JP2006176760A - Synthetic lubricating oil and lubricating oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic lubricating oil and a lubricating oil composition which have high heat-resistant oxidation stability and a high viscosity index, and is excellent in low-temperature viscosity characteristics and shear stability. <P>SOLUTION: The synthetic lubricating oil comprises α-olefin (co) polymer specified by the following (i)-(iv): (i) the (i)-(iv) contain a constituting unit derived from 8-20C α-olefin in a range of 90-100 mol% and a constituting unit derived from ethylene in a range of 0-10 mol.%; (ii) kinematic viscosity (K) at 100°C is in a range of 8-500 mm<SP>2</SP>/s; (iii) a number average molecular weight (Mn) is 500-15,000; (iv) formula (I): A≤24.0×Exp (-0.0239×K) and formula (II): B≤0.0775×K are satisfied; and (v) a molecular weight distribution (Mw/Mn) is in a range of 1.1-1.8, wherein A represents the content (%) of a (co)polymer having a molecular weight of ≤1,000 and B represents the content (%) of a (co)polymer having a molecular weight of ≥20,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a synthetic lubricating oil and a lubricating oil composition having high heat-resistant oxidation stability and having a high viscosity index, low-temperature viscosity characteristics, and excellent shear stability.

  A variety of performances are required for grease lubricants, engine oils, gear oils, hydraulic oils, etc., and in recent years, internal combustion engines have become more powerful due to higher performance, higher output, and severer operating conditions. High performance such as wear resistance, heat resistance, sludge resistance, lubricating oil consumption characteristics, and fuel efficiency of each part has been required. In particular, there is a demand for a longer drain (longer life), and for this reason, it is necessary to further reduce the lowering of viscosity due to evaporation loss and shearing of the lubricating oil. On the other hand, in order to ensure fuel efficiency, a wide range has been developed, and a good low temperature viscosity property of lubricating oil is required. Accordingly, greases for lubricating oils, engine oils, gear oils, hydraulic oils and the like are required to have long life, that is, low evaporability and good temperature viscosity characteristics.

  As synthetic lubricating oils used as lubricating base oils for automobile gear oils, engine oils, industrial lubricating oils, hydraulic oils, and the like, many poly-α-olefins (PAO) are industrially used. Such a PAO can be obtained by oligomerizing a higher α-olefin with an acid catalyst as described in US Pat. Nos. 3,780,128, 4032591, and JP-A-1-163136. .

  On the other hand, as described in JP-A-57-117595, an ethylene / α-olefin copolymer can also be used as a synthetic lubricating oil excellent in viscosity index, oxidation stability, shear stability, and heat resistance. It has been known.

  As a method for producing an ethylene / α-olefin copolymer used as a synthetic lubricating oil, a vanadium compound and an organoaluminum compound as described in JP-B2-1163 and JP-B-2-7998 are conventionally used. A vanadium-based catalyst method has been used. As such an ethylene / α-olefin copolymer, an ethylene / propylene copolymer is mainly used.

  Further, as a method for producing a copolymer with high polymerization activity, metallocene compounds such as zirconocene and organoaluminum oxy compounds (aluminoxanes) as described in JP-A-61-221207 and JP-B-7-121969. There is known a method using a catalyst system comprising, and Japanese Patent No. 2796376 discloses a synthetic lubricant comprising an ethylene / α-olefin copolymer obtained by using a catalyst system in which a specific metallocene catalyst and an aluminoxane are combined. A method for producing oil is disclosed.

In recent years, the use environment of lubricating oil has become severe, but there has been a tendency to extend the service life in consideration of environmental problems. PAO or ethylene / propylene copolymers with excellent low-temperature viscosity characteristics, heat resistance and oxidation stability, etc. However, there is a demand for further improvement in viscosity index and low temperature viscosity characteristics from the viewpoint of fuel efficiency and energy saving.
U.S. Pat. No. 3,780,128 US 4032591 JP-A-1-163136 JP-A-57-117595 Japanese Patent Publication No.2-1163 Japanese Patent Publication No.2-7998 JP-A 61-221207 Japanese Patent Publication No. 7-121969 Japanese Patent No. 2796376

  The problem to be solved by the present invention relates to a synthetic lubricating oil and a lubricating oil composition having high heat-resistant oxidation stability and having a high viscosity index, low-temperature viscosity characteristics, and excellent shear stability.

  As a result of intensive studies to solve the above problems, a low molecular weight polymer having a specific molecular weight distribution obtained by homopolymerization or copolymerization with ethylene of an α-olefin having a specific number of carbon atoms is a synthetic lubricant. It has been found that it exhibits excellent heat-resistant oxidation stability, viscosity index, and low-temperature viscosity characteristics as an oil, and the present invention has been completed.

That is, the present invention
A synthetic lubricating oil comprising an α-olefin (co) polymer defined by the following (i) to (v):
(I) containing (a) a structural unit derived from at least one monomer selected from α-olefins having 8 to 20 carbon atoms in a range of 90 to 100 mol%, and (b) derived from ethylene. Containing structural units in an amount ranging from 0 to 10 mol%,
(Ii) the kinematic viscosity at 100 ° C. is in the range of 8 to 500 mm ² / s,
(Iii) Number average molecular weight (Mn) measured by gel permeation chromatography
) Is in the range of 500-15,000,
(Iv) satisfying the following formulas (I) and (II):
A ≦ 24.0 × Exp (−0.0239 × K) (I)
B ≦ 0.0775 × K (II)
(In the formula, A is the content (%) of (co) polymer having a molecular weight of 1,000 or less measured by gel permeation chromatography, and B is the content (% of (co) polymer having a molecular weight of 20,000 or more). ), K is the kinematic viscosity at 100 ° C. (mm ² / s))
(V) The molecular weight distribution (Mw / Mn) is in the range of 1.1 to 1.8.
And a lubricating oil composition comprising the synthetic lubricating oil and a low viscosity base oil.

  The synthetic lubricating oil of the present invention has low evaporation at high temperatures and excellent heat-resistant oxidation stability as compared with conventional mineral oils or synthetic oils, and is excellent in high viscosity index and low temperature viscosity characteristics. Therefore, it can be used alone or mixed with other base oils such as mineral oils and α-olefin oligomers to make lubricating base oils. Stability can be greatly improved.

The synthetic lubricating oil of the present invention comprises the following α-olefin (co) polymer.
In the present invention, the monomer (a) having 8 to 20 carbon atoms constituting the α-olefin (co) polymer is 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefin, 8-methyl-1-nonene, 7-methyl Examples include α-olefins having a branch such as -1-decene, 6-methyl-1-undecene, and 6,8-dimethyl-1-decene, preferably linear α having 8 to 12 carbon atoms. -Olefin, particularly preferably 1-decene.

  The content of the structural unit derived from the monomer comprising the α-olefin (co) polymer (a) the α-olefin having 8 to 20 carbon atoms is in the range of 90 to 100 mol%, preferably Is 95 to 100 mol%.

Moreover, the content rate of the structural unit derived from (b) ethylene which comprises an alpha olefin (co) polymer is the range of 0-10 mol%, Preferably it is the range of 0-5 mol%.
Furthermore, it is preferable that the content rate of the structural unit guide | induced from the (c) C3-C6 alpha-olefin added as needed is the range of 0-30 mol%.

  The α-olefin (co) polymer is a polymer of a monomer composed of at least one or more of the above (a) α-olefins having 8 to 20 carbon atoms (α-olefin content 100 mol%), or ( b) Copolymer with ethylene. Furthermore, (c) C3-C6 alpha olefin can also be contained as a copolymerization component as needed. Examples of the α-olefin having 3 to 6 carbon atoms include linear α-olefins such as propylene, 1-butene, 1-pentene, and 1-hexene, and branched α-olefins such as 4-methyl-1-pentene. Mention may be made of olefins. These α-olefins can be used alone or in combination of two or more.

The kinematic viscosity at 100 ° C. of the α-olefin (co) polymer in the present invention is 8 to 500 mm ^2.
/ S, preferably 20 to 150 mm ² / s.
Moreover, the number average molecular weight (Mn) of the α-olefin (co) polymer in the present invention is in the range of 500 to 15,000, preferably in the range of 1,500 to 4,300.

  The number average molecular weight can be measured by gel permeation chromatography (GPC) calibrated using a standard substance (monodisperse polystyrene (PSt)) having a known molecular weight.

Further, the α-olefin (co) polymer in the present invention has a molecular weight of 1,000 or less as measured by gel permeation chromatography in the range of the formula (I) and a molecular weight of 20,000 or more. The amount is in the range of formula (II).
A ≦ 24.0 × Exp (−0.0239 × K) (I)
B ≦ 0.0775 × K (II)
(In the formula, A is a content (%) having a molecular weight of 1,000 or less measured by gel permeation chromatography, B is a content (%) having a molecular weight of 20,000 or more, and K is a kinematic viscosity at 100 ° C. (mm ² / S).)
The molecular weight distribution (Mw / Mn) of the α-olefin (co) polymer in the present invention is 1.
It exists in the range of 1-1.8, Preferably it exists in the range of 1.2-1.7.

The unsaturated group content at the molecular end can be obtained from the ratio of the proton peak area of the unsaturated group portion and the peak area of all protons by ¹ H-NMR to obtain the number N of unsaturated groups relative to the total number of protons, The unsaturated group content at the molecular end can be calculated from N × M × 2/14 using the absolute molecular weight M. In this invention, the content rate of the unsaturated group in the molecule | numerator piece terminal exists in the range of 0.001 to 10%, Preferably it exists in the range of 0.05 to 8%.

(Production of α-olefin (co) polymer)
In the production of the α-olefin (co) polymer as described above, JP-A-2-41303, JP-A-2-41305, JP-A-2-274703, and JP-A-2-274704 are disclosed. JP-A-3-179005, JP-A-3-179006, JP-A-3-1.
No. 93796, JP-A-4-69394, JP-A-5-17589, JP-A-6-122718, JP-A-8-120127, JP-A-8-239414, JP-A-10-087716 Publication, JP2000-212194A or WO
01/27124, WO 02/074855, WO 04/029062, EP 0881
236, EP 1416000, can be produced by reference to the catalyst used in producing the α-olefin (co) polymer.

Specifically, when the α-olefin (co) polymer is produced, for example, the transition metal compound is a transition metal compound (A) belonging to Group 4 of the periodic table,
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum compound,
(B-3) an organoaluminum oxy compound,
(B-4) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair,
In the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of: α-olefin homopolymerization having 8 to 20 carbon atoms, α-olefin having 8 to 20 carbon atoms, ethylene, and further if necessary Thus, a homopolymer or a copolymer can be obtained by copolymerizing an α-olefin having 3 to 6 carbon atoms.

More specifically, (A) and (B) used this time are as follows.
(A) Transition metal compound The transition metal compound (A) used in the present invention can be used without particular limitation as long as it is a transition metal compound of groups 4 to 6 in the periodic table having a known olefin polymerization ability. Examples of transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds of Tables 4 to 6 can be given.
Preferred are transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds of Group 4 of the periodic table. Hereinafter, preferred forms of these transition metal compounds (A) will be described.

  Specific examples of transition metal halides, transition metal alkylates, and transition metal alkoxylates include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium.

  Examples of the non-crosslinkable or crosslinkable metallocene compound include compounds represented by the following general formula [1] as a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton.

ML _x --------- [1]
In the formula, M represents one kind of transition metal atom selected from Group 4 of the periodic table, and is preferably zirconium, titanium, or hafnium. x is the valence of the transition metal and represents the number of L. L represents a ligand or group coordinated to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a halogen atom and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand or a lone electron pair. One group or atom selected from the same or different combinations from the active ligands.

  Examples of ligands having a cyclopentadienyl skeleton include cyclopentadienyl group, alkyl-substituted cyclopentadienyl group, indenyl group, alkyl-substituted indenyl group, 4,5,6,7-tetrahydroindenyl group, and fluorenyl. Groups, alkyl-substituted fluorenyl groups, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the general formula [1] includes two or more ligands having a cyclopentadienyl skeleton, among the ligands having two cyclopentadienyl skeletons, an alkylene group, It may be bonded through a substituted alkylene group, a silylene group, a substituted silylene group or the like. (In the following description, such a compound may be referred to as a “crosslinkable metallocene compound”. Other than such a compound may be referred to as a “non-bridged metallocene compound”.)
Of these, preferred are compounds represented by the above general formula [2].

ML _a X _b --------- [2]
(In the formula, M is a transition metal of Group 4 of the periodic table, specifically, zirconium, titanium, or hafnium, L is a ligand that coordinates to the transition metal, and a is 1 An integer greater than or equal to the above, wherein X represents the number of L, X represents a halogen bonded to a transition metal, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or non-carbon atom having 10 or less carbon atoms One group or atom selected from a conjugated diene, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, b is an integer of 1 or more, and X Indicates the number of
In the general formula [2], L is a ligand coordinated to a transition metal, and at least one of them is a ligand having a cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl And an alkyl-substituted cyclopentadienyl group such as a hexylcyclopentadienyl group; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; a fluorenyl group, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

In the above general formula [2], a is an integer of 1 or more and represents the number of L. In the general formula [2], M is zirconium, titanium, or hafnium. X represents a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene, an anionic ligand or a lone electron pair having a carbon number of 10 or less, which is bonded to a transition metal. A group or atom selected from the same or different combinations from the neutral ligands capable of coordinating with each other. Specific examples of halogen include fluorine, chlorine, bromine and iodine. Specific examples of hydrocarbon groups Examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, , 1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1- Such as chill-1-cyclohexyl. Neutral with 10 or less carbon atoms,
Specific examples of conjugated or non-conjugated dienes include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-1,3. -Butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, s -Cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-
eta ^{4-1,4-ditolyl-1,3-butadiene,} s- cis - or s- transformer or eta ^4-1,4-bis (trimethylsilyl) -1,3-butadiene. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations. In the said General formula [2], b is an integer greater than or equal to 1, and shows the number of X.

  When the compound represented by the general formula [2] includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons include ethylene, propylene and the like A substituted alkylene group such as diphenylmethylene; an alkylidene group such as isopropylidene; a silylene group; a substituted silylene group such as dimethylsilylene, diphenylsilylene, methylphenylsilylene, and the like. Further, the ligands having two or more cyclopentadienyl skeletons may be the same or different.

  When the compound represented by the general formula [2] is a ligand having two cyclopentadienyl skeletons, it is more specifically represented by the following general formula [3] or [4].

(In the formula, M is zirconium, titanium or hafnium, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen and hydrocarbon groups. , Selected from silicon-containing hydrocarbon groups,
Each may be the same or different, and adjacent substituents from R ¹ to R ¹⁰ may be bonded to each other to form a ring, and X is a halogen, a hydrogen atom, or a carbon number of 1 to 10 One kind selected from hydrocarbon groups or neutral, conjugated or nonconjugated dienes having 10 or less carbon atoms, anionic ligands or neutral ligands capable of coordinating with a lone pair of electrons in the same or different combinations A group or an atom, n is 1 or 2, and represents the number of X. )

(Wherein M is zirconium, titanium or hafnium, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are hydrogen, hydrocarbon group, silicon-containing hydrocarbon group. Each may be the same or different, and adjacent substituents from R ¹ to R ⁸ may be bonded to each other to form a ring, and X is a halogen atom, a hydrogen atom, or a carbon number. 1 to 10 hydrocarbon groups, or neutral, conjugated or nonconjugated dienes having 10 or less carbon atoms, anionic ligands or neutral ligands capable of coordinating with a lone pair of electrons are selected in the same or different combinations. A group or atom, n is 1 or 2, and represents the number of X, Q is selected from carbon, silicon or germanium, Y ¹ and Y ² are hydrogen, hydrocarbon group, silicon Selected from the hydrocarbon groups contained, They may be different from each other and may be bonded to each other to form a ring.)
In the general formula [3] or [4], the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. These are alkylaryl groups of several 7 to 20, and may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, and 1-ethyl-1-methylpropyl. 1,1,2,2-tetramethylpropyl, sec-butyl, tert-
Butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, 1-adamantyl, 2-
Examples thereof include adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl and the like.

In the general formula [3] or [4], the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, Examples thereof include tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ in the general formula [3]
R ¹⁰ is selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above. In the above general formula [4], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and are the same. But it can be different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ¹⁰ on the cyclopentadienyl ring of the general formula [3] are:
They may combine with each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like. Moreover, the adjacent substituents from R ¹ to R ⁸ on the cyclopentadienyl ring of the general formula [4] may be bonded to each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

In the present invention, M in the general formula [3] or [4] is zirconium, titanium, or hafnium.
X is a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone electron pair. One group or atom selected from the same or different combinations from the organic ligands. Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, Ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2 -Tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl And the like. Specific examples of neutral, conjugated or non-conjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-
Butadiene, s-cis- or s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene, s-
Cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, s-cis- or s -Trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -1,4-
Examples thereof include bis (trimethylsilyl) -1,3-butadiene. Specific examples of anionic ligands include alkoxy groups such as methoxy, tert-butoxy, phenoxy, acetate,
Examples thereof include carboxylate groups such as benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations.
n is 1 or 2, and indicates the number of X.

  Among the compounds represented by the above general formula [4], a preferred specific structure is represented by the following general formula [5] or [6].

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are hydrogen and hydrocarbon. Selected from a group and a silicon-containing group, which may be the same or different, and adjacent substituents from R ¹ to R ¹⁴ may be bonded to each other to form a ring, and M is zirconium, titanium or hafnium. Y is a group 14 atom, Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone pair of electrons And may be selected from the same or different combinations from the neutral ligands that can be coordinated with each other, n is an integer of 2 or 3, and j is an integer of 1 to 4.)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ are hydrogen atoms, R ⁶ and R ¹¹ may be selected from a hydrocarbon group and a silicon-containing group, and each may be the same or different, and adjacent groups may be bonded to each other to form a ring. , The same atom selected from silicon-containing groups or the same group, which may be bonded to each other to form a ring, and R ⁷ and R ¹⁰ are the same atom selected from hydrogen, a hydrocarbon group and a silicon-containing group. Or R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ may not be hydrogen atoms at the same time, and R ¹⁵ and R ¹⁶ may be the same or different from each other. M is zirconium, titanium or hafnium, preferably Zr or Hf, and Y is carbon or ketone. Is hydrogen, Q is halogen, hydrocarbon group, may be selected in the same or different combination from a neutral ligand capable of coordination by an anionic ligand or a lone pair, j is 1
It is an integer of 4. )
Hereinafter, a cyclopentadienyl group, a fluorenyl group, a bridging portion, and other characteristics, which are characteristics of the chemical structure of the bridged metallocene compound, will be described in order, and then preferred bridged metallocene compounds having these characteristics and examples thereof will be exemplified.

Cyclopentadienyl group The cyclopentadienyl group may or may not be substituted. The cyclopentadienyl group which may or may not be substituted is all of R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the general formula [5] or [6]. A hydrogen atom or R ¹
Any one or more of R ² , R ³ and R ⁴ is a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or a silicon-containing group (f2), Preferably, it means a cyclopentadienyl group substituted with a silicon-containing group (f2 ′) having 1 to 20 carbon atoms in total. The hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl, alkenyl, alkynyl, or aryl group composed of only carbon and hydrogen. These include those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring. The hydrocarbon group having 1 to 20 carbon atoms (f1 ′) includes, in addition to alkyl, alkenyl, alkynyl and aryl groups composed only of carbon and hydrogen, a part of hydrogen atoms directly connected to these carbon atoms are halogen atoms. , An oxygen-containing group, a nitrogen-containing group, a heteroatom-containing hydrocarbon group substituted with a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group. Examples of such a group (f1 ′) include methyl group, ethyl group, n-propyl group, allyl group, n-
Linear hydrocarbon groups such as butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl; isopropyl, t-butyl, amyl Group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-
Branched hydrocarbon groups such as 1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, Cyclic saturated hydrocarbon groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group and their nuclei Alkyl-substituted product; saturated hydrocarbon group substituted with aryl group such as benzyl group, cumyl group; methoxy group, ethoxy group, phenoxy group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, A hetero atom-containing hydrocarbon group such as a pentafluorophenyl group can be exemplified.

The silicon-containing group (f2) is, for example, a group in which a ring carbon of a cyclopentadienyl group is directly covalently bonded to a silicon atom, and specifically an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2 ′) having a total carbon number of 1 to 20 include a trimethylsilyl group and a triphenylsilyl group.

Fluorenyl Group The fluorenyl group in the above general formula [5] may or may not be substituted. The fluorenyl group which may or may not be substituted is R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² possessed by the fluorenyl group moiety in the above general formula [5]. Are all hydrogen atoms, or at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably Means a fluorenyl group substituted with a hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, or a silicon-containing group (f2), preferably a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. To do. The important point in the fluorenyl group moiety in the chemical structural formula represented by the general formula [5] used in the polymerization method of the present invention is that from the viewpoint of synthesizing the α-olefin (co) polymer of the present invention. R ⁶ and R ¹¹ in the formula [5] are the same atom or the same group selected from hydrogen, hydrocarbon group (f1), and silicon-containing group (f2), and may be bonded to each other to form a ring. well, R ⁷ and R ¹⁰ are hydrogen, a hydrocarbon group (f1), linked to each other are the same atoms or the same group selected from silicon-containing group (f2) may form a ring, R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms at the same time. Among these, R ⁶
, R ⁷ , R ¹⁰ and R ¹¹ are preferably not all hydrogen atoms. Among them, R ⁶ and R ⁷ ,
More preferably, R ¹⁰ and R ¹¹ are each bonded to form a ring. As a result, in synthesizing the α-olefin (co) polymer of the present invention, it became possible to reduce the narrow molecular weight distribution and the content of unsaturated groups at the molecular piece terminals. A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).

The important point in the fluorenyl group part in the chemical structural formula represented by the general formula [6] is that R ⁶ and R ¹¹ in the general formula [6] are hydrogen, hydrocarbon group (f1), silicon-containing group (f2 ) May be the same atom or the same group selected from the above, and may be bonded to each other to form a ring, and R ⁷ and R ¹⁰ are selected from hydrogen, hydrocarbon group (f1), and silicon-containing group (f2). The same atom or the same group may be bonded to each other to form a ring, and R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not hydrogen atoms at the same time. Among these, from the viewpoint of synthesizing the α-olefin (co) polymer of the present invention, it is preferable that R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are not all hydrogen atoms. Among them, it is more preferable that R ⁶ and R ⁷ , R ¹⁰ and R ¹¹ are bonded to form a ring. Thereby, in synthesizing the α-olefin (co) polymer of the present invention, it became possible to reduce the narrow molecular weight distribution and the content of unsaturated groups at the molecular piece terminals. A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having 1 to 20 carbon atoms, and a preferred example of the silicon-containing group (f2) is the above-mentioned 1 to 20 carbon atoms. Silicon-containing group (
f2 ′).

The fluorene is specifically unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene, or 2,3,6,7-tetrasubstituted fluorene. Examples of fluorenyl groups in which R ⁵ to R ¹² adjacent substituents on the fluorene ring are bonded to each other to form a ring include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyl And octahydrodibenzofluorenyl. Here, the 2nd, 3rd, 6th and 7th positions on the fluorene ring correspond to R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ , respectively.

In the main chain portion of the bond connecting the covalently bonded cyclopentadienyl group and the fluorenyl group, in the above general formula [5] or [6], the bridge atom Y is a Group 14 atom, preferably carbon and silicon. .

In the general formula [5], n is an integer of 2 or 3, more preferably 2. The important point in the present invention is that the bridging atom Y has R ¹³ and R ¹⁴ which may be the same or different from each other. R ¹³ and R ¹⁴ may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), a silicon-containing group having 1 to 20 carbon atoms (f2 ′), or a halogen atom.

As a result, in synthesizing the α-olefin (co) polymer of the present invention, it became possible to reduce the narrow molecular weight distribution and the content of unsaturated groups at the molecular fragment ends.
In the general formula [6], the bridging atom Y has R ¹⁵ and R ¹⁶ which may be the same or different from each other. Examples of R ¹⁵ and R ¹⁶ include the aforementioned hydrocarbon group having 1 to 20 carbon atoms (f1 ′), the aforementioned silicon-containing group having 1 to 20 carbon atoms (f2 ′), and a halogen atom.
The important point in the present invention is that the bridging atom Y of the covalent bond bridging moiety has a group [R ¹⁵ and R ¹⁶ ] which may be the same or different from each other. Among these, an aryl group or a substituted aryl group is preferable. Illustrative, phenyl group, naphthyl group, anthracenyl group and can be one or more of these aromatic hydrogen (sp ² type hydrogen) illustrate been substituted with a substituent. As the substituent, the total number of carbon atoms is 1 to 20 as described above.
Hydrocarbon groups (f1 ′), silicon-containing groups (f2 ′) having 1 to 20 carbon atoms, and halogen atoms. Aryl groups include phenyl, tolyl, t-butylphenyl, dimethylphenyl, biphenyl, cyclohexylphenyl, (trifluoromethyl) phenyl, bis (trifluoromethyl) phenyl, chlorophenyl and dichlorophenyl groups More preferred are those in which a halogen atom is introduced into a substituent, such as a substituted phenyl group in which these substituents are located at the meta position and / or the para position. In the bridged metallocene compound according to the present invention, those in which R ¹⁵ and R ¹⁶ are the same are preferably used because of their ease of production.

As will be described later, the component of the olefin polymerization catalyst according to the present invention uses the general formula [6] when the transition metal compound is used as the transition metal compound (A) of Group 4 of the periodic table. (B-1) an organometallic compound and / or (B-2) an organoaluminum compound and / or (B-4) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair. It is preferable. In particular, when R ¹⁵ and R ^{16 in} the general formula [6] are phenyl groups, the compound (B) that is a constituent of the olefin polymerization catalyst according to the present invention includes (B-1) an organometallic compound and Or (B-2) an organoaluminum compound and / or (B-4) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair, and (B-3) an organoaluminum oxy No compound is used.

Other characteristics of the bridged metallocene compound In the general formula [5] or [6], Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, They are selected from the same or different combinations from anionic ligands or neutral ligands that can coordinate with a lone pair of electrons. Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl Etc. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene, and the like. Specific examples of anionic ligands include methoxy, tert-
Examples include alkoxy groups such as butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.

Preferred bridged metallocene compounds and examples thereof Specific examples of Group 4 transition metal compounds represented by the above general formulas [3], [4], [5] and [6] are shown below. However, the range is not limited.

Specific examples of the general formula [3] include cyclopentadienyl trichloride, cyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (penta Methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Bis (butylcyclopentadienyl) zirconium including propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, etc. Bis (dimethylcyclopentadienyl) zirconium dichloride, including bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, etc. Bis (methylpropylcyclopentadienyl) including diethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride, etc. ) Zirconium dichloride, bis (1-
Examples thereof include bis (methylbutylcyclopentadienyl) zirconium dichloride containing methyl-3-n-butylcyclopentadienyl) zirconium dichloride and the like.

Specific examples of the general formula [4] include ethylene bis (indenyl) zirconium dichloride, ethylene bis (1-indenyl) titanium dichloride, ethylene bis (4,5
, 6,7-Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (di-tert-butylcyclopentadiene) Enyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethylsilylenebis (2- Methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, di Tylethylenebis (2-methylindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylethylenebis (2-Methyl-4-naphthylindenyl) zirconium dichloride.

Specific examples of the general formula [5] include ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) ) (Benzofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, ethylene (cycline) Lopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorene) Nyl) zirconium dichloride, ethylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) ) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7- (trimethylphenyl)- 3,6-ditert-butylfluorenyl) zirconium dichloride,

Ethylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,3,6,7-tetratert -Butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, propylene
(Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) ) (Benzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) ) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) ) Zirconium Rholide, Tetramethyldisilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, Tetramethyldisilylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, Tetramethyldisilylene ( Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, tetramethyldisilene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride,

Tetramethyldisilylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, tetramethyldisilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, tetramethyldisilylene (cyclopentadienyl) (octa Hydrodibenzofluorenyl) zirconium dichloride, tetramethyldisilene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl)
Zirconium dichloride, tetramethyldisilene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (fluorenyl) ) Zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (Benzofluorenyl) zirconium dichlor Id, ethylene (methyl-tert-butylcyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, ethylene (methyl- tert-butylcyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (methyl-tert-butylcyclopentadienyl) (2,7-dimethyl- 3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (3,6-di-tert -Butylfluorenyl) zirconium dichloride,
Ethylene (tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride , Ethylene (tert-
Butylcyclopentadienyl) (benzofluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (octahydrodibenzofluorene) Nyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl)
(2,7-Diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, ethylene (tert-butylcyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluoride) Olenyl) zirconium dichloride.

Specific examples of the general formula [6] include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride and isopropylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride. Isopropylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride, isopropylidene (Cyclopentadienyl) (benzofluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octahydrodiben) Zofluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-dimethyl) -3,6-di-tert-butylfluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (1 , 3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7- (trimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,
6-ditert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl) (Fluorenyl) zirconium dichloride, isopropylidene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride,

Isopropylidene (methyl-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-) tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydro Dibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (dibenzofluorenyl) zirco Um dichloride, cyclohexylidene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorene) Nyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (1,3,3', 6,6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, cyclohexylidene (cyclopente) Tadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

Cyclohexylidene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,3,6, 7-tetra-tert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) ) Zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) Zirconium dichloride, adamantylidene (cyclopentadienyl) (ben Zofluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, adamantylidene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride,
Adamantylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (
1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (1,3,3 ′, 6, 6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfur Oleenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) ( 2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) (3,6-di -tert- butyl fluorenyl) zirconium dichloride,

Dimethylsilylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzfluorenyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) (benzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, Dimethylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-dimethyl) Ru-3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclo Pentafluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,
7-dihydrodicyclopentafluorenyl) zirconium dichloride, dimethylsilylene (
Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3, 6-ditert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ( 2,7-ditert-butylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopenta Dienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (1,1 ', 3, 6,8,8'-
Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2
, 7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadi) Enyl) (2,7-dimethyl-3
, 6-Ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl)
Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,3,6 , 7-Tetra-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di ( p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, Di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8,8'- Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7 -Dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2 , 7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl)-
3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di ( p-chlorophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfullyl) Oleenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodi) (Cyclopentafluorenyl) zirconium dichloride, di (p-
Chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8
, 8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl -2,7-dihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p- Chlorophenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) ( 2,7-ditert-butylfluorenyl) zirconium dichloride,

Di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorene Nyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) ) Zirconium dichloride, di (m-chlorophenyl)
Methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadiene) Enyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) Phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2, 3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p -Bromophenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl ) Zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium Dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1,1 ', 3,6,8 , 8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (1,3,3 ', 6,6', 8- Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

Di (p-bromophenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopenta Dienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,3,6,7 -Tetra-tert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tri Fluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadiene) Nyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m- Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8 , 8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-
Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′,
8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butyl fluorenyl) zirconium dichloride,

Di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (Cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra tert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (
2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di ( p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodi Cyclopentafluorenyl) Zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadiene) Enil) (1,1 ', 3
6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6 , 6 ', 8-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,
6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorene Nyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -Trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) ) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium Chloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) ( Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride,

Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6- Di-tert-butylfluorenyl) zirconium Lido, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p- n-
(Butyl-phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (
Octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, di (p-n-butyl -Phenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-n-butyl-
Phenyl) methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2
7-dihydrodicyclopentafluorenyl) zirconium dichloride,

Di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butyl-phenyl) methylene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- ( Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6- Ditert-butylfluorenyl) zirconium dichlorine , Di (p-n-butyl -
Phenyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (
Octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (1 , 1 ', 3,6,8,8'-
Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-biphenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride,

Di (p-biphenyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3
, 6-Ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2 , 7-Ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydride) Dicyclopentafluorenyl) Zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,1 ' , 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (1,3,3 ′, 6, 6 ', 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3
, 6-Ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7- (Dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert- Butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) ( , 6-di-tert- butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (2-
Naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (2-naphthyl) ) Methylene (cyclopentadienyl) (1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopenta Dienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl)
Zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) ) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7- (trimethylphenyl) -3,6- Ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-
Di-tert-butylfluorenyl) zirconium dichloride,

Di (2-naphthyl) methylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7- Ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (dibenzofluoride) Oleenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) Lodibenzofluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2 , 7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopenta Dienyl) (3,6-ditert-
Butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (Cyclopentadienyl) (3,6-ditert-butyl (Luolenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclohexane) Pentadienyl) (dibenzofluorenyl) zirconium dichloride,

Diphenethylmethylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclohexane) Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) ) Methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadi) Nyl) (dibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclo Pentafluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium Dichloride, di (cumyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, di (cumyl) methylene (Cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octahydrodibenzo Fluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl- Ethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) di Luconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium Dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride,

Di (1-phenyl-ethyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (
Cyclopentadienyl) (fluorenyl) zirconium dichloride, di (biphenylmethyl)
Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride Di (biphenylmethyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (benzofluorenyl) zirconium dichloride, di (biphenyl) Methyl) methylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (octahydrodibenzofluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopenta Dienyl) (octamethyltetra De Logistics cyclopentadienyl fluorenyl) zirconium dichloride, di (p- tolyl) methylene (cyclopentadienyl) (2,3,6,7
Tetramethylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (
Octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,1 ', 3,6,8, 8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (1,3,3 ', 6,6', 8-hexamethyl-2,7-dihydro Dicyclopentafluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2 , 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphe Rushiriren (cyclopentadienyl) (2,7 (trimethylphenyl) -3,6-di-tert- butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7 (dimethyl phenyl) -
3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (Methyl-tert-butylcyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (3,6- Di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene ( Methyl-tert-butylcyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-te rt-Butylcyclopentadienyl) (dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (1,1 ', 3,6,8,8'- Hexamethyl-2
, 7-Dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2 , 7-dihydrodicyclopentafluorenyl) zirconium dichloride,

Di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (2,7-diphenyl-
3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di ( p-tolyl) methylene (methyl-tert-butylcyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methyl -tert-butylcyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (2,7-ditert -Butylfluorenyl) zirconium Dichloride,
Di (p-tolyl) methylene (methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (octamethyloctahydrodibenzo (Fluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) ( Dibenzofluorenyl) Zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (1,1 ', 3,6,8,8'-hexamethyl-2,7-dihydrodicyclopentafluorenyl ) Zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-di) Drodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -Tolyl) methylene (methylcyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (2, 7- (Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (2,7- (dimethylphenyl) -3,6- Di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (methylcyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di (p-to Le) methylene (tetramethylcyclopentadienyl) (2
, 7-Ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (tetramethylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium Dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (1,1 ', 3,6) , 8,8'-Hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tri L) methylene (tetramethylcyclopentadienyl) (1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl) zirconium dichloride, di (p-tolyl) methylene (Tetramethylcyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (2,7- Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

Di (p-tolyl) methylene (tetramethylcyclopentadienyl) (2,7- (trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (tetramethyl Cyclopentadienyl) (2,7- (dimethylphenyl) -3,6-ditert-
Examples thereof include butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (tetramethylcyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, and the like.

  In addition to titanium compounds and hafnium compounds having the same steric structure, bromide, iodide, etc., for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, Examples thereof include transition metal compounds described in Kaihei 3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300877, WO01 / 27124A1, and the like. .

  Here, octamethyloctahydrodibenzofluorene refers to a compound having the structure represented by the formula [7], and octamethyltetrahydrodicyclopentafluorene refers to a compound having the structure represented by the formula [8], and dibenzofluorene and Indicates a compound having the structure represented by the formula [9], and 1,1 ′, 3,6,8,8′-hexamethyl-2,7-dihydrodicyclopentafluorenyl is represented by the formula [10]. It refers to a compound having a structure, and 1,3,3 ′, 6,6 ′, 8-hexamethyl-2,7-dihydrodicyclopentafluorenyl refers to a compound having the structure represented by the formula [11].

Specifically, the transition metal compound (A) used in this example is represented by the following formulas [12], [13], [14]
, [15], [16], [17], [18] and [19], but the present invention is not limited to these compounds.

The structure of the obtained transition metal compound was 270 MHz ¹ H-NMR (JEOL GSH-27
0), determined by FD-mass spectrometry (JEOL SX-102A).
When the bridged metallocene compound of the present invention is used as an olefin polymerization catalyst, the catalyst component is represented by (A) the general formulas [1], [2], [3], [4], [5] and [6]. Bridged metallocene compounds, (B) (B-1) organometallic compounds, (B-2) organoaluminum compounds, (B-
3) Organoaluminumoxy compound, (B-4) It is composed of at least one compound selected from compounds that react with the Group 4 transition metal compound (A) to form ion pairs.

Hereinafter, the component (B) will be specifically described.
(B-1) Organometallic compound (B-1) As the organometallic compound used in the present invention, the following organometallic compounds are specifically used.

General formula R ^a R ^b M ³ ------------- [20]
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.
Moreover, such an organometallic compound (B-1) may be used individually by 1 type, and may be used in combination of 2 or more type.
(B-2) Organoaluminum compound Forming the catalyst for olefin polymerization (B-2) As the organoaluminum compound, for example, an organoaluminum compound represented by the following general formula [21], represented by the following general formula [22] Or a complex alkylated product of a Group 1 metal and aluminum, or an organoaluminum oxy compound.

R ^a _m Al (OR ^b ) _n H _p X _q ------------- [21]
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

M ² AlR ^a ₄ ------------- [22]
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Alkylate complex of aluminum and aluminum. Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the organoaluminum compound represented by the general formula [21] include compounds represented by the following general formula [23], [24], [25], or [26].
R ^a _m Al (OR ^b ) _3-m ------------- [23]
(In the formula, R ^a and R ^b may be the same or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ A number of 3.)
R ^a _m AlX _3-m ------------- [24]
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3.)
R ^a _m AlH _3-m ------------- [25]
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3.)
R ^a _m Al (OR ^b ) _n X _q ------------- [26]
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3.)
More specifically, examples of the aluminum compound represented by the general formula [23], [24], [25], or [26] include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, Tri-n-alkylaluminums such as pentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri 3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexyl Tri-branched alkylaluminum such as aluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritylaluminum; diisopropylaluminum hydride dialkylaluminum hydride such as; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (. wherein, x, y, z are each a positive number, and z ≦ 2x), etc. Alkenyl aluminum such as isoprenyl aluminum represented by: Alkyl aluminum such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; general formula ^Ra _2.5 Al (OR ^b ) _0.5 A partially alkoxylated alkylaluminum having an average composition represented by: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6- Di-t-butyl-4-methylphenoxide), diisobutylaluminum (2
, 6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), and the like; dimethylaluminum chloride, diethylaluminum chloride, Dialkylaluminum halides such as dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Partially halogenated alkyl aluminums such as alkyl aluminum dihalides; Dialkylaluminum hydrides such as minium hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxychloride, butylaluminum butoxycyclide, Mention may be made of partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxybromide.

A compound similar to the compound represented by the general formula [21] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AlN (C ₂
H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of the compound represented by the general formula [22] include LiAl (C ₂ H ₅ ) ₄ , Li
Such as Al (C ₇ H _{15) 4} may be cited.
In addition, a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can be used.

Of these, organoaluminum compounds are preferred.
The organoaluminum compound represented by the general formula [21] or the complex alkylated product of the Group 1 metal and aluminum represented by the general formula [22] may be used singly or in combination of two or more. .
(B-3) Organoaluminum Oxy Compound As the organoaluminum oxy compound used in the present invention, a conventionally known aluminoxane can be used as it is. Specifically, the following general formula [27]

  And / or general formula [28]

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more). Particularly, R is a methylaluminoxane having a methyl group, and n is 3 More preferably, 10 or more are used. These aluminoxanes may be mixed with some organoaluminum compounds. A characteristic property in the high-temperature solution polymerization of the present invention is that a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more types of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the high temperature solution polymerization of the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less. Is 2% or less, and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in [29] below.

(Here, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [29] is generally called MMAO. Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd. and the like are commercially produced under the names MMAO and TMAO where R is an isobutyl group prepared using trimethylaluminum and triisobutylaluminum. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability.

Furthermore, as the organoaluminum oxy compound used in the present invention, the following general formula [3
An organoaluminum oxy compound containing boron represented by 0] can also be mentioned.

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
The organoaluminum oxy compound containing boron represented by the general formula [30] is obtained by combining an alkyl boronic acid represented by the following general formula [31] and an organoaluminum compound in an inert solvent under an inert gas atmosphere. Thus, it can be produced by reacting at -80 ° C to room temperature for 1 minute to 24 hours.

R ^c B (OH) ₂ ------------ [31]
(In the formula, R ^c represents the same group as described above.)
Specific examples of the alkyl boronic acid represented by the general formula [31] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,
And 5-bis (trifluoromethyl) phenylboronic acid. Among these,
Methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferred. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the general formula [21] or [22]. .

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
(B-4) A compound that reacts with the Group 4 transition metal compound (A) to form an ion pair. A compound (B-4) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter referred to as “
It may be abbreviated as “ionic compound”. ) As disclosed in JP-A-1-501950,
JP-A-1-502036, JP-A-3-179005, JP-A-3-179006
And Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-3-207703, JP-A-3-207704, USP5321106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula [32].

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, Re ^{e +} is preferably a carbenium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl). (Phenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (
And 3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-
Butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ) Ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium Tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) Borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl)
Examples thereof include borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate and dioctadecylmethylammonium.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylaniliniumtetrakis (pentafluorophenyl) borate, N, N-
Diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N
, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.
The ionic compound (B-4) as described above can be used in combination of two or more.

As the component (B) used in this example, when the transition metal compound (A) is the general formula [12], the organoaluminum oxy compound (B-3) shown above was used. Specifically, it is a commercially available MAO / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd. In the case where the transition metal compound (A) is represented by the general formulas [13], [14], [15], [16], [17], [18] and [19] (B- 2) an organoaluminum compound and (B-4) the fourth
And a compound that forms an ion pair by reacting with the group III transition metal compound (A). Specifically, triisobutylaluminum and N, N-dimethylanilinium tetraphenylborate.
Among the compounds mentioned so far, the compound most suitable for producing the α-olefin (co) polymer of the present invention is a compound represented by the general formula [5] or [6], which is used in this case (B ) Compounds include (B-1) organometallic compounds and / or (B-2) organoaluminum compounds and / or (B-4) reacting with the Group 4 transition metal compounds (A) to form ion pairs. It is preferred that a compound is used. Particularly in the case of [6], when R ¹⁵ and R ¹⁶ are phenyl groups, they are constituents of the olefin polymerization catalyst according to the present invention in order to produce the α-olefin (co) polymer of the present invention. (B) The compound reacts with (B-1) an organometallic compound and / or (B-2) an organoaluminum compound and / or (B-4) the Group 4 transition metal compound (A) to form an ion pair. And (B-3) an organoaluminum oxy compound is never used.

  In the preparation of the olefin polymerization catalyst used in the present invention, a carrier can be used as necessary. The carrier is usually an inorganic or organic compound and is a granular or particulate solid. Among these, examples of the inorganic compound include porous oxides, inorganic chlorides, clays, clay minerals, and ion exchange layered compounds.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these, eg natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO.

  In the present invention, an α-olefin having 6 to 20 carbon atoms is homopolymerized in the presence of the olefin polymerization catalyst as described above, or olefins are copolymerized to produce an olefin low molecular weight polymer.

  Here, as the α-olefin having 6 to 20 carbon atoms, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, Examples thereof include α-olefins having 6 to 20, preferably 6 to 16, carbon atoms such as -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene. In the case of a copolymer, two or more kinds of an olefin having 6 to 20 carbon atoms and an α-olefin having 2 to 20 carbon atoms are arbitrarily used in combination.

Here, the α-olefin having 2 to 20 carbon atoms includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, Examples include 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. Among these, an α-olefin having 2 to 16 carbon atoms is particularly preferable.

It is a preferred embodiment of the olefin that at least one of the olefins is 1-octene, 1-decene, 1-dodecene or 1-tetradecene. Particularly preferred are 1-octene homopolymerization, 1-decene homopolymerization, 1-dodecene homopolymerization or 1-tetradecene homopolymerization, and copolymerization using these as main monomers.

The specific aspect which manufactures the olefin low molecular weight polymer which is the alpha-olefin (co) copolymer used for this invention is demonstrated in detail below.
In the present invention, the polymerization reaction is carried out in a hydrocarbon medium. Specific examples of such hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic carbons such as cyclopentane, cyclohexane, and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as hydrogen, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and petroleum fractions such as gasoline, kerosene and light oil. Furthermore, the olefin used for superposition | polymerization can also be used.

In the present invention, the polymerization is carried out in the presence of the olefin polymerization catalyst as described above. In this case, the Group 4 transition metal compound (A) is usually used as the concentration of transition metal atoms in the polymerization reaction system. ,
When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of reaction volume.
It is used in such an amount that it becomes a mole.
Component (B-1) contains a molar ratio of component (B-1) to all transition metal atoms (M) in component (A) [(B-
1) / M] is usually used in an amount of 1 to 5,000, preferably 10 to 2,000. Component (B-2) has a molar ratio [(B-2) / M] of component (B-2) to transition metal atom (M) in component (A) of usually 100 to 25,000, Preferably, it is used in such an amount as to be 200 to 10,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) of usually 10 to 5,000, Preferably, it is used in such an amount that it is 20 to 2,000. Component (B-4) has a molar ratio [(B-4) / M] of component (B-4) to all transition metals (M) in component (A) of usually 1 to 1,000, preferably Is used in an amount of 1.5 to 500. More preferably, it is used in an amount of 2 to 200.

  Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-180 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

The lubricating oil composition of the present invention comprises:
(A) 15 to 90 parts by weight of the above α-olefin (co) polymer,
(B) A low-viscosity base oil consisting of at least one base oil selected from mineral oils, synthetic hydrocarbon oils and ester oils and having a kinematic viscosity at 100 ° C. in the range of ² to 10 mm ² / s, 10 to 85 wt. And
(C) It consists of detergent dispersant, viscosity index improver, antioxidant, corrosion inhibitor, antiwear agent, friction modifier, pour point depressant, rust inhibitor, antifoaming agent and extreme pressure agent as necessary. It consists of at least one additive selected from the group.

The low-viscosity base oil used in the lubricating oil composition of the present invention is selected from conventionally known mineral oils, synthetic hydrocarbon oils, and ester oils having a kinematic viscosity at 100 ° C. in the range of ² to 10 mm ² / s. At least one base oil is used.

  Mineral oils generally have several grades depending on the method of refining, but generally mineral oils containing 0.5 to 10% wax are used. For example, a highly refined oil having a composition mainly composed of isoparaffin having a low pour point and a high viscosity index produced by a hydrocracking refining method can be used.

  Examples of the synthetic hydrocarbon oil include α-olefin oligomers, alkylbenzenes, alkylnaphthalenes and the like, and these can be used alone or in combination of two or more. Among these, as the α-olefin oligomer, a low molecular weight oligomer of at least one olefin selected from olefins having 8 to 12 carbon atoms can be used. Such an α-olefin oligomer can be produced by cationic polymerization, thermal polymerization, or radical polymerization using a Ziegler catalyst or a Lewis acid as a catalyst.

  Alkylbenzenes and alkylnaphthalenes are usually mostly dialkylbenzene or dialkylnaphthalene having an alkyl chain length of 6 to 14 carbon atoms. Such alkylbenzenes or alkylnaphthalenes are Friedel of benzene or naphthalene and olefin. Produced by kraft alkylation reaction. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be a linear or branched olefin or a combination thereof. These production methods are described, for example, in US Pat. No. 3,909,432.

  As ester oils, monoesters produced from monobasic acids and alcohols; diesters produced from dibasic acids and alcohols, or diols and monobasic acids or acid mixtures; diols, triols (eg trimethylolpropane) And polyol ester produced by reacting tetraol (for example, pentaerythritol), hexaol (for example, dipentaerythritol) and the like with a monobasic acid or an acid mixture. Examples of these esters include tridecyl pelargonate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, trimethylolpropane triheptanoate, pentaerythritol tetraheptanoate, and the like.

The following can be illustrated as an additive used for the lubricating oil composition of this invention, These can be used individually or in combination of 2 or more types.
Detergent / dispersant: Examples thereof include metal sulfonates, metal phenates, metal phosphonates, succinimides and the like, and they are usually used in the range of 0 to 15% by weight.
Pour point depressant: Polymethacrylate, alkylnaphthalene and the like can be exemplified, and usually used in the range of 0 to 3% by weight.
Extreme pressure agent: Sulfur-based extreme pressure agent such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurized olefins; phosphate ester, phosphite ester, phosphate ester amine salt, Illustrative are phosphoric acids such as phosphite amines; halogen compounds such as chlorinated hydrocarbons. The extreme pressure agent is used in the range of 0 to 15% by weight as necessary.
Antiwear: Inorganic or organic molybdenum compounds such as molybdenum disulfide, organic boron compounds such as alkyl mercaptyl borates; graphite, antimony sulfide, boron compounds, polytetrafluoroethylene, and the like. The antiwear agent is used in the range of 0 to 3% by weight as required.
Antioxidant: Phenolic and amine compounds such as 2,6-di-tert-butyl-4-methylphenol are exemplified. Antioxidants are used in the range of 0 to 3% by weight as required.
Rust preventive agent: Compounds such as various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates. A rust preventive is used in the range of 0 to 3% by weight as required.
Antifoaming agent: Silicone compounds such as dimethylsiloxane and silica gel dispersion, alcohol compounds or ester compounds can be exemplified. The antifoaming agent is used in the range of 0 to 0.2% by weight as necessary.

In addition to the above additives, a demulsifier, a colorant, an oily agent (oiliness improver), and the like can be used as necessary.
[Example]
The synthetic lubricating oil of the present invention is used as lubricating oil (engine oil, transmission gear oil, ATF, CVT-F, differential gear oil), industrial lubricating oil (gear oil, hydraulic oil), and grease base oil. EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.
Average molecular weight / number distribution of molecular weight Average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured as follows using GPC (Chromatopack C-R4A) manufactured by Shimadzu Corporation. TSK as a separation column
G6000H XL, G4000H XL, G3000H XL, G2000H XL are used, the column temperature is 40 ° C., tetrahydrofuran (Wako Pure Chemical Industries) is used as the mobile phase, the development rate is 0.8 ml / min, and the sample concentration is 0.2. The amount of sample injection was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used.
Unsaturated group content at molecular end The content of unsaturated group at the molecular end was measured as follows using an EX400 nuclear magnetic resonance apparatus manufactured by JEOL. ^{In 1} H-NMR, a polymer was measured in a sample tube in a deuterated chloroform (Aldrich, 99.8 atom% D) as a lock solvent and adjusted to 2% by weight at room temperature. The peak of each hydrogen of the polymer has a peak (A) based on a terminal saturated methyl group of 0.65 to 0.85 ppm and a peak (B) based on a vinylidene group of 4.7.
From 0 ppm to 4.80 ppm, peaks (C) and (D) based on vinyl groups are 4.85 each.
-5.0 ppm and 5.7-5.9 ppm, peaks (E) based on internal olefins are observed at 5.10-5.30 ppm, and peaks (F) based on methylene groups are observed at 0.90-2.0 ppm. . If the peak areas of each peak (A), (B), (C), (D), (E), (F) are SA, SB, SC, SD, SE, SF, respectively, The number N of unsaturated bonds is calculated by the following formula (33) from the peak intensities of (A), (B), (C), (D), (E), and (F).
A: Methyl 0.65-0.85 ppm
B: Vinylidene 4.70-4.80 ppm
C: Vinyl 4.85-5.00 ppm
D: Vinyl 5.70-5.90ppm
E: Internal olefin (tri-substituted product) 5.1 to 5.3 ppm
F: Methylene 0.9-2.0 ppm
The unsaturated group content at the molecular end is calculated by the following formula (34) using the absolute average molecular weight M measured by N and VPO determined from the above formula (33).

Unsaturated group content [%] at molecular terminal end = N × M × 2/14 (34)

N: number of unsaturated groups [units / total protons]
M: Absolute molecular weight
The kinematic viscosity and viscosity index at 100 ° C. and 40 ° C. of the viscosity characteristic polymer were measured and calculated by the method described in JIS K2283.

The viscosity characteristics of the blended oil are such that the kinematic viscosity at 100 ° C. is 14 mm ² / s and the polymer and PAO-6 (Nippon Steel Chemical Co., Ltd., Shinflud 601), ester oil (Daihachi Chemical Industry Co., Ltd.) Company DIDA) 15%, extreme pressure agent (LUBRIZOL Angramol 98A) 6.5% mixed, kinematic viscosity and viscosity index of the resulting mixed oil at 100 ° C. and 40 ° C. according to the method described in JIS K2283 , Measured and calculated.

The pour point of the blended oil was measured by the method described in JIS K2269.
The low temperature viscosity of the blended oil was measured at −40 ° C. with a Brookfield viscometer in accordance with ASTM D2983.
Shear stability The shear stability of the blended oil was evaluated using a KRL shear stability tester in accordance with the method described in DIN 52350-6. The blended oil was placed under shearing conditions (1450 rpm) at 60 ° C. for 20 hours, and the rate of decrease in kinematic viscosity at 100 ° C. before and after the test was evaluated.
Thermal oxidation stability The thermal oxidation stability was tested as follows. 30 g of the sample was put in a glass petri dish having a diameter of 55 mm, left in a circulating drier kept at 180 ° C. for 24 hours, then taken out, allowed to cool to room temperature, and the mass of the sample before and after the test was measured. The amount of evaporation was determined from equation (35).

Weight loss ratio [wt%] = (W1-W2) / W1 × 100 (35)

W1: Weight before test
W2: Weight after test

The kinematic viscosity at 100 ° C. before and after the test was measured by the method described in JIS K2283, and the increase in viscosity was calculated by the following formula (36).

Kinematic viscosity change rate [%] = V2 / V1 × 100 (36)

V1: Kinematic viscosity before test
V2: Kinematic viscosity after the test

The total acid value of the sample before and after the test was measured by the method described in JIS K2501, and the following formula (
37) The total acid value increase was calculated.

Total acid value increase [mg KOH / g] = Total acid value after test—Total acid value before test (37)

  A glass autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and thoroughly purged with nitrogen. Thereafter, 250 ml of n-decane and 250 ml of 1-decene were charged, and the temperature was set to 100 ° C. while flowing nitrogen at 50 L / hour. On the other hand, a magnetic stirrer tip was placed in a 30 ml branch flask with a sufficient nitrogen content and ethylene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium dichloride as a transition metal compound. Toluene solution (0.002 mmol) and methylaluminoxane in toluene solution (Al = 1.53 M) were added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, hydrogen was then allowed to flow in an amount of 20 L / hour, and ethylene was flowed in an amount of 5 L / hour, and then the above solution was added and the stirring rotation speed was set to 650 rpm to initiate polymerization. During the polymerization, hydrogen was continuously supplied at a rate of 20 L / hour and ethylene at a rate of 5 L / hour, and polymerization was performed at 100 ° C. for 60 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg).

  The obtained transparent liquid polymer was 81.07 g, and the polymerization activity was 40.5 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 1,950 and Mw / Mn = 1.70.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen is charged with 300 ml of n-heptane and 200 ml of 1-decene, followed by ethylene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium. 0.0015 mmol of dichloride in toluene and 1.5 mmol of methylaluminoxane in toluene (Al = 1.53M) were added, and then the autoclave was pressurized with hydrogen gas to 0.785 MPa-G,
Polymerization was carried out while stirring at 63 ° C. for 60 minutes at a stirring speed of 350 rpm. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

  The obtained transparent liquid polymer (1-decene polymer) was 34.18 g, and the polymerization activity was 22.8 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 2,080 and Mw / Mn = 1.80.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

  A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen was charged with 630 ml of n-heptane and 70 ml of 1-decene, followed by 0.2 mmol of triisobutylaluminum, diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzo). Fluorenyl) zirconium dichloride in 0.0021 mmol of toluene, and finally, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene of 0.0084 mmol was added, and then the autoclave was adjusted to 0.785 MPa-G with hydrogen gas. The polymerization was carried out while applying pressure and stirring at a rotation speed of 350 rpm at 63 ° C. for 180 minutes. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg).

  The obtained transparent liquid polymer (1-decene polymer) was 15.29 g, and the polymerization activity was 2.4 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 2,130 and Mw / Mn = 1.51.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

N-heptane 630m in a 1L stainless steel autoclave thoroughly purged with nitrogen
l, 70 ml of 1-decene was charged, followed by 0.2 mmol of triisobutylaluminum, toluene solution of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride. 002 mmol, and finally, 0.008 mmol of a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added, and then the autoclave was pressurized to 0.785 MPa-G with hydrogen gas, and the stirring rotation speed was 350 rpm. Polymerization was conducted with stirring at 60 ° C. for 60 minutes. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

The obtained transparent liquid polymer (1-decene polymer) was 40.03 g, and the polymerization activity was 20.0 kg-polymer / mmol-Zr · hr. As a result of polymer analysis,
Mn = 3,850 and Mw / Mn = 1.58.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

A stainless steel autoclave with an internal volume of 2 L that has been sufficiently purged with nitrogen is charged with 850 ml of n-heptane and 150 ml of 1-decene, the temperature inside the system is raised to 85 ° C., and hydrogen is supplied to bring the total pressure to 4 MPa. -G. Next, 0.4 mmol of triisobutylaluminum,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 0.004 mmol and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 0.016 mmol were injected with nitrogen. Then, the polymerization was carried out at 90 ° C. for 60 minutes at a stirring rotational speed of 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

  The obtained transparent liquid polymer (1-decene polymer) was 83.00 g, and the polymerization activity was 20.8 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 2110 and Mw / Mn = 1.52.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

A stainless steel autoclave with an internal volume of 1 L that has been sufficiently purged with nitrogen is charged with 400 ml of n-heptane and 100 ml of 1-decene, followed by 0.2 mmol of triisobutylaluminum, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofur). Oleenyl) zirconium dichloride in toluene (0.0025 mmol) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene (0.01 mmol) were added, and then the autoclave was added with hydrogen gas to 0.785 MPa-G. The polymerization was conducted while stirring at 65 ° C. for 60 minutes at 350 rpm. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

  The obtained transparent liquid polymer (1-decene polymer) was 28.44 g, and the polymerization activity was 11.4 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 2180 and Mw / Mn = 1.46.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

A stainless steel autoclave with an internal volume of 1 L that was sufficiently purged with nitrogen was charged with 630 ml of n-heptane and 70 ml of 1-decene, followed by 0.2 mmol of triisobutylaluminum, di (p-tolyl) methylene (cyclopentadienyl) ( 2,7-dimethyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride in 0.002 mmol and finally N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene in 0.008 mmol. Thereafter, the autoclave was pressurized to 0.785 MPa-G with hydrogen gas, and the polymerization was carried out with stirring at 90 rpm and stirring at 90 ° C. for 60 minutes. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

  The obtained transparent liquid polymer (1-decene polymer) was 39.97 g, and the polymerization activity was 20.0 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 4,740 and Mw / Mn = 1.60.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

  In Example 7, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopenta The same operation as in Example 7 was performed except that dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was used.

  The obtained transparent liquid polymer (1-decene polymer) was 43.07 g, and the polymerization activity was 21.5 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 4,240 and Mw / Mn = 1.60.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

  In Example 7, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopenta The same operation as in Example 7 was carried out except that dienyl) (2,7-diphenyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride was used.

  The obtained transparent liquid polymer (1-decene polymer) was 43.95 g, and the polymerization activity was 22.0 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 8,150 and Mw / Mn = 1.71.

Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

In Example 7, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butyl-fluorenyl) zirconium dichloride was converted to di (p-chlorophenyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-
The same operation as in Example 7 was carried out except that di-tert-butyl-fluorenyl) zirconium dichloride was used.

The obtained transparent liquid polymer (1-decene polymer) was 42.72 g, and the polymerization activity was 21.4 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 5,130 and Mw / Mn = 1.64.
Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.
[Comparative Example 1]
A stainless steel autoclave having an internal volume of 1 L that has been sufficiently purged with nitrogen was charged with 300 ml of n-heptane and 200 ml of 1-decene, followed by toluene solution of di (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. 002 mmol and 2 mmol of methylaluminoxane in toluene (Al = 1.53 M) were added, and then the autoclave was pressurized to 0.785 MPa-G with hydrogen gas, and the stirring speed was 350 rpm.
The polymerization was conducted with stirring at 90 ° C. for 60 minutes. After the polymerization, the pressure was released, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

  The obtained transparent liquid polymer (1-decene polymer) was 28.89 g, and the polymerization activity was 14.4 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 6,800 and Mw / Mn = 2.02.

Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.
[Comparative Example 2]
After charging 1000 ml of 1-decene into a 2 L stainless steel autoclave sufficiently purged with nitrogen and raising the temperature in the system to 145 ° C., the total pressure was adjusted to 2.5 MPa-G by supplying hydrogen. did. Next, 0.005 mmol of a toluene solution of di (phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium dichloride and a toluene solution of methylaluminoxane (Al = 1.53M) 2. Polymerization was performed at 150 ° C. for 60 minutes by injecting 0 mmol with nitrogen and setting the stirring rotation speed to 400 rpm. Polymerization was stopped by adding a small amount of isopropanol into the system. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. The solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C.

The obtained transparent liquid polymer (1-decene polymer) was 305.40 g, and the polymerization activity was 61.1 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mn = 4,280 and Mw / Mn = 1.62.

  Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.

[Comparative Example 3]
A 100 ml glass flask purged with nitrogen was charged with 100 ml of toluene and 3 mmol of bis (1,3dimethylcyclopentadienyl) zirconium dichloride to prepare a catalyst.

Using a continuous polymerization reactor, purified toluene at 1 L / hr, purified 1-decene at 1 L / hr methylaluminoxane at 11 mmol / L, and the zirconium catalyst prepared above in zirconium at a rate of 0.02 mmol / L. In the polymerization vessel, the conditions are such that ethylene 50 L / hr, nitrogen 120 L / hr, hydrogen 30 L / hr are continuously fed at the same time, polymerization temperature 45 ° C., normal pressure, residence time 1.0 hour. Polymerization was performed below. The polymer solution was continuously withdrawn from the polymerization vessel, and the polymerization was stopped by adding a small amount of methanol. 1 L of water and a little hydrochloric acid (about 20 mL) were added to the polymer solution, stirred for 15 minutes, and then allowed to stand.
Separate the aqueous layer. Next, 2 L of water is added and stirred for 10 minutes, and then allowed to stand to separate the aqueous layer. This was repeated twice. Thereafter, toluene was removed from the polymer solution to obtain a colorless and transparent liquid polymer (ethylene / 1-decene copolymer). Further, this liquid polymer is heated to 180 ° C.
For 1 hour under reduced pressure (15 mmHg).

The activity per unit zirconium was 1.02 Kg-polymer / mmol-Zr · hr. As a result of polymer analysis, Mw = 4,310, Mn = 2,890, and Mw / Mn = 1.49.
Table 1 shows the kinematic viscosity, viscosity index, molecular weight (Mn) measured by gel permeation chromatography of 20,000 or more, content of 1,000 or less, and heat-resistant oxidation stability of the obtained transparent liquid polymer. Indicated. Table 2 shows the temperature-viscosity characteristics and shear stability of the blended oil.
[Comparative Example 4]
Evaluation was conducted in the same manner as in Example 1 except that a commercially available ethylene / propylene copolymer (Mitsui Chemicals, Inc. Lucant HC-40) was used as the liquid polymer in Example 1. Tables 1 and 2 show the results. Indicated.

  As described above, the α-olefin (co) polymer of the present invention has high thermal oxidation stability, and has an excellent viscosity index, low temperature viscosity, and shear stability.

  The synthetic lubricating oil comprising the α-olefin (co) polymer of the present invention has low evaporation at a high temperature, excellent heat-resistant oxidation stability as compared with conventional mineral oil or synthetic oil, and has a high viscosity index and low temperature. Excellent viscosity characteristics and shear stability.

Therefore, lubrication with excellent temperature-viscosity characteristics, shear stability and thermal oxidation stability can be achieved by using alone or mixed with other base oils, such as mineral oil and α-olefin oligomers, to make lubricating base oils. Oil can be provided.

Claims (6)

A synthetic lubricating oil comprising an α-olefin (co) polymer defined by the following (i) to (v). (I) containing (a) a structural unit derived from at least one monomer selected from α-olefins having 8 to 20 carbon atoms in a range of 90 to 100 mol%, and (b) derived from ethylene. Containing structural units in an amount ranging from 0 to 10 mol%,
(Ii) the kinematic viscosity at 100 ° C. is in the range of 8 to 500 mm ² / s,
(Iii) Number average molecular weight (Mn) measured by gel permeation chromatography
) Is in the range of 500-15,000,
(Iv) satisfying the following formulas (I) and (II):
A ≦ 24.0 × Exp (−0.0239 × K) (I)
B ≦ 0.0775 × K (II)
(In the formula, A is the content (%) of (co) polymer having a molecular weight of 1,000 or less measured by gel permeation chromatography, and B is the content (% of (co) polymer having a molecular weight of 20,000 or more). ), K is the kinematic viscosity at 100 ° C. (mm ² / s))
(V) The molecular weight distribution (Mw / Mn) is in the range of 1.1 to 1.8. The synthetic lubricating oil according to claim 1, wherein the α-olefin (co) polymer has (vi) a content of unsaturated groups at one molecular end of 0.001 to 10%. The synthetic lubricating oil according to claim 1 or 2, wherein the α-olefin (co) polymer satisfies the following formula (III).
C ≧ 0.3178 × K + 140 (III)
(In the formula, C is a viscosity index measured by the method of JIS K2283, where K is a kinematic viscosity (mm ² / s) at 100 ° C.) The synthetic lubricating oil according to claim 1, wherein the kinematic viscosity at 100 ° C. is in the range of 20 to 150 mm ² / s and the number average molecular weight (Mn) is in the range of 1,500 to 4,300.   The synthetic lubricating oil according to any one of claims 1 to 4, wherein the α-olefin is 1-decene. (A) 15 to 90 parts by weight of the synthetic lubricating oil according to any one of claims 1 to 5;
(B) A low-viscosity base oil consisting of at least one base oil selected from mineral oils, synthetic hydrocarbon oils and ester oils and having a kinematic viscosity at 100 ° C. in the range of ² to 10 mm ² / s. Part by weight,
(C) It consists of detergent dispersant, viscosity index improver, antioxidant, corrosion inhibitor, antiwear agent, friction modifier, pour point depressant, rust inhibitor, antifoaming agent and extreme pressure agent as necessary A lubricating oil composition comprising at least one additive selected from the group.