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methoxide,

(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) phenoxytitanium, (1,2-dimethyl-4,5,6,7)
-Tetrahydroindenyl) bis (diethylamido) phenoxytitanium, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) bis (dibutylamido) phenoxytitanium, (1,2-dimethyl-4,
5,6,7-Tetrahydroindenyl) bis (diphenylamido) phenoxytitanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) phenoxytitanium, (1,2
-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (bistrimethylsilylamido) phenoxytitanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) (acetoxy ) Titanium, (1,2-dimethyl-4,5,6,6)
7-Tetrahydroindenyl) bis (diethylamide)
(Acetoxy) titanium, (1,2-dimethyl-4,
5,6,7-tetrahydroindenyl) bis (dibutylamido) (acetoxy) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) (acetoxy) titanium,
(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) (acetoxy) titanium, (1,2-dimethyl-4,5,6,7)
-Tetrahydroindenyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) (trimethylacetoxy) titanium, (1,2 -Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) (trimethylacetoxy) titanium, (1,2-dimethyl-4,
5,6,7-Tetrahydroindenyl) bis (dibutylamido) (trimethylacetoxy) titanium, (1,
2-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) (trimethylacetoxy) titanium, (1,2-dimethyl-4,5,6,7)
-Tetrahydroindenyl) bis (methylphenylamido) (trimethylacetoxy) titanium, (1,2-
Dimethyl-4,5,6,7-tetrahydroindenyl)
Bis (bistrimethylsilylamide) (trimethylacetoxy) titanium,

(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) titanium dimethyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (diethylamide) ) Titanium dimethyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamido) titanium dimethyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) ( (Diphenylamido) titanium dimethyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamido) titanium dimethyl, (1,2-dimethyl-4,5,6,7-tetrahydroindene) Nil) (bistrimethylsilylamide)
Titanium dimethyl, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) (dimethylamide)
Titanium diphenyl, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) (diethylamide)
Titanium diphenyl, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) (dibutylamide)
Titanium diphenyl, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) (diphenylamido) titanium diphenyl, (1,2-dimethyl-4,
5,6,7-Tetrahydroindenyl) (methylphenylamido) titanium diphenyl, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium diphenyl, (1,
2-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) titanium dimethoxide,
(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) titanium dimethoxide, (1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamide) Titanium dimethoxide, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) titanium dimethoxide, (1,2-dimethyl-4,5,6,7-
Tetrahydroindenyl) (methylphenylamido) titanium dimethoxide, (1,2-dimethyl-4,
5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium dimethoxide,

(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) diphenoxytitanium, (1,2-dimethyl-4,5,6,7-
Tetrahydroindenyl) (diethylamido) diphenoxytitanium, (1,2-dimethyl-4,5,6,7
-Tetrahydroindenyl) (dibutylamido) diphenoxytitanium, (1,2-dimethyl-4,5,6,6)
7-tetrahydroindenyl) (diphenylamido) diphenoxytitanium, (1,2-dimethyl-4,5,
6,7-Tetrahydroindenyl) (methylphenylamido) diphenoxytitanium, (1,2-dimethyl-
4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) diphenoxytitanium, (1,
2-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) di (acetoxy) titanium,
(1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) di (acetoxy) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamide) ) Di (acetoxy)
Titanium, (1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) di (acetoxy) titanium, (1,2-Dimethyl-4,5,5
6,7-Tetrahydroindenyl) (methylphenylamido) di (acetoxy) titanium, (1,2-Dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) di (acetoxy) titanium, ( 1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) di (trimethylacetoxy) titanium, (1,2-dimethyl-4,5,5
6,7-Tetrahydroindenyl) (diethylamide)
Di (trimethylacetoxy) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl)
(Dibutylamido) di (trimethylacetoxy) titanium, (1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) di (trimethylacetoxy) titanium, (1,2-dimethyl-4,
5,6,7-tetrahydroindenyl) (methylphenylamido) di (trimethylacetoxy) titanium,
(1,2-dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) tris (dimethylamido) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) tris ( Diethylamido) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) tris (dibutylamido) titanium,
(1,3-dimethyl-4,5,6,7-tetrahydroindenyl) tris (diphenylamido) titanium,
(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) tris (methylphenylamido) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) tris (bistrimethylsilyl) Amide)
Titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) titanium methyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis ( Diethylamido) titanium methyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titanium methyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) ) Bis (diphenylamido) titanium methyl, (1,3-dimethyl-4,5,6,7-
Tetrahydroindenyl) bis (methylphenylamido) titanium methyl, (1,3-dimethyl-4,5,5
6,7-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) titaniumphenyl, (1,3-dimethyl) -4,5,6,7-Tetrahydroindenyl) bis (diethylamido) titaniumphenyl, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
Bis (dibutylamido) titaniumphenyl, (1,3
-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titaniumphenyl,
(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamido) titaniumphenyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (bis Trimethylsilylamido) titanium phenyl, (1,3-dimethyl-4,
5,6,7-Tetrahydroindenyl) bis (dimethylamido) titanium methoxide, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) titanium methoxide, (1,3 -Dimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) titanium methoxide, (1,
3-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) titanium methoxide, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamide) Titanium methoxide, (1,3-dimethyl-4,5,6,7
-Tetrahydroindenyl) bis (bistrimethylsilylamido) titanium methoxide, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) phenoxytitanium, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
Bis (diethylamido) phenoxytitanium, (1,
3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dibutylamido) phenoxytitanium,
(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) phenoxytitanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenyl Amido) phenoxytitanium, (1,3-dimethyl-4,5,6,7
-Tetrahydroindenyl) bis (bistrimethylsilylamido) phenoxytitanium,

(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) (acetoxy) titanium, (1,3-dimethyl-4,5,5)
6,7-Tetrahydroindenyl) bis (diethylamido) (acetoxy) titanium, (1,3-dimethyl-
4,5,6,7-Tetrahydroindenyl) bis (dibutylamido) (acetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) (acetoxy) titanium ,
(1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (methylphenylamide) (acetoxy) titanium, (1,3-dimethyl-4,5,6,7)
-Tetrahydroindenyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (dimethylamido) (trimethylacetoxy) titanium, (1,3 -Dimethyl-4,5,6,7-tetrahydroindenyl) bis (diethylamido) (trimethylacetoxy) titanium, (1,3-dimethyl-4,
5,6,7-Tetrahydroindenyl) bis (dibutylamido) (trimethylacetoxy) titanium, (1,
3-dimethyl-4,5,6,7-tetrahydroindenyl) bis (diphenylamido) (trimethylacetoxy) titanium, (1,3-dimethyl-4,5,6,7)
-Tetrahydroindenyl) bis (methylphenylamido) (trimethylacetoxy) titanium, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
Bis (bistrimethylsilylamide) (trimethylacetoxy) titanium, (1,3-dimethyl-4,5,5
6,7-Tetrahydroindenyl) (dimethylamide)
Titanium dimethyl, (1,3-dimethyl-4,5,
6,7-Tetrahydroindenyl) (diethylamide)
Titanium dimethyl, (1,3-dimethyl-4,5,
6,7-Tetrahydroindenyl) (dibutylamide)
Titanium dimethyl, (1,3-dimethyl-4,5,
6,7-Tetrahydroindenyl) (diphenylamido) titanium dimethyl, (1,3-dimethyl-4,
5,6,7-Tetrahydroindenyl) (methylphenylamido) titanium dimethyl, (1,3-dimethyl-
4,5,6,7-Tetrahydroindenyl) (bistrimethylsilylamido) titanium dimethyl, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
(Dimethylamido) titanium diphenyl, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
(Diethylamido) titanium diphenyl, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
(Dibutylamido) titanium diphenyl, (1,3-
Dimethyl-4,5,6,7-tetrahydroindenyl)
(Diphenylamide) titanium diphenyl, (1,3
-Dimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamido) titanium diphenyl,
(1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium diphenyl,

(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) titanium dimethoxide, (1,3-dimethyl-4,5,6,7)
-Tetrahydroindenyl) (diethylamido) titanium dimethoxide, (1,3-dimethyl-4,5,
6,7-Tetrahydroindenyl) (dibutylamide)
Titanium dimethoxide, (1,3-dimethyl-4,
5,6,7-Tetrahydroindenyl) (diphenylamido) titanium dimethoxide, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (methylphenylamido) titanium dimethoxide, (1 , 3
-Dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) titanium dimethoxide, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) diphenoxy Titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) diphenoxytitanium, (1,3-dimethyl-4,5,6,7-
Tetrahydroindenyl) (dibutylamido) diphenoxytitanium, (1,3-dimethyl-4,5,6,7
-Tetrahydroindenyl) (diphenylamido) diphenoxytitanium, (1,3-dimethyl-4,5,
6,7-Tetrahydroindenyl) (methylphenylamido) diphenoxytitanium, (1,3-dimethyl-
4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) diphenoxytitanium, (1,
3-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) di (acetoxy) titanium,
(1,3-Dimethyl-4,5,6,7-tetrahydroindenyl) (diethylamido) di (acetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (dibutylamide) ) Di (acetoxy)
Titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) di (acetoxy) titanium, (1,3-dimethyl-4,5,5
6,7-Tetrahydroindenyl) (methylphenylamido) di (acetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) di (acetoxy) titanium, ( 1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (dimethylamido) di (trimethylacetoxy) titanium, (1,3-dimethyl-4,5,5
6,7-Tetrahydroindenyl) (diethylamide)
Di (trimethylacetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl)
(Dibutylamido) di (trimethylacetoxy) titanium, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (diphenylamido) di (trimethylacetoxy) titanium, (1,3-dimethyl-4,
5,6,7-tetrahydroindenyl) (methylphenylamido) di (trimethylacetoxy) titanium,
(1,3-dimethyl-4,5,6,7-tetrahydroindenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(1,2,3,4,5,6,7,8-octahydrofluorenyl) tris (dimethylamido) titanium, (1,2,3,4,5,6,7,8- Octahydrofluorenyl) tris (diethylamido) titanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) tris (dibutylamido) titanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) tris (diphenylamido) titanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) tris (methylphenylamido) titanium, (1,2,3,4,5,6,7,8-octahydro Fluorenyl) tris (bistrimethylsilylamide)
Titanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) titanium methyl, (1,2,3,4,5,6,7,8- Octahydrofluorenyl) bis (diethylamido) titanium methyl, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) titanium methyl, (1,2,3 , 4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) titanium methyl, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis ( Methylphenylamido) titanium methyl, (1, 2, 3, 4, 5, 6,
7,8-Octahydrofluorenyl) bis (bistrimethylsilylamido) titanium methyl, (1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) titaniumphenyl, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (diethylamido) titaniumphenyl, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) titaniumphenyl,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) titaniumphenyl, (1,2,3,4,5,6,7,8-octahydro Fluorenyl) bis (methylphenylamido) titaniumphenyl, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (bistrimethylsilylamido) titaniumphenyl, (1,2,2 3, 4, 5,
6,7,8-octahydrofluorenyl) bis (dimethylamido) titanium methoxide, (1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) titanium methoxide, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) titanium methoxide,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) titanium methoxide, (1,2,3,4,5,6,7,8-octa Hydrofluorenyl) bis (methylphenylamido) titanium methoxide, (1,2,3,4,5,6,7,
8-octahydrofluorenyl) bis (bistrimethylsilylamido) titanium methoxide, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (dimethylamido) phenoxytitanium, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) phenoxytitanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) phenoxytitanium, (1,2,3,4,5,6,7,8-octahydro Fluorenyl) bis (diphenylamido) phenoxytitanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (methylphenylamido) phenoxytitanium, (1,2,3 , 4, 5, 6, 7,
8-octahydrofluorenyl) bis (bistrimethylsilylamido) phenoxytitanium,

(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) (acetoxy) titanium, (1,2,3,4,5,6,7) ，
8-octahydrofluorenyl) bis (diethylamido) (acetoxy) titanium, (1,2,3,4,
5,6,7,8-octahydrofluorenyl) bis (dibutylamido) (acetoxy) titanium, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (diphenylamide) (acetoxy) titanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (methylphenylamide) (acetoxy) titanium, (1,2,3,4,5,6,7,8 −
Octahydrofluorenyl) bis (bistrimethylsilylamido) (acetoxy) titanium, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (dimethylamido) (trimethylacetoxy) titanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) (trimethylacetoxy) titanium, (1,2,3 , 4, 5,
6,7,8-octahydrofluorenyl) bis (dibutylamido) (trimethylacetoxy) titanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diphenylamide) (trimethylacetoxy) titanium, (1,2,3,4,5,6,7,
8-octahydrofluorenyl) bis (methylphenylamido) (trimethylacetoxy) titanium, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (bistrimethylsilylamide) (trimethylacetoxy) titanium, (1,2,3,4,5,6,6)
7,8-Octahydrofluorenyl) (dimethylamido) titanium dimethyl, (1,2,3,4,5,6,6)
7,8-Octahydrofluorenyl) (diethylamido) titanium dimethyl, (1,2,3,4,5,6,6)
7,8-Octahydrofluorenyl) (dibutylamido) titanium dimethyl, (1,2,3,4,5,6,
7,8-Octahydrofluorenyl) (diphenylamido) titanium dimethyl, (1,2,3,4,5,6,6)
7,8-Octahydrofluorenyl) (methylphenylamido) titanium dimethyl, (1,2,3,4,5,5
6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) titanium dimethyl, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Dimethylamido) titanium diphenyl, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Diethylamido) titanium diphenyl, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Dibutylamido) titanium diphenyl, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Diphenylamide) titanium diphenyl, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) (methylphenylamido) titanium diphenyl,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) titanium diphenyl, (1,2,3,4,5,6,7,8-octahydro Fluorenyl) (dimethylamido) titanium dimethoxide, (1,2,3,4,5,6,7,8-
Octahydrofluorenyl) (diethylamido) titanium dimethoxide, (1,2,3,4,5,6,7,
8-octahydrofluorenyl) (dibutylamido) titanium dimethoxide, (1,2,3,4,5,6,6)
7,8-octahydrofluorenyl) (diphenylamido) titanium dimethoxide, (1,2,3,4,
5,6,7,8-octahydrofluorenyl) (methylphenylamido) titanium dimethoxide, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) titanium dimethoxide,

(1,2,3,4,5,6,7,8-octahydrofluorenyl) (dimethylamido) diphenoxytitanium, (1,2,3,4,5,6,7,8) -Octahydrofluorenyl) (diethylamido) diphenoxytitanium, (1,2,3,4,5,6,7,8-
Octahydrofluorenyl) (dibutylamido) diphenoxytitanium, (1,2,3,4,5,6,7,8
-Octahydrofluorenyl) (diphenylamido) diphenoxytitanium, (1,2,3,4,5,6,
7,8-octahydrofluorenyl) (methylphenylamido) diphenoxytitanium, (1,2,3,4,
5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) diphenoxytitanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) (dimethylamido) di (acetoxy) titanium, (1,2,3,4,5,6,7,8- Octahydrofluorenyl) (diethylamido) di (acetoxy)
Titanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) (dibutylamido) di (acetoxy) titanium, (1,2,3,4,5,6,7, 8
-Octahydrofluorenyl) (diphenylamido) di (acetoxy) titanium, (1,2,3,4,5,
6,7,8-octahydrofluorenyl) (methylphenylamido) di (acetoxy) titanium, (1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Bistrimethylsilylamido) di (acetoxy) titanium, (1,2,3,4,5,6,7,8-octahydrofluorenyl) (dimethylamido) di (trimethylacetoxy) titanium, (1,2,2 3, 4, 5, 6,
7,8-Octahydrofluorenyl) (diethylamido) di (trimethylacetoxy) titanium, (1,
2,3,4,5,6,7,8-octahydrofluorenyl) (dibutylamido) di (trimethylacetoxy) titanium, (1,2,3,4,5,6,7,8-octahydro Fluorenyl) (diphenylamido) di (trimethylacetoxy) titanium, (1,2,3,4,5,
6,7,8-octahydrofluorenyl) (methylphenylamido) di (trimethylacetoxy) titanium,
(1,2,3,4,5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium,

(9-methyl-1,2,3,4,5,6,6)
7,8-Octahydrofluorenyl) tris (dimethylamido) titanium, (9-methyl-1,2,3,4,
5,6,7,8-octahydrofluorenyl) tris (diethylamido) titanium, (9-methyl-1,
2,3,4,5,6,7,8-octahydrofluorenyl) tris (dibutylamido) titanium, (9-methyl-1,2,3,4,5,6,7,8-octahydro Fluorenyl) tris (diphenylamido) titanium,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) tris (methylphenylamido) titanium, (9-methyl-1,2,3,4,5,5
6,7,8-Octahydrofluorenyl) tris (bistrimethylsilylamido) titanium, (9-methyl-
1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) titanium methyl,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) titanium methyl, (9-methyl-1,2,3,4,5,6 ，
7,8-Octahydrofluorenyl) bis (dibutylamido) titanium methyl, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) titanium methyl, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl ) Bis (methylphenylamido) titanium methyl, (9-methyl-1,2,3,4,5,6,7,8
-Octahydrofluorenyl) bis (bistrimethylsilylamido) titanium methyl, (9-methyl-1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) titaniumphenyl, (9
-Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) titaniumphenyl, (9-methyl-1,2,3,4,5,6,6
7,8-octahydrofluorenyl) bis (dibutylamido) titaniumphenyl, (9-methyl-1,2,2
3,4,5,6,7,8-octahydrofluorenyl)
Bis (diphenylamido) titanium phenyl, (9-
Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (methylphenylamido) titaniumphenyl, (9-methyl-1,2,3,4,5,5
6,7,8-Octahydrofluorenyl) bis (bistrimethylsilylamido) titaniumphenyl, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis ( (Dimethylamido) titanium methoxide, (9-methyl-1,2,3,4,5,6,6
7,8-octahydrofluorenyl) bis (diethylamido) titanium methoxide, (9-methyl-1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) titanium methoxide,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) titanium methoxide, (9-methyl-1,2,3,4,4)
5,6,7,8-octahydrofluorenyl) bis (methylphenylamido) titanium methoxide, (9-
Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (bistrimethylsilylamide)
Titanium methoxide, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (dimethylamido) phenoxytitanium, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl ) Bis (diethylamido) phenoxytitanium, (9-methyl-1,2,3,4,5,6,7,8
-Octahydrofluorenyl) bis (dibutylamide)
Phenoxytitanium, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (diphenylamido) phenoxytitanium, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl ) Bis (methylphenylamido) phenoxytitanium, (9-methyl-1,2,3,4,5,5
6,7,8-octahydrofluorenyl) bis (bistrimethylsilylamido) phenoxytitanium,

(9-methyl-1,2,3,4,5,6
7,8-Octahydrofluorenyl) bis (dimethylamido) (acetoxy) titanium, (9-methyl-1,
2,3,4,5,6,7,8-octahydrofluorenyl) bis (diethylamido) (acetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,8-
Octahydrofluorenyl) bis (dibutylamide)
(Acetoxy) titanium, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (diphenylamide) (acetoxy) titanium,
(9-Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (methylphenylamide)
(Acetoxy) titanium, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
Bis (bistrimethylsilylamide) (acetoxy) titanium, (9-methyl-1,2,3,4,5,6,6
7,8-Octahydrofluorenyl) bis (dimethylamido) (trimethylacetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) bis ( Diethylamido) (trimethylacetoxy) titanium, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (dibutylamido) (trimethylacetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,8-
Octahydrofluorenyl) bis (diphenylamide)
(Trimethylacetoxy) titanium, (9-methyl-
1,2,3,4,5,6,7,8-octahydrofluorenyl) bis (methylphenylamide) (trimethylacetoxy) titanium, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) bis (bistrimethylsilylamide) (trimethylacetoxy) titanium, (9-methyl-1,2,3,4,5,5
6,7,8-octahydrofluorenyl) (dimethylamido) titanium dimethyl, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Diethylamido) titanium dimethyl, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (dibutylamido) titanium dimethyl,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (diphenylamido) titanium dimethyl, (9-methyl-1,2,3,4,5,6 ，
7,8-Octahydrofluorenyl) (methylphenylamido) titanium dimethyl, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Bistrimethylsilylamide) titanium dimethyl,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (dimethylamido) titanium diphenyl, (9-methyl-1,2,3,4,5,6 ，
7,8-Octahydrofluorenyl) (diethylamido) titanium diphenyl, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Dibutylamido) titanium diphenyl, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (diphenylamido) titanium diphenyl, (9-methyl-1,2, 3,4,5,6,7,8-
Octahydrofluorenyl) (methylphenylamide)
Titanium diphenyl, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) titanium diphenyl,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (dimethylamido) titanium dimethoxide, (9-methyl-1,2,3,4,5 ，
6,7,8-octahydrofluorenyl) (diethylamido) titanium dimethoxide, (9-methyl-1,
2,3,4,5,6,7,8-octahydrofluorenyl) (dibutylamido) titanium dimethoxide,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (diphenylamido) titanium dimethoxide, (9-methyl-1,2,3,4,4)
5,6,7,8-Octahydrofluorenyl) (methylphenylamido) titanium dimethoxide, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl ) (Bistrimethylsilylamide) titanium dimethoxide,

(9-methyl-1,2,3,4,5,6,6
7,8-Octahydrofluorenyl) (dimethylamido) diphenoxytitanium, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Diethylamido) diphenoxytitanium, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (dibutylamido) diphenoxytitanium, (9-methyl-1,2) , 3, 4, 5, 6, 7, 8
-Octahydrofluorenyl) (diphenylamido) diphenoxytitanium, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) (methylphenylamido) diphenoxytitanium, (9-
Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (bistrimethylsilylamido) diphenoxytitanium, (9-methyl-1,2,3,4,
5,6,7,8-octahydrofluorenyl) (dimethylamido) di (acetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl ) (Diethylamido) di (acetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,8
-Octahydrofluorenyl) (dibutylamido) di (acetoxy) titanium, (9-methyl-1,2,
3,4,5,6,7,8-octahydrofluorenyl)
(Diphenylamide) di (acetoxy) titanium,
(9-methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (methylphenylamido) di (acetoxy) titanium, (9-methyl-1,2,2
3,4,5,6,7,8-octahydrofluorenyl)
(Bistrimethylsilylamido) di (acetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,
8-octahydrofluorenyl) (dimethylamido) di (trimethylacetoxy) titanium, (9-methyl-
1,2,3,4,5,6,7,8-octahydrofluorenyl) (diethylamido) di (trimethylacetoxy) titanium, (9-methyl-1,2,3,4,5,5
6,7,8-octahydrofluorenyl) (dibutylamido) di (trimethylacetoxy) titanium, (9-
Methyl-1,2,3,4,5,6,7,8-octahydrofluorenyl) (diphenylamido) di (trimethylacetoxy) titanium, (9-methyl-1,2,3,
4,5,6,7,8-octahydrofluorenyl) (methylphenylamido) di (trimethylacetoxy) titanium, (9-methyl-1,2,3,4,5,6,7,
8-octahydrofluorenyl) (bistrimethylsilylamido) di (trimethylacetoxy) titanium, and the like.

Further, there can be mentioned similar compounds in which each amide group in these compounds is substituted with a corresponding phosphide group. Furthermore, zirconium or hafnium may be substituted for titanium in these compounds, or compounds similar to transition metal elements of other group or lanthanoid series may be mentioned, but the compounds are not limited thereto. Of these, titanium compounds are preferable from the viewpoint of catalytic activity. Moreover, you may use the mixture which combined these compounds arbitrarily.

Next, as the component (b) used in the present invention, a compound capable of reacting with the transition metal compound of the component (a) (a) to form an ionic complex, or (b) an oxygen-containing compound is used. Used. The component (a), that is, the compound capable of reacting with the transition metal compound of the component (a) to form an ionic complex, is a coordination complex compound composed of an anion having a plurality of groups bound to a metal and a cation, or Mention may be made of Lewis acids. There are various coordination complex compounds composed of an anion in which a plurality of groups are bound to a metal and a cation. For example, the following general formula (17) or (1
The compound represented by 8) can be preferably used. ([L ¹ -H] ^{p +} ) _q ([M ² X ² X ³ ... X ⁿ ] ^(nm)- ) _l ... (17) ([L ² ] ^{p +} ) _q ([M ³ X ² X ³ ... X ⁿ ] ^(nm)- ) _l ... (18) [In the formula (17) or (18), L ² is M ⁴ or R ³ described later.
R ⁴ M ⁵ or R ⁵ ₃ C, L ¹ is a Lewis base, M ² and M ³ are metals selected from Groups 5 to 15 of the periodic table, and M ⁴ is Group 1 and 8 of the periodic table. A metal selected from Groups 12 to 12, M ⁵ is a metal selected from Groups 8 to 10 of the periodic table, X ^{2 to} X ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a carbon number of 1, respectively. ~ 2
0 alkyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, substituted alkyl group,
An organic metalloid group or a halogen atom is shown. R ³ and R
⁴ is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ⁵
Represents an alkyl group. m is the valence of M ² and M ³ and is 1 to 7
, N is an integer of 2 to 8, p is an integer of 1 to 7 as an ionic valence of L ¹ -H and L ² , q is an integer of 1 or more, l = q × p
/ (Nm). ]

M ² and M ³ are, respectively, groups 5 to 5 of the periodic table.
A metal selected from Group 15 and specific examples include B, Al,
Each atom such as P, As and Sb, M ⁴ is a metal selected from Group 1 and Groups 8 to 12 of the periodic table, and specific examples are A
Each atom such as g, Cu, Na and Li, M ⁵ is a metal selected from Groups 8 to 10 of the periodic table, and specific examples are Fe,
Each atom such as Co and Ni can be mentioned. Specific examples of X ^{2 to} X ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group, and a phenoxy group as a aryloxy group, 2,6. -Dimethylphenoxy group, naphthyloxy group, etc., having 1 to 20 carbon atoms
As the alkyl group of, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group,
2-ethylhexyl group, etc. aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl)
Phenyl group, 4-tert-butylphenyl group, 2,
6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group and the like, F, Cl, Br, I as halogen, pentamethylantimony group as organic metalloid group, Examples thereof include a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of the substituted cyclopentadienyl group represented by R ³ and R ⁴ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

In the present invention, a plurality of groups are bound to the metal.
As the anion, specifically, B (C₆F_Five)_Four ^-, B
(C₆HF_Four)_Four ^-, B (C₆H_TwoF_Three)_Four ^-, B (C₆H
_ThreeF _Two)_Four ^-, B (C₆H_FourF)_Four ^-, B (C₆CF_Three F_Four)
_Four ^-, B (C₆H_Five)_Four ^-, BF_Four ^-, PF₆ ^-, P (C
₆F_Five)₆ ^-, Al (C₆HF_Four)_Four ^-And the like.
Further, as the metal cation, Cp_TwoFe⁺, (MeC
p)_TwoFe⁺, (TBuCp)_TwoFe⁺, (Me_TwoC
p)_TwoFe⁺, (Me_ThreeCp)_TwoFe⁺, (Me _FourC
p)_TwoFe⁺, (Me_FiveCp)_TwoFe⁺, Ag⁺, Na
⁺, Li⁺And other cations.
Is pyridinium, 2,4-dinitro-N, N-diethyl
Luanilinium, diphenylammonium, p-nitro
Anilinium, 2,5-dichloroaniline, p-nitro
-N, N-dimethylanilinium, quinolinium, N,
N-dimethylanilinium, N, N-diethylanilini
Nitrogen-containing compounds such as um, triphenylcarbenium
Mum, tri (4-methylphenyl) carbenium, tri
Carbeni such as (4-methoxyphenyl) carbenium
Um compounds, CH_ThreePH_Three ⁺, C_TwoH_FivePH_Three ⁺, C_Three
H₇PH_Three ⁺, (CH_Three)_TwoPH_Two ⁺, (C_TwoH_Five)_Two
PH_Two ⁺, (C_ThreeH₇)_TwoPH_Two ⁺, (CH_Three)_ThreePH
⁺, (C_TwoH_Five)_ThreePH⁺, (C_ThreeH₇)_ThreePH⁺,
(CF_Three)_ThreePH⁺, (CH_Three)_FourP⁺, (C_TwoH_Five)
_FourP⁺, (C_ThreeH₇)_FourP⁺Alkylphosphoni such as
Um ion and C₆H_FivePH_Three ⁺, (C₆H_Five)_TwoP
H_Two ⁺, (C₆H _Five)_ThreePH⁺, (C₆H_Five)_FourP⁺,
(C_TwoH_Five)_Two(C₆H_Five) PH⁺, (CH_Three) (C₆
H_Five) PH_Two ⁺, (CH_Three)_Two(C₆H_Five) PH⁺,
(C_TwoH_Five) _Two(C₆H_Five)_TwoP⁺Arylpho
Sponium ions and the like can be mentioned. In the present invention
In any combination of the above metal cations and anions
Coordination complex compounds can be mentioned.

Among the compounds of the general formulas (17) and (18), the following compounds can be used particularly preferably.
Examples of the compound of the general formula (17) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl). Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (Pentafluorophenyl) methyl diphenylammonium borate and the like can be mentioned. On the other hand, as the compound of the general formula (18), for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Decamethylferrocenium borate, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) formylferrocenium borate, tetrakis (pentafluorophenyl) cyanoferrocenium borate, silver tetraphenylborate, tetrakis ( Pentafluorophenyl) silver borate, tetraphenyl trityl borate, tetrakis (pentafluorophenyl)
Examples thereof include trityl borate, silver hexafluoroarsenate, silver hexafluoroantimonate, and silver tetrafluoroborate.

Further, in the present invention, as the Lewis acid,
For example, B (C ₆ F ₅ ) ₃ , B (C ₆ HF ₄ ) ₃ , B (C ₆ H
_{2 F 3) 3, B (} C 6 H 3 F 2) 3, B (C 6 H 4 F) 3, B (C
_{6 CF 3 F 4) 3,} BF 3, PF 5, P (C 6 F 5) 5, Al (C
₆ HF ₄ ) _{3 and the} like can also be used. In the present invention, the compound capable of reacting with the transition metal compound (A) to form an ionic complex may be used alone or in combination of two or more.

On the other hand, the oxygen-containing compound as the component (b) is represented by the general formula (3)

Embedded image

Having a chain structure represented by:
Or general formula (4)

Embedded image

Those having a cyclic structure represented by the following are used. In the general formulas (3) and (4), R ^{11 to} R
Each of ¹⁷ represents an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups. Groups. R
^{11 to} R ¹⁵ may be the same or different from each other, and R ¹⁶
And R ¹⁷ may be the same or different. Y ²
To Y ⁶ each represent an element of Group 13 of the periodic table, and specific examples thereof include B, Al, Ga, In and Tl. Of these, B and Al are preferable. Y ^{2 to} Y ⁴ may be the same or different from each other, and Y ⁵ and Y ⁶ may be the same or different from each other. Further, f to i are integers of 0 to 50, respectively, but (f + g) and (h + i)
Are 1 or more, respectively. f to i are 1
The range of -20 is preferable, and the range of 1-5 is particularly preferable. As the oxygen-containing compound represented by the general formula (3) or (4), a reaction product of an organoaluminum compound and water can be preferably used. The reaction product of this organoaluminum compound and water is mainly represented by the general formula (19)

[0064]

Embedded image A chain alkylaluminoxane represented by or a general formula (20)

[0065]

Embedded image It is a cyclic alkyl aluminoxane represented by.

In the above general formulas (19) and (20), R ¹⁸ represents an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group and various butyl groups. , Various pentyl groups, various hexyl groups,
Examples include various heptyl groups and various octyl groups. j is 1
The number is from 50 to 50, preferably from 1 to 20, more preferably from 1 to 5. The organoaluminum compound to be reacted with water is usually a trialkylaluminum, specifically trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t. -Butyl aluminum, tripentyl aluminum, trihexyl aluminum, triheptyl aluminum and the like are preferably used. The reaction products of these trialkylaluminums and water are generally mainly composed of the chain alkylaluminoxane and cyclic alkylaluminoxane, unreacted trialkylaluminum and various condensation products, and further, molecules in which these are complicatedly associated. It contains various substances and becomes various products depending on the contact conditions of trialkylaluminum and water. The reaction method of the trialkylaluminum and water at this time is not particularly limited, and a known method can be used.

Specific examples of the reaction product of the above organoaluminum compound and water include methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane,
Examples thereof include isobutylaluminoxane, t-butylaluminoxane, pentylaluminoxane, hexylaluminoxane and heptylaluminoxane. Also,
As the oxygen-containing compound containing both aluminum and boron, those described in, for example, JP-A-6-172438 and JP-A-6-172439 are known. In the present invention, the oxygen-containing compound as the component (B) may be used alone or in combination of two or more. Further, as the component (B), one or more compounds of the component (a) and one or more compounds of the component (b) can be used in combination.

In the present invention, an alkylating agent is further used as the component (c). Here, there are various alkylating agents, for example, general formula (21) R ¹⁹ _m Al (OR ²⁰ ) _n V _3-mn (21) [wherein R ¹⁹ and R ²⁰ Each represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and V represents a hydrogen atom or a halogen atom. Also, m is 0 <m ≦ 3, preferably 2 or 3, and most preferably 3. n is 0 ≦ m ≦ 3.
n <3, preferably 0 or 1. ] An alkyl group-containing aluminum compound represented by the formula or a general formula (22) R ¹⁹ ₂ Mg (22) [In the formula, R ¹⁹ is the same as the above. ] An alkyl group-containing magnesium compound represented by the formula
_{^{3) R 19 2 Zn ··· (}} 23) wherein, R ¹⁹ is as defined above. And the like.

Of these alkyl group-containing compounds, alkyl group-containing aluminum compounds, especially trialkylaluminum and dialkylaluminum compounds, are preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkylaluminum. Dialkylaluminum halides such as n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride and di-t-butylaluminum chloride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and dimethylaluminum ethoxide, Dimethyl aluminum hydride, diethyl aluminum hydride, Dialkyl aluminum hydride such as isobutyl aluminum hydride and the like. Furthermore, dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium and diisopropyl magnesium and dialkyl zinc such as dimethyl zinc, diethyl zinc, di-n-propylethyl zinc and diisopropyl zinc can be mentioned.

The present invention is a polymerization catalyst composed of the components (a), (b) and (c) as described above. When polymerizing various monomers, an alkyl group is used as a chain transfer agent. It is also possible to add a reaction product of a linear alkylaluminum having 2 or more carbon atoms and water.

When the polymerization catalyst of the present invention is prepared, the above-mentioned components (a), (b) and (c) may be added separately to the monomer, and the addition timing is not particularly limited. In addition, before mixing the catalyst component with the monomer, the catalyst dilution solvent (aromatic hydrocarbon such as toluene and ethylbenzene or aliphatic hydrocarbon such as hexane and heptane) is added to (a),
The components (b) or (c) may be premixed, and the addition timing is not particularly limited. Furthermore, if necessary (c)
All or part of the components may be added to the monomer later. The above components (a), (b) and (c) can be added at a polymerization temperature, as a matter of course, at 0 to 100 ° C.
It is also possible to carry out at the temperature of. The catalyst as described above exhibits high activity in the production of a styrene polymer having a syndiotactic structure and the like.

To produce a polymer by the method of the present invention, various monomers are polymerized (or, in the presence of a catalyst containing the above-mentioned components (a), (b) and (c) as a main component. Copolymerize). Examples of the monomer used for the polymerization include aromatic vinyl compounds such as styrene, substituted aromatic vinyl compounds such as paramethylstyrene, C _{2 to} C ₂₀ α-olefins, dienes such as isoprene, and acetylene. Alkynes, preferably C ₂ -C ₁₀ such as ethylene and propylene
.Alpha.-olefins and the like. These monomers can be used either in their own homopolymerization or in the copolymerization of two or more of the above monomers. Also, when copolymerizing, the content of each monomer component is not particularly limited. Further, the compound contained in the monomer used is not particularly limited, but the content of the phenylacetylene compound or the indene compound contained in the monomer is preferably 5 or less.
It is 0 ppm or less. The monomer preferably used in the present invention is represented by the following general formula (24)

[0073]

Embedded image

[In the formula, R ¹⁰ represents a hydrogen atom, a halogen atom or a hydrocarbon group having 20 or less carbon atoms, and k is 1 to 3
Indicates an integer. When k is 2 or more, each R ¹⁰ may be the same or different. ] The compound represented by these is mentioned, Specifically, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4
-Dimethylstyrene, 2,5-dimethylstyrene, 3,
4-dimethylstyrene, 3,5-dimethylstyrene, p
-Alkyl styrene such as ethyl styrene, m-ethyl styrene, p-tertiary butyl styrene; vinyl benzene such as p-divinyl benzene, m-divinyl benzene and tridivinyl benzene; p-chloro styrene, m-chloro styrene, o- Chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, halogenated styrene such as o-methyl-p-fluorostyrene, methoxystyrene. , Ethoxystyrene, t-butoxystyrene, and other alkoxystyrenes, or a mixture of two or more thereof.

In the polymerization of monomers using the polymerization catalyst of the present invention, there are no particular restrictions on the polymerization method and polymerization conditions. Therefore, it is also possible to use the bulk polymerization method under the condition that there is substantially no inert hydrocarbon medium or the like, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane or benzene and toluene. It is also possible to use a solvent polymerization method which is carried out in an inert hydrocarbon medium such as aromatic hydrocarbon such as xylene. The polymerization temperature is not particularly limited, but is generally 0 to 120 ° C, preferably 20 to 90 ° C. Further, the polymerization reaction may be carried out in the presence of hydrogen in order to control the molecular weight of the obtained styrene polymer.

The polymer produced using the polymerization catalyst of the present invention has a syndiotactic structure.
Here, the syndiotactic structure in the styrene-based polymer means that the stereochemical structure is a syndiotactic structure, that is, a phenyl group or a substituted phenyl group, which is a side chain, alternates with respect to the main chain formed from carbon-carbon bonds. Has a steric structure located in the opposite direction, and its tacticity is based on the nuclear magnetic resonance method using isotope carbon ( ¹³ C-NM
R method). ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3 and pentad in the case of 5. However, the "styrene-based polymer having a syndiotactic structure" referred to in the present invention is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more, preferably 50% in racemic pentad. It means polystyrene having the above syndiotacticity, poly (alkylstyrene), poly (halogenated styrene), etc., and a mixture thereof, or a copolymer containing these as the main components.

[0077]

EXAMPLES Next, the present invention will be explained more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Production Example 1 [Synthesis of (pentamethylcyclopentadienyl) (diethylamido) titanium dimethyl] 30 ml of tetrahydrofuran (THF) and (pentamethylcyclopentadienyl) (diethylamido) titanium were placed in a reactor having sufficient nitrogen substitution. 2 grams of dichloronium (Cp ^* TiCl ₂ (NEt ₂ )) was added. Furthermore, 4.09 ml of a diethyl ether solution of 3.0 mol / L of MeMgBr was added at a low temperature,
Stir at room temperature. Then, the precipitate was filtered off, and 0.85 g of a compound having the following measurement data was obtained from the filtrate. ¹ H-NMR (200 MHz, C ₆ D ₆ ) (ppm) 0.13 (s, 6H) 1.16 (t, 6H) 1.91 (s, 15H) 3.45 (q, 4H) were obtained. The compound was found to be the desired (pentamethylcyclopentadienyl) (diethylamido) titanium dimethyl (Cp ^* TiMe ₂ (NEt ₂ )).

Example 1 Dry, nitrogen-substituted container having an internal volume of 50 ml
Toluene 43 ml, 2.0 mol / liter
Triisobutylaluminum solution 0.94 ml,
Dimethyl anilium tetra (pentafluorophenyl)
Borate [HN (Me)_TwoC₆H_Five] [B (C₆F_Five)_Four] 74
Obtained in milligrams and in Production Example 1 (Pentamethyl
Lopentadienyl) (diethylamido) titanium dime
Chill (Cp ^*TiMe_Two(NEt_Two)) 0.05 mol / l
1.85 ml of the solution in the bottle is mixed, and the pre-mixing is performed.
46 ml of the medium solution was prepared. Dry and replace with nitrogen
10 ml of styrene in a container with an internal volume of 30 ml
Add 1 liter and heat to 70 ° C to dissolve the above premixed catalyst.
Add 250 microliters of the solution and load at 70 ° C for 4 hours.
I went together. After the reaction was completed by adding methanol, the product was
Dried and syndiotactic polystyrene (SPS)
Obtained 4.36 grams. Weight average molecular weight of the obtained polymer
Was 837,000 (SPS activity 181 kg / gT
i).

Example 2 To a container having an inner volume of 50 ml which had been dried and purged with nitrogen, 30.4 ml of toluene, 1.5 ml of a 2.0 mol / liter triisobutylaluminum solution,
0.5 ml of a 1.6 mol / l toluene solution of methylaluminoxane and (pentamethylcyclopentadienyl) (diethylamido) titanium dimethyl (Cp ^* TiMe ₂ (NEt ₂ )) obtained in Preparation Example 1 were used. 0
2.4 ml of a 5 mol / liter solution was mixed to prepare 40 ml of a premixed catalyst solution. 10 ml of styrene was placed in a container having an inner volume of 30 ml which was dried and purged with nitrogen, heated to 70 ° C., added with 83 μl of the above premixed catalyst solution, and heated to 70 ° C.
Polymerization was carried out for 4 hours. After the reaction was completed by adding methanol, the product was dried to obtain 3.41 g of SPS. The weight average molecular weight of the obtained polymer was 1191,000 (SPS activity 340 kg / gTi).

Comparative Example 1 31 ml of toluene, 0.8 ml of a 2.0 mol / l triisobutylaluminum solution, 0.8 ml of dimethylanilium tetra (pentafluorophenyl) borate were placed in a container having a volume of 50 ml which had been dried and purged with nitrogen. 64 mg of [HN (Me) ₂ C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] and Cp ^* Ti of 0.0977 mol / l.
A premixed catalyst solution (40 ml) was prepared by mixing 8.2 ml of a Cl ₃ solution. 10 ml of styrene was placed in a container having an inner volume of 30 ml which had been dried and purged with nitrogen, and heated to 70 ° C. to prepare the above premixed catalyst solution 2
50 microliters was added and polymerization was performed at 70 ° C. for 4 hours. After the reaction was completed by adding methanol, the product was dried to obtain 0.77 g of SPS. The weight average molecular weight of the obtained polymer was 455,000 (SPS activity 32 k
g / gTi).

Comparative Example 2 In a container having an internal volume of 50 ml which had been dried and purged with nitrogen, 20.5 ml of toluene, 1.50 ml of a 2.0 mol / l triisobutylaluminum solution, and 1.6 mol / l of methyl were added. 5.63 ml of aluminoxane in toluene and 12.3 ml of 0.01 mol / l Cp ^* TiCl ₃ solution are mixed,
Forty milliliters of premixed catalyst solution was prepared. 10 ml of styrene was placed in a container having an inner volume of 30 ml which was dried and purged with nitrogen, heated to 70 ° C., added with 83 μl of the above premixed catalyst solution, and heated to 70 ° C.
Polymerization was carried out for 4 hours. After the reaction was completed by adding methanol, the product was dried to obtain 0.72 g of SPS. The weight average molecular weight of the obtained polymer was 810000 (SPS activity 63 kg / gTi).

[0082]

As described in detail above, by using the polymerization catalyst of the present invention, residual metal in the obtained polymer is reduced, and the polymer production process is simplified and the production cost is reduced. be able to. Further, the number of halogen atoms remaining in the obtained polymer is reduced, the physical properties of the polymer are less affected, and complicated post-treatment equipment is not required. Moreover, according to the polymerization catalyst of the present invention, a polymer having a high molecular weight can be obtained as compared with a polymer produced using a conventional catalyst system.

Claims (6)

[Claims] 1. (a) In one molecule, the following general formula (1) MX- ¹ (1) [wherein, M is a metal element of Group 3 to 6 of the periodic table or a lanthanoid series, X ¹ represents an element of Group 15 of the periodic table. ] At least one bond represented by the following general formula (2) MY ¹ ... (2) [In the formula, M is a metal element of the periodic table 3 to 6 group or lanthanoid series, Y ¹ represents an element belonging to Group 17 of the periodic table. ] A transition metal compound having no bond represented by: (b) (a) a compound capable of reacting with the transition metal compound of the component (a) to form an ionic complex, or (b) a general formula ( 3) [Chemical 1] [In the formula, R ^{11 to} R ¹⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and Y ^{2 to} Y ⁴ each represent an element of Group 13 of the periodic table,
They may be the same or different, and f and g each represent a number of 0 to 50, and f + g is 1 or more. ] And / or general formula (4) [In the formula, R ¹⁶ and R ¹⁷ each represent an alkyl group having 1 to 8 carbon atoms, and they may be the same or different; Y ⁵ and Y ⁶ each represent an element of Group 13 of the periodic table; They may be the same or different, h
And i each represent a number of 0 to 50, and h + i is 1 or more. ] The oxygen-containing compound represented by these, and (c) alkylating agent are contained, The polymerization catalyst characterized by the above-mentioned. 2. The transition metal compound (a) is the following general compound:
Formula (5) or general formula (6) M (R¹R^Two-A)_aX_bY_cZ_{4- (a + b + c)} ... (5) M (R¹R^Two-A)_dX_eY_{3- (d + e)} (6) [In the formula, M represents a group 3 to 6 of the periodic table or a lanthanoid series.
Metal element, A is nitrogen atom or phosphorus atom, R¹, R^TwoIs it
Hydrogen atom, alkyl group, aryl group, alkyl ant
Group, arylalkyl group, silyl group, vinyl group,
Represents a ryl group, an ethynyl group or an acyl group, which are mutually
May be the same or different, and R¹And R ^TwoIs that
It may be combined with each other. X, Y and Z are each
Independently hydrogen atom, alkyl group, alkoxy group, aryl
Group, alkylaryl group, arylalkyl group, ant
Group, acyloxyl group, vinyl group, allyl
Group, ethynyl group, alkylthio group, arylthio group, or
Is a Cp group (cyclopentadienyl group, substituted cyclopenta
Dienyl group, indenyl group, substituted indenyl group, fluoro
Renyl group, substituted fluorenyl group), a is 1 to 4
Integer, b and c are integers of 0 to 3, d is an integer of 1 to 3
Number and e show the integer of 0-2. (R¹R^Two-A), X,
Any two of Y and Z may be crosslinked. 〕so
The catalyst for polymerization according to claim 1, which is represented. 3. The polymerization catalyst according to claim 2, wherein the transition metal compound represented by the general formula (5) or the general formula (6) has one or two Cp groups. 4. In the transition metal compound represented by the general formula (5) or (6), at least one of X, Y and Z is a hydrogen atom, an alkyl group, an alkoxy group,
Aryl group, alkylaryl group, arylalkyl group, aryloxy group, acyloxyl group, vinyl group,
The catalyst for polymerization according to claim 2 or 3, which is an allyl group, an ethynyl group, an alkylthio group or an arylthio group. 5. A method for producing a styrene-based polymer having a syndiotactic structure, which comprises polymerizing a styrene-based monomer in the presence of the polymerization catalyst according to any one of claims 1 to 4. 6. A styrene-olefin-based copolymerization characterized by copolymerizing a styrene-based monomer and an olefin-based monomer in the presence of the polymerization catalyst according to any one of claims 1 to 4. Manufacturing method of coalescence.