JP2005200452A - METHOD FOR PRODUCING alpha-OLEFIN (CO)POLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for polymerizing an olefin in the presence of a catalyst containing a transition metal compound having polymerization activity not lower than that of a well-known metallocene compound when a polymer using a 6-20C α-olefin as a main monomer is produced. <P>SOLUTION: The method for producing a homopolymer or a copolymer is carried out as follows. The homopolymerization of the 6-20C α-olefin or copolymerization of the 6-20C α-olefin and at least one or more kinds of olefins selected from ethylene and a 3-20C α-olefin is carried out in the presence of the catalyst for polymerizing the olefin composed of (A) the group 4 transition metal compound represented by general formula [1] and (B) at least one or more kinds of compounds selected from (B-1) an organometallic compound, (B-2) an organoaluminum compound, (B-3) an organoaluminumoxy compound and (B-4) a compound reactive with the group 4 transition metal compound (A) and forming an ion pair. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an α-olefin (co) polymer in the presence of a catalyst containing a metallocene compound having a specific structure.

  As a homogeneous catalyst for olefin polymerization, a so-called metallocene compound is well known. A method for polymerizing olefins using metallocene compounds, particularly a method for stereoregularly polymerizing α-olefins, has been reported by W. Kaminsky et al. (Ingew. Chem. Int. Ed. Engl., 24, 507 (1985)), many improvements have been made, but further improvement is desired from the viewpoint of polymerization activity or from the viewpoint of stereoregularity. As part of such research, propylene polymerization using a metallocene compound in which a cyclopentadienyl ligand and a fluorenyl ligand are bridged has been reported by JAEwen (J. Am. Chem. Soc., 110, 6255). (1988)). W. Kaminsky has also reported ethylene polymerization using the same catalyst (Makromol. Chem., 193, 1643 (1992)).

  Further, as described in JP-A-57-117595, ethylene / α-olefin is used as a synthetic lubricating oil used as a lubricating base oil for automobile gear oil, engine oil, industrial lubricating oil, hydraulic oil, etc. It is known that polymers can also be used as synthetic lubricating oils that are excellent in viscosity index, oxidation stability, shear stability, and heat resistance.

  As a method for producing an ethylene / α-olefin copolymer used as a synthetic lubricating oil, vanadium comprising a vanadium compound and an organoaluminum compound as described in JP-B-2-1633 and JP-B-2-7998 has been conventionally used. System-catalyzed methods have been used. As such an ethylene / α-olefin copolymer, an ethylene / propylene copolymer is mainly used.

  Further, as a method for producing a copolymer, a method using a catalyst system comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) as described in JP-A-61-221207 and JP-B-7-121969. Patent No. 2,796,376 discloses a method for producing a synthetic lubricating oil comprising an ethylene / α-olefin copolymer obtained by using a catalyst system in which a specific metallocene catalyst and an aluminoxane are combined. Yes.

However, no polymer having a narrow molecular weight distribution and high activity has been found in polymerization using an α-olefin having 6 to 20 carbon atoms as a main monomer. Therefore, the appearance of transition metal compounds exhibiting higher performance has been desired.
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 Patent No. 2796376 Angew. Chem. Int. Ed. Engl., 24, 507 (1985) J. Am. Chem. Soc., 110, 6255 (1988) Makromol.Chem., 193,1643 (1992)

  The present invention has been made in order to solve the above-described problems. In producing a polymer using an α-olefin having 6 to 20 carbon atoms as a main monomer, the polymerization activity is higher than that of a known metallocene compound. The present invention provides a method for olefin polymerization in the presence of a catalyst containing a transition metal compound having

  In the method for producing an α-olefin (co) polymer according to the present invention, the transition metal compound (A) is a Group 4 transition metal compound represented by the following general formula [1].

…[１]

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は水素、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよく、ＭはＴｉ、ＺｒまたはＨｆであり、Ｙは第１４族原子であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数であり、Ａは不飽和結合を含んでいてもよい炭素原子数２〜２０の二価の炭化水素基を示し、ＡはＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。）、および（Ｂ）(B-1)有機金属化合物、(B-2)有機アルミニウム化合物、(B-3)有機アルミニウムオキシ化合物、および(B-4)前記第４族遷移金属化合物（Ａ）と反応してイオン対を形成する化合物から選ばれる少なくとも１種以上の化合物とからなるオレフィン重合用触媒の存在下に炭素数６〜２０のα−オレフィンを単独重合させるか、あるいは炭素数６〜２０のα−オレフィンと炭素原子数が２以上のオレフィンとを共重合させて、極限粘度［η］が０．６ｄｌ／ｇ以下である、炭素数６〜２０を主モノマーとするα−オレフィン（共）重合体を形成させることを特徴としている。

... [1]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are from hydrogen, hydrocarbon groups, silicon-containing groups. Each may be the same or different, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is coordinated by a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons May be selected from the possible neutral ligands in the same or different combinations, j is an integer from 1 to 4 and A is a divalent hydrocarbon of 2 to 20 carbon atoms which may contain an unsaturated bond A represents a group, and A may contain two or more ring structures including a ring formed with Y.), and (B) (B-1) an organometallic compound and (B-2) an organoaluminum compound , (B-3) an organoaluminum oxy compound, and (B-4) a reaction with the Group 4 transition metal compound (A). An α-olefin having 6 to 20 carbon atoms is homopolymerized in the presence of an olefin polymerization catalyst consisting of at least one compound selected from compounds that form ion pairs, or α having 6 to 20 carbon atoms. -Α-olefin (co) heavy having 6 to 20 carbon atoms as a main monomer, having an intrinsic viscosity [η] of 0.6 dl / g or less by copolymerizing an olefin and an olefin having 2 or more carbon atoms It is characterized by forming a coalescence.

The low molecular weight α-olefin (co) polymers obtained by the present invention are paint modifiers, polishes, pigment dispersants (particularly pigment masterbatch raw materials), polyvinyl chloride lubricants, resin molding lubricants, rubber processing aids. Agent, toner release agent, paper quality improver, ink anti-wear agent, fiber processing aid, hot melt adhesive additive, electrical insulator, natural wax compounding agent, asphalt fluidity improver, various oil solidifying agents, Communication cable filler, moisture-proof coating material, paper coat disaggregation imparting agent, suspension or emulsion polymerization polymer emulsification aid, antistatic agent or weathering stabilizer base material, automotive engine oil, gear oil, ATF, base oil and viscosity index improver for industrial lubricants, grease base oil, metalworking oil, rubber / resin modifier, aluminum die-cast release agent, fuel oil additive, paint, ink modifier For applications such as Those that can be used to apply.

  Hereafter, the manufacturing method of the (co) polymer which uses a C6-C20 alpha olefin which concerns on this invention as a main monomer is demonstrated concretely. In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.

  First, each component which forms the olefin polymerization catalyst used in the present invention will be described. The transition metal compound forming the olefin polymerization catalyst is (A) a group 4 transition metal compound represented by the following general formula [1].

…[１]

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は水素、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよく、ＭはＴｉ、ＺｒまたはＨｆであり、Ｙは第１４族原子であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数であり、Ａは不飽和結合を含んでいてもよい炭素原子数２〜２０の二価の炭化水素基を示し、ＡはＹと共に形成する環を含めて二つ以上の環構造を含んでいてもよい。）

... [1]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are from hydrogen, hydrocarbon groups, silicon-containing groups. Each may be the same or different, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is coordinated by a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons May be selected from the possible neutral ligands in the same or different combinations, j is an integer from 1 to 4 and A is a divalent hydrocarbon of 2 to 20 carbon atoms which may contain an unsaturated bond A represents a group, and A may contain two or more ring structures including a ring formed with Y.)

  In the general formula [1], 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 7 to 20 carbon atoms. 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, 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- Such as cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.

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

In the present invention, R ¹ to R ^{14 in} the general formula [1] are 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.

The adjacent substituents from R ¹ to R ¹⁴ on the cyclopentadienyl ring of the general formula [1] may be bonded to each other to form a ring.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, positions 2, 3, 6, and 7 on the fluorene ring correspond to R ⁶ , R ⁷ , R ¹⁰ , and R ¹¹ , respectively.

  Y is a Group 14 atom, preferably carbon and silicon. Y is partially bonded to an unsaturated bond and / or a divalent hydrocarbon group A having 2 to 20 carbon atoms which may contain an aromatic ring, and constitutes a cycloalkylidene group or a cyclomethylenesilylene group. Preferable specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene , Cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

In the present invention, M in the general formula [1] is zirconium, titanium, or hafnium. Q is a 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 neutral ligand capable of coordinating with a lone electron pair. Selected in the same or different combinations. Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are 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, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. 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 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 the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations. j represents an integer of 1 to 4;

  Specific examples of the Group 4 transition metal compound represented by the general formula [1] are shown below, but the scope of the present invention is not particularly limited thereby.

Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylidene ( Clopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) Hafnium dichloride, cyclopentylidene ( (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, adamantylidene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) ) (3,6-Dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene
(Cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 3,6-dimethyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert- Fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclo Heptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl Zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cyclopentylidene (Cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-dicumyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 3,6-Dicumyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-di) (Trimethylsilyl) -fluorenyl) Luconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium Dichloride, cycloheptylidene (cyclopentadienyl) (3,6-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclobuty Liden (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ( 3,6-Diff Nyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, Cyclobutylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ) (3,6-Dibenzyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dibenzyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-difluoro) -Fluoresce Nyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclohexylidene (Cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-difluoro-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) ( 3,6-dibromo-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) Zirconium dichroic Cyclohexylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-dibromo-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopropylene) Pentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (3, 6-ditert-fluorenyl) zirconium dibromide, cyclopropylidene (cyclopentadienyl) ( 3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) Zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (3,6-dimethyl-fluorenyl) zirconium dimethyl, cyclopropylidene ( Cyclopentadienyl) (3,6-ditert-fluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl)
Hafnium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Hafnium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Hafnium dichloride, cycloheptyl Liden (cyclopentadienyl) (3,6-ditert-fluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Titanium dichloride, cyclobutylidene (cyclopentadienyl) ) (3,6-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (3,6- Di-tert-fluorenyl)
Titanium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclobutylidene (Cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclopentylidene
(Cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) ( 2,7-Dimethyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-ditert
-Fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, Cyclohexylidene
(Cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) ) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dicumyl- Fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cycloheptylidene
(Cyclopentadienyl) (2,7-dicumyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) ) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ( 2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-di (trimethylsilyl) -fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2 , 7-diphenyl-fluorenyl) Zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclohexylidene (cyclohexane) Pentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2, 7-dibenzyl-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride Lido, cyclohexylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibenzyl-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopropylene) Pentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7 -Difluoro-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-difluoro-fluorenyl) zirconium dichloride , Cyclop Piriden (cyclopentadienyl) (2,7-dibromo - fluorenyl
) Zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclohexylidene ( (Cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dibromo-fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2 , 7-ditert-fluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) zirconium dibromide, cyclohexylide (Cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) zirconium dibromide, cyclopropylidene (cyclopenta (Dienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (2,7- Dimethyl-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-fluorenyl) zirconium dimethyl, Cyclopropylidene (cyclopentadienyl) (2,7-ditert-fluorenyl ) Hafnium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) Hafnium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-di tert-fluorenyl) Hafnium dichloride, cyclohexyl Den (cyclopentadienyl) (2,7-ditert-fluorenyl) Hafnium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadiene) Enyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (2,7 -Di-tert-fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) ( 2,7-ditert-fluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-ditert-fluorenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, Cyclobutylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cycloheptylidene ( Cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (fluorenyl) zirconium dibromide, cyclobutylidene (cyclopentadienyl) (fluorenyl) zirconium dibromide , Cyclopentylidene (cyclopentadienyl) (fluorenyl) zirconium dibromide, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (fluorenyl) zirconium dibromide , Cyclopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, cyclohexylidene ( Cyclopentadienyl) (fluorenyl) zirconium dimethyl, cycloheptylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (fluorenyl) Funium dichloride, cyclobutylidene (cyclopentadienyl) (fluorenyl) Hafnium dichloride, cyclopentylidene (cyclopentadienyl) (fluorenyl) Hafnium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) Hafnium dichloride, cyclo Heptylidene (cyclopentadienyl) (fluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (fluorenyl) Titanium dichloride, cyclobutylidene (cyclopentadienyl) (fluorenyl) Titanium dichloride, cyclopentylidene (cyclo Pentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) ( (Luolenyl) titanium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclo Pentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cycloheptylidene (cyclopenta Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dibromide, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide Cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dibromide, cyclopropyl Liden (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl Cyl, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cycloheptylidene (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, cyclopropylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclobutylidene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, cyclohexylidene ( Clopentadienyl) (octamethyloctahydrodibenzofluorenyl) Hafnium dichloride, cycloheptylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, cyclopropylidene (cyclopentadienyl) (Octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclobutylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzo) Fluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, cycloheptylidene (cyclopentadienyl) (octa An example is methyloctahydrodibenzofluorenyl) titanium dichloride.

(B-1) Organometallic Compound As the organometallic compound used in the present invention, specifically, the following organometallic compounds are used.

General formula R ^a R ^b M ³
(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 a catalyst for olefin polymerization (B-2) The organoaluminum compound is, for example, an organoaluminum compound represented by the following general formula [2], represented by the following general formula [3] And a complex alkylated product of a Group 1 metal and aluminum, or an organic aluminum oxy compound.

R ^a _m Al (OR ^b ) _n H _p X _q ... [2]
(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 a number of 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 [3]
(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 [2] include compounds represented by the following general formula [4], [5], [6], or [7].

R ^a _m Al (OR ^b ) _3-m ... [4]
(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 … [5]
(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 … [6]
(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 ... [7]
(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 [4], [5], [6], or [7] 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-methylhexylaluminum, tri-2 -Tri-branched alkyl aluminum such as ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tolyl aluminum; hydride; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, a is z ≦ 2x.) represented by like Alkenyl aluminum such as isoprenyl aluminum; Alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide; Table by the general formula _{^{R a 2.5 Al (OR b)}} 0.5 and the like; methyl aluminum methoxide, diethyl aluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui Bed alkylaluminum sesqui alkoxides such butoxide Partially alkoxylated alkylaluminum having the average composition: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t Alkyl such as -butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) Aluminum aryloxide; Dialkylaluminum halides such as methylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; including partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. Can do.

A compound similar to the compound represented by the general formula [2] 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 a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound represented by the general formula [3] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

  Of these, organoaluminum compounds are preferred.

  The organoaluminum compound represented by the general formula [2] or the complex alkylated product of the Group 1 metal and aluminum represented by the general formula [3] is used singly or in combination of two or more. .

(B-3) Organoaluminum oxy compound (B-3) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-2).

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The above organoaluminum compounds are used singly or in combination of two or more.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred. These organoaluminum oxy compounds (B-3) are used singly or in combination of two or more.

  Aluminoxane prepared from trimethylaluminum is called methylaluminoxane or MAO and is a particularly frequently used compound.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  Examples of the organoaluminum oxy compound used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula [8].

…[８]

（式中、Ｒ^cは炭素原子数が１〜１０の炭化水素基を示す。Ｒ^dは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素原子数が１〜１０の炭化水素基を示す。）

... [8]

(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 [8] is obtained by combining an alkyl boronic acid represented by the following general formula [9] 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 [9]
(In the formula, R ^c represents the same group as described above.)
Specific examples of the alkyl boronic acid represented by the general formula [9] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. 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 above general formula [2] or [3]. .

  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 that reacts with the Group 4 transition metal compound (A) to form an ion pair (B-4) ) As JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Laid-Open Patent Publications, US5321106.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, trimethylboron, triisobutylboron and the like can be mentioned.

  Examples of the ionic compound include a compound represented by the following general formula [10].

…[１０]

式中、Ｒ^e+としては、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を
有するフェロセニウムカチオンなどが挙げられる。Ｒ^f〜Ｒⁱは、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。

... [10]

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 or a substituted 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 these, as R ^e , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (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) borate, dioctadecylmethylammonium Mo tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  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-diethylanilinium tetrakis (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, etc. .

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

  Further, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, or the following formula [11] or [12] Or a borate compound containing an active hydrogen represented by the following formula [13], a borate compound containing a silyl group represented by the following formula [14], or the like.

…[１１]

（式中、Ｅｔはエチル基を示す。）

... [11]

(In the formula, Et represents an ethyl group.)

…[１２]

［Ｂ− Ｑｎ（Ｇｑ（Ｔ−Ｈ）ｒ）ｚ］^-Ａ⁺ …[１３]
式[１３]中、Ｂはホウ素を表す。Ｇは多結合性ヒドロカーボンラジカルを表し、好ましい多結合性ヒドロカーボンとしては炭素数１〜２０を含むアルキレン、アリレン、エチレン、アルカリレンラジカルであり、Ｇの好ましい例としては、フェニレン、ビスフェニレン、ナフタレン、メチレン、エチレン、プロピレン、1,4-ブタジエン、p-フェニレンメチレンがあげられる。多結合性ラジカルＧはｒ＋１の結合、すなわち一つの結合はボレートアニオンと結合し、Ｇのその他の結合ｒは（Ｔ−Ｈ）基と結合する。Ａ⁺はカチオンである。

... [12]

[B- Qn (Gq (T- H) r) z] - A + ... [13]
In the formula [13], B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Naphthalene, methylene, ethylene, propylene, 1,4-butadiene, p-phenylenemethylene. The multi-bond radical G is an r + 1 bond, that is, one bond is bonded to a borate anion, and the other bond r of G is bonded to a (TH) group. A ⁺ is a cation.

T in the above formula [13] represents O, S, NR ^j , or PR ^j , and R ^j represents a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride. q is an integer of 1 or more, preferably 1. The TH group includes —OH, —SH, —NRH, or —PR ^j H, where R ^j is a hydrocarbyl radical or hydrogen having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. is there. Preferred R ^j groups are alkyl, cycloalkyl, allyl, allylalkyl or alkylallyl having 1 to 18 carbon atoms. -OH, -SH, -NR ^j H or -PR ^j H may be, for example, -C (O) -OH, -C (S) -SH-C (O) -NR j H, and C (O) - PR ^j H is also acceptable. The most preferred group having active hydrogen is the -OH group. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical and the like. Here, n + z is 4.

[B-Qn (Gq (TH) r) z] of the formula [13] is, for example, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) Borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris [3,5-di (trifluoromethyl) phenyl] (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxy Butyl) borate, tris (pentafluorophenyl) (4-hydroxycyclohexyl) borate, tris ( Ntafluorophenyl) [4- (4-hydroxyphenyl) phenyl] borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate and the like, most preferably tris (pentafluorophenyl) (4- Hydroxyphenyl) borate. Furthermore, it is preferable to substitute the —OH group of the borate compound with —NHR ^j (where R ^j is methyl, ethyl, t-butyl).

Examples of A ⁺ that is a counter cation of the borate compound include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Also included are metal cations and organometallic cations whose confidence is easily reduced. Specific examples of these cations include triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tributylammonium, dimethylammonium, dipropylammonium, dicyclohexylammonium, trioctylammonium, N, N-dimethylammonium, diethylammonium, 2,4,6-pentamethylammonium, N, N-dimethylphenylammonium, di- (i-propyl) ammonium, dicyclohexylammonium, triphenylphosphonium, triphosphonium, tridimethylphenyl Phosphonium, tri (methylphenyl) phosphonium, triphenylphosphonium ion, triphenyloxonium ion , Triethyloxonium ion, pyrinium, silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion and the like. Of these, ammonium ions are particularly preferred.
[B-Qn (Gq (SiR k R l R m) r) z] - A + ... [14]
In the formula [14], B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Examples include naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bond radical G is bonded to r + 1, that is, one bond is bonded to the borate anion, and the other bond r of G is bonded to the (SiR ^k R ^l R ^m ) group. A ⁺ is a cation.

R ^k , R ¹ and R ^m in the above general formula represent a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, a hydrogen radical, an alkoxy radical, a hydroxy radical or a halogen compound radical. R ^k , R ^l and R ^m may be the same or independent. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical, and more preferably a pentafluorobenzyl radical. Here, n + z is 4.

In the formula [14] [B-Qn ( Gq (SiR k R l R m) r) z] - as, for example, triphenyl (4-dimethylchlorosilyl phenyl) borate, diphenyl chromatography di (4-dimethylchlorosilyl phenyl ) Borate, triphenyl (4-dimethylmethoxysilylphenyl) borate, tri (p-tolyl) (4-triethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-dimethylchlorosilylphenyl) borate, tris (penta Fluorophenyl) (4-dimethylmethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-trimethoxysilylphenyl) borate, tris (pentafluorophenyl) (6-dimethylchlorosilyl-2-naphthyl) borate, etc. .

A is A ⁺ is the counter cation of the borate compound include the same as the A ⁺ in the above formula [13].

  Specific examples of the borane compound include decaborane (14), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1,3 -Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane ( 13), 2,7-dicarbaound decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-carbadecaborate -1-carbadeca Rate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-Butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate , Tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundeborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbounde Caborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc. Anion salts of: tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis ( Undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-bu ) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeca Borate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) chromate (III), tri (n-butyl) ammonium Bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate ( III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7 -Carbaound Decaborate) Examples thereof include salts of metal carborane anions such as tomate (III) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

  In addition, the compound (B-4) which reacts with the above Group 4 transition metal compound (A) to form an ion pair can be used in combination of two or more.

  In preparing the olefin polymerization catalyst of 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.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, 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 , SiO ₂ —TiO ₂ —MgO, etc. Can be used. 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, 1 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.

  Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, Examples thereof 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 homopolymerization of 1-octene, homopolymerization of 1-decene, homopolymerization of 1-dodecene or homopolymerization of 1-tetradecene, and copolymerization using these as main monomers.
Specific embodiments for producing the olefin low molecular weight polymer of the present invention will be described 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. It is used in an amount ranging from 10 ⁻⁸ to 10 ⁻² gram atoms / liter, preferably from 10 ⁻⁷ to 10 ⁻³ gram atoms / liter.

Component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) and all transition metal atoms (M) in the component (A) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (B-2) has a molar ratio [(B-2) / M] of component (B-2) to all transition metal atoms (M) in component (A) of usually 100 to 25000, preferably The amount used is 500 to 10,000. Component (B-3) has a molar ratio [(B-3) / M] of the aluminum atoms in component (B-3) to the total transition metals (M) in component (A) of usually 10 to 10. The amount used is 5000, preferably 20-2000. Component (B-4) has a molar ratio [(B-4) / M] of component (B-4) to transition metal atom (M) in component (A) of usually 1 to 50, preferably 1 It is used in such an amount that it becomes ˜20.
Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from ordinary pressure to 5 MPa pressure, and the polymerization reaction can be carried out by 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 obtained α-olefin (co) polymer is a liquid or amorphous polymer.

  In the present invention, the α-olefin (co) polymer is obtained by treating the polymerization reaction mixture after the completion of the polymerization reaction by a conventional method. The polymer thus obtained is an olefin (co) polymer that is liquid or semi-solid at 25 ° C., and its intrinsic viscosity [η] measured in 135 ° C. decalin is preferably 0.60 dl / g or less, preferably Is 0.005 to 0.60 dl / g, more preferably 0.005 to 0.40 dl / g, and particularly preferably 0.01 to 0.30 dl / g. The content of the α-olefin unit having 6 to 20 carbon atoms in the α-olefin (co) polymer is in the range of 50 to 100 mol%, preferably 55 to 100 mol%. The content of the α-olefin component unit of 2 to 20 is 0 to 50 mol%, preferably 0 to 45 mol%.

  The molecular weight distribution (Mw / Mn) of the α-olefin (co) polymer measured by gel permeation chromatography (GPC) is usually 3 or less, preferably 2.5 or less.

Moreover, the kinematic viscosity at 100 ° C. of the α-olefin (co) polymer is 10 to 10,000 mm ^2.
/ S, preferably 15 to 5,000 mm ² / S, and more preferably 20 to 3,000 mm ² / S.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Weight average molecular weight (Mw), number average molecular weight (Mn)]
The number 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., the mobile phase is tetrahydrofuran (Wako Pure Chemical Industries), the development rate is 0.8 ml / min, and the sample concentration is 0.2. The amount of sample injection was 200 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used.

[Intrinsic viscosity ([η])]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of the polymer is dissolved in 15 ml of decalin, and the specific viscosity η _sp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation is further repeated twice, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0)

[Viscosity characteristics]
The kinematic viscosity at 100 ° C. of the polymer was measured and calculated by the method described in JIS K2283.

A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of n-decane and 250 ml of 1-decene were charged, and the temperature was adjusted to 60 ° C. while flowing nitrogen at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml-branch flask with an internal volume sufficiently purged with nitrogen, and cyclohexylidene (1-cyclopentadienyl) (2,7-di-tert-butylfluorene) was used as a transition metal compound. Nyl) zirconium dichloride in toluene (0.002 mmol) and methylaluminoxane in toluene (Al = 1.53 M) were added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, and then hydrogen was passed in an amount of 35 liters / hour, and then the above solution was added to initiate polymerization. During the polymerization, hydrogen was continuously supplied in an amount of 35 liters / hour, polymerization was performed at 60 ° 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 117.20 g, and the polymerization activity was 58.60 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.11 dl / g, Mw = 16,780, Mn = 10,430, Mw / Mn = 1.61, and the kinematic viscosity at 100 ° C. was 458 mm ² / s. It was.

  In Example 1, the same operation as in Example 1 was performed except that the polymerization temperature was changed to 160 ° C. and the flow rate of hydrogen was changed to 100 liters / hour.

The obtained transparent liquid polymer was 40.97 g, and the polymerization activity was 20.49 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.04 dl / g, Mw = 8,960, Mn = 5,970, Mw / Mn = 1.50, and kinematic viscosity at 100 ° C. is 23.52 mm ² / s. Met.

  The same operation as in Example 1 was carried out except that the transition metal compound was changed to cyclohexylidene (1-cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride in Example 1. .

The obtained transparent liquid polymer was 29.90 g, and the polymerization activity was 14.95 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.15 dl / g, Mw = 25,700, Mn = 16,570, Mw / Mn = 1.55, kinematic viscosity at 100 ° C. is 1,100 mm ² / s Met.

  The same operation as in Example 1 was performed except that the transition metal compound was changed to adamantylidene (1-cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride in Example 1. .

The obtained transparent liquid polymer was 25.00 g, and the polymerization activity was 12.50 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.14 dl / g, Mw = 24,940, Mn = 16,520, Mw / Mn = 1.51, and the kinematic viscosity at 100 ° C. was 891 mm ² / s. It was.

A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of n-decane and 250 ml of 1-decene were charged, and the temperature was adjusted to 60 ° C. while flowing nitrogen at 50 liters / hour. Nitrogen in the glass autoclave was stopped, then hydrogen was passed in an amount of 35 liters / hour, then 2 mmol of n-decane solution of triisobutylaluminum was added, and then cyclohexylidene (1 -Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride in 0.002 mmol in toluene, and finally N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene in 0.04 mmol Was added to initiate polymerization. During the polymerization, hydrogen was continuously supplied in an amount of 35 liters / hour, polymerization was performed at 60 ° 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 108.0 g, and the polymerization activity was 54.0 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.13 dl / g, Mw = 20,260, Mn = 13,240, Mw / Mn = 1.53, and the kinematic viscosity at 100 ° C. was 764 mm ² / s. It was.

  In Example 1, the same operation as Example 1 was performed except having changed 1-decene which is a monomer into 1-octene.

The obtained transparent liquid polymer was 72.50 g, and the polymerization activity was 36.25 kg-po.
Lymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.12 dl / g, Mw = 15,230, Mn = 10,150, Mw / Mn = 1.50, and kinematic viscosity at 100 ° C. was 371 mm ² / s. It was.

  In Example 1, the same operation as Example 1 was performed except having changed 1-decene which is a monomer into 1-dodecene.

The obtained transparent liquid polymer was 90.20 g, and the polymerization activity was 45.10 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.10 dl / g, Mw = 16,890, Mn = 10,970, Mw / Mn = 1.54, and kinematic viscosity at 100 ° C. was 463 mm ² / s. It was.

  In Example 1, the same operation as Example 1 was performed except having changed 1-decene which is a monomer into 1-tetradodecene.

The obtained transparent liquid polymer was 80.20 g, and the polymerization activity was 40.10 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.09 dl / g, Mw = 16,110, Mn = 10,530, Mw / Mn = 1.53, and the kinematic viscosity at 100 ° C. was 387 mm ² / s. It was.

[Comparative Example 1]
In Example 1, cyclohexylidene (1-cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride was polymerized to dimethylmethylene (1-cyclopentadienyl) (fluorenyl) zirconium dichloride. The same operation as in Example 1 was performed except that the temperature was changed to 80 ° C. and hydrogen was changed to 35 liters / hour.

The obtained transparent liquid polymer was 4.18 g, and the polymerization activity was 2.09 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.08 dl / g, Mw = 23,050, Mn = 14,770, Mw / Mn = 1.56, and the kinematic viscosity at 100 ° C. was 913 mm ² / s. It was.

[Comparative Example 2]
In Example 1, cyclohexylidene (1-cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride was converted to bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, polymerization temperature Was changed to 50 ° C. and hydrogen was changed to 35 liters / hour, and the same operation as in Example 1 was performed.

The obtained transparent liquid polymer was 24.98 g, and the polymerization activity was 12.49 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.03 dl / g, Mw = 2,320, Mn = 1,700, Mw / Mn = 1.36, and kinematic viscosity at 100 ° C. is 12.9 mm ² / s. Met.

Claims (12)

(A) Group 4 transition metal compound represented by the following general formula [1], and (B) (B-1) 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 consisting of at least one compound selected from the group consisting of homopolymerization of α-olefins having 6 to 20 carbon atoms, α-olefins having 6 to 20 carbon atoms and ethylene, and carbon numbers 3 A method for producing a homopolymer or a copolymer by copolymerizing using at least one olefin selected from?

... [1]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are from hydrogen, hydrocarbon groups, silicon-containing groups. Each may be the same or different, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is coordinated by a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons May be selected from the possible neutral ligands in the same or different combinations, j is an integer from 1 to 4 and A is a divalent hydrocarbon of 2 to 20 carbon atoms which may contain an unsaturated bond A represents a group, and A may contain two or more ring structures including a ring formed with Y.) 2. The production method according to claim 1, wherein a catalyst containing a metallocene compound in which R ¹ to R ⁴ are all hydrogen atoms in the general formula [1] is used. In the general formula [1], R ⁵ to R ¹² are not hydrogen at the same time, and any two or more substituents of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ have a total carbon number of 1 The production method according to claim 1 or 2, wherein a catalyst containing a metallocene compound which is a hydrocarbon group of 20 and a silicon-containing group and in which adjacent substituents do not form a ring is used. 3. The production method according to claim 1, wherein a catalyst containing a metallocene compound in which R ⁶ , R ⁷ , R ¹⁰ , and R ¹¹ are not hydrogen atoms in the general formula [1] is used. In the general formula [1], a catalyst containing a metallocene compound in which R ⁶ and R ⁷ are bonded to each other to form a ring and R ¹⁰ and R ¹¹ are bonded to each other to form a ring is used. The manufacturing method according to claim 1 or 2. 3. The catalyst according to claim 1, wherein in the general formula [1], R ⁶ and R ¹¹ are hydrocarbon groups having 1 to 20 carbon atoms in total, and a catalyst containing such a metallocene compound is used. Production method. 3. The catalyst according to claim 1, wherein in the general formula [1], R ⁷ and R ¹⁰ are hydrocarbon groups having 1 to 20 carbon atoms in total, and a catalyst containing such a metallocene compound is used. Production method. The production method according to any one of claims 1 to 7, wherein a polymer containing an α-olefin having 6 to 20 carbon atoms in an amount of 10 to 100 mol% is formed. The production method according to any one of claims 1 to 7, wherein a polymer containing an α-olefin having 6 to 20 carbon atoms in an amount of 50 to 100 mol% is formed. The production method according to claim 8 or 9, wherein an α-olefin (co) polymer having an intrinsic viscosity [η] of 0.6 dl / g or less is formed. The molecular weight distribution (Mw / Mn, Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography is in the range of 1 to 4, and the number average molecular weight is in the range of 500 to 10,000. -Olefin (co) polymer is formed, The manufacturing method of Claim 8 or 9 characterized by the above-mentioned. The production method according to claim 8 or 9, wherein an α-olefin (co) polymer having a kinematic viscosity at 100 ° C in a range of 10 to 10,000 mm ² / S is formed.