JP2010077336A - METHOD FOR PRODUCING alpha-OLEFIN (CO)POLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a 6-20C &alpha;-olefin polymer capable of simplifying an ash-removing process by polymerizing the olefin by a high polymerization activity. <P>SOLUTION: This method for producing the polymer is provided by performing the homopolymerization or (co)polymerization of the 6-20C &alpha;-olefin (M) at 95 to 200&deg;C temperature in the presence of a polymerization catalyst consisting of (A) a forth group transition metal compound which is a specific metallocene catalyst, (B) a compound forming an ion pair by reacting with the compound (A), and (C) at least one compound selected from (C-1) an organometallic compound containing a second group or twelfth group metal and (C-2) an organoaluminum compound. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an α-olefin (co) polymer at a specific polymerization temperature 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. Isotactic polymerization was reported by W. Kaminsky et al. (Angew. Chem. Int. Ed. Engl., 24). , 507 (1985)), many improvements have been made, but further improvements are desired from the viewpoint of polymerization activity or from the viewpoint of stereoregularity. As part of such research, propylene polymerization using a metallocene compound obtained by crosslinking a cyclopentadienyl ligand and a fluorenyl ligand has been reported by JA Ewen (J. Am. Chem. Soc., 110, 6255). (1988)). W. Kaminsky 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, a conventional method comprises a vanadium compound and an organoaluminum compound as described in JP-B2-1163 and JP-B-2-7998. Vanadium-based catalyst 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, etc. 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. .

  On the other hand, a method for producing a polymer using, as a main monomer, an α-olefin having 6 to 20 carbon atoms using a catalyst system made of a specific metallocene compound, use as a lubricating oil, etc. are disclosed (Patent Document 7). ~ 12).

In order to use these α-olefin (co) polymers as a lubricating oil or the like, it is preferable that the catalyst residue is small, and it is generally removed by a complicated deashing step. Accordingly, there has been a demand for simplification and omission of the deashing step due to the appearance of a transition metal compound having a higher catalytic activity and a polymerization method.
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 Japanese Patent Laying-Open No. 2005-200449 JP 2005-200450 A JP 2005-200451 A JP 2005-200452 A JP 2005-200453 A JP 2006-176760 A 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-mentioned problems, and in producing a polymer of an α-olefin having 6 to 20 carbon atoms as a main monomer, an olefin having a higher polymerization activity than a known polymerization method. It is to provide a method for producing an olefin polymer having a small amount of catalyst residue to the extent that simplification and omission of the deashing step are possible.

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

(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 and R ¹² are a hydrogen atom, a hydrocarbon group, a silicon-containing group. Each of R ¹³ and R ¹⁴ may be the same or different from a hydrocarbon group, a halogen atom-containing carbon hydrogen group, a halogen atom, an oxygen-containing group, a nitrogen-containing group or a silicon-containing group; A substituted aryl group having one or more selected substituents, R ¹³ and R ¹⁴ may be the same or different from each other, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is selected from a halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair, in the same or different combination, and j is an integer of 1 to 4.) and (B ) Group 4 transition metal A compound which reacts with compound (A) to form an ion pair, (C) (C-1) an organometallic compound containing a Group 2 or Group 12 metal in the periodic table, and (C-2) an organoaluminum Homopolymerization of a C6-C20 alpha-olefin (M) at the temperature of 95-200 degreeC in the presence of the olefin polymerization catalyst which consists of at least 1 or more types of compounds chosen from a compound, or a main monomer (Co) polymerization using α-olefin (M) having 6 to 20 carbon atoms and α-olefin having 2 to 20 carbon atoms (excluding α-olefin (M)) as It is characterized by forming a (co) polymer.

In the production method of the present invention, a homopolymer or copolymer having a kinematic viscosity at 100 ° C. in the range of 10 to 10,000 mm ² / S, measured according to JIS K2283, is preferably produced. The

  The present invention can produce an α-olefin (co) polymer having 6 to 20 carbon atoms as a main monomer with high polymerization activity. According to the manufacturing method of the present invention, the deashing process can be simplified and omitted, and the manufacturing apparatus can be reduced in size and the equipment cost can be reduced. Furthermore, it was also found that the α-olefin (co) polymer obtained by the method of the present invention exhibits excellent heat resistance (suppression of a decrease in hue after heat history, no gel-like precipitate is generated even after heat treatment, etc.). .

  Hereinafter, the manufacturing method of the alpha olefin (co) polymer which uses the C6-C20 alpha olefin (M) which concerns on this invention as a main monomer is demonstrated concretely. In the present specification, the term “(co) polymerization” may be used not only for homopolymerization but also for the purpose of including copolymerization, and the term “(co) polymer” refers to a homopolymer. In addition, it may be used in the meaning including a copolymer. In the present invention, “α-olefin” is defined as including ethylene, and the expression “as the main monomer” refers to a monomer having a skeleton content of 50 mol% or more derived from the monomer in the produced polymer. Defined as a term to indicate.

  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].

(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 and R ¹² are a hydrogen atom, a hydrocarbon group, a silicon-containing group. Each of R ¹³ and R ¹⁴ may be the same or different from a hydrocarbon group, a halogen atom-containing carbon hydrogen group, a halogen atom, an oxygen-containing group, a nitrogen-containing group or a silicon-containing group; A substituted aryl group having one or more selected substituents, R ¹³ and R ¹⁴ may be the same or different from each other, M is Ti, Zr or Hf, Y is a Group 14 atom, Q is selected from a halogen, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4.)

In the general formula [1], as the hydrocarbon groups as 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 , , 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 an alkylaryl group having 7 to 20 carbon atoms. The ring structure may be included. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1,1,3-trimethylbutyl group , Neopentyl group, cyclohexylmethyl group, cyclohexyl group, 1-methyl-1-cyclohexyl group, 1-adamantyl group, 2-adamantyl group, 2-methyl-2-adamantyl group, menthyl group, norbornyl group, benzyl group, 2- Examples include phenylethyl group, 1-tetrahydronaphthyl group, 1-methyl-1-tetrahydronaphthyl group, phenyl group, naphthyl group, tolyl group and the like.

In the above general formula [1], silicon-containing hydrocarbon groups as 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 Is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group. It is done.

The adjacent substituents from R ¹ to R ⁴ on the cyclopentadienyl ring in the general formula [1] may be bonded to each other to form a ring. In the present invention, R ¹ to R ⁴ are preferably hydrogen atoms.

The adjacent substituents from R ⁵ to R ¹² on the fluorene ring in the general formula [1] may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

In addition, the substituents or atoms of R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of the synthesis of the ligand, that is, R ⁵ and R ¹² are the same substituent or atom, R ⁶ and R 12 ¹¹ is preferably the same substituent or atom, R ⁷ and R ¹⁰ are preferably the same substituent or atom, and R ⁸ and R ⁹ are preferably the same substituent or atom. More preferred are substituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 2-position, 3-position, 6-position and 7-position on the fluorene ring correspond to R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ in the general formula [1], respectively.

It is preferable that any three or more groups selected from R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ on the fluorene ring are not hydrogen atoms at the same time, and four groups of R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ are used. Are preferably not simultaneously hydrogen atoms, and R ⁶ and R ⁷ are bonded to each other to form a ring (1), and R ¹⁰ and R ¹¹ are bonded to each other to form a ring (2). Particularly preferred. Ring (1) and ring (2) may have the same structure or different structures, but usually ring (1) and ring (2) have the same structure because the ligand is easily synthesized. Is preferred.

In the above general formula [1], R ¹³ and R ¹⁴ are substituted aryl groups and have a substituent on the aromatic nucleus. The “aryl group” defined in the present invention is defined as a group in which all of the aromatic nucleus hydrogen atoms except the aromatic nucleus hydrogen atom bonded to Y are not substituted. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group, but a phenyl group and a naphthyl group are preferable. When the aromatic nucleus hydrogen atom is substituted with a substituent, the substituent may be substituted for all aromatic nucleus hydrogen atoms, may be substituted with a specific number of aromatic nucleus hydrogen atoms, Substitution with only nuclear hydrogen may be used. Examples of the substituent include a hydrocarbon group, a halogen atom-containing carbon hydrogen group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, and a silicon-containing group.

  A preferred form of the hydrocarbon group is a hydrocarbon group having 1 to 20 carbon atoms in total. Examples of the hydrocarbon group having 1 to 20 carbon atoms in total include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Linear hydrocarbon group such as heptyl group, n-octyl group, n-nonyl group, n-decanyl group; isopropyl group, t-butyl group, amyl group, t-amyl group, 3-methylpentyl group, 1, 1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, methyl-1-isopropyl- Branched hydrocarbon groups such as 2-methylpropyl group and cyclopropylmethyl group; alkenyl groups such as vinyl group, isopropenyl group, butenyl group and pentenyl group; alkynyl group having an acetylenic triple bond; cyclopentyl group, cyclohexyl Group, cycloheptyl Cyclic saturated hydrocarbon groups such as cyclooctyl group, norbornyl group and adamantyl group; cyclic unsaturated hydrocarbon groups such as phenyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group; aryl groups such as benzyl group and cumyl group Can be mentioned.

  A preferred form of the halogen atom-containing hydrocarbon group is a group in which one or more hydrogen atoms of the hydrocarbon group having 1 to 20 carbon atoms are substituted with a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. is there. Examples of such a halogen atom-containing hydrocarbon group include a trifluoromethyl group and a tribromomethyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the oxygen-containing group include a methoxy group, an ethoxy group, and a phenoxy group.

  Examples of nitrogen-containing groups include N-methylamino group, N, N-dimethylamino group, and N-phenylamino group.

  The silicon atom-containing hydrocarbon group is a substituent formed by a chemical bond between a silicon atom and an aromatic nucleus, specifically, a trimethylsilyl group, a triethylsilyl group, or a hydrocarbon group substituted with these trialkylsilyl groups. Specific examples thereof include a mono (trimethylsilyl) methyl group and a di (trimethylsilyl) methyl group.

Each of R ¹³ and R ¹⁴ is a substituted aryl group having one or more of the above-described substituents. When each of R ¹³ and R ¹⁴ is a substituted aryl group having two or more of the substituents, the two or more substituents may be the same or different from each other. R ¹³ and R ¹⁴ are each a substituted aryl group which may be the same or different.

  In the present invention, the substituted aryl group is preferably a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group substituted with a halogen atom-containing hydrocarbon group.

  In the present invention, M in the general formula [1] is zirconium, titanium, or hafnium.

Y is a Group 14 atom, preferably a carbon atom and a silicon atom. Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral coordination that can be coordinated by a neutral, conjugated or nonconjugated diene, an anionic ligand or a lone electron pair having 10 or less carbon atoms. The same or different combinations are selected from the children. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 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, ter t-butyl, 1, 1 -Dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Examples having 10 or less neutral, conjugated or nonconjugated dienes carbon, 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 -2,2, 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- trans eta 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 neutral ligands that can be coordinated by a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations. j is an integer of 1-4.

  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.

  Di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di ( p-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butyl Fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadieni ) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -n-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride Di (pn-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (3, 6 -Di-tert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) ( (Luolenyl) 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 (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (cyclo Pentadienyl) (fluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluoro Nyl) zirconium dimethyl, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (cyclopentadiyl) (Enyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di ( p-tert-butylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (cyclopentadienyl) Enyl) (octamethyloctahydride Dibenzofluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopenta (Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride , Di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (3,6- Ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3,6-ditert- Tylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-tert-butylphenyl) (phenyl ) Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorene) Nyl) zirconium dichloride, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadiene) (3,6-ditert-butylfluorenyl) zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-n-ethylphenyl) (Phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (pn-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethyl Fluorenyl) zirconium dichloride, (p-n-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (Cyclopentadienyl) (fluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadiene) Nyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (4-biphenyl) ) (Phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (4- Biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride Di (4-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium It can be exemplified dichloride.

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

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 Examples thereof include (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, trimethylboron, and triisobutylboron.
Examples of the ionic compound include a compound represented by the following general formula [2].

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-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation 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.

  Of these, Re 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) 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 2, 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 Over DOO, dioctadecyl methyl ammonium tetrakis (3, 5 - ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  Specific examples of N, N -dialkylanilinium salts include N, N -dimethylanilinium tetraphenyl borate, 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 1, N-2, 4, 6 -pentamethylanilinium tetraphenylborate, N 2, N-2, 4, 6 -pentamethylanilinium tetrakis (pentafluorophenyl) borate .

  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 [3] or [4] Or a borate compound containing an active hydrogen represented by the following formula [5], a borate compound containing a silyl group represented by the following formula [6], or the like.

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

[B-Qn (Gq (T -H) r) z] - A + ... [5]
In the formula [5], 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 [5] 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 are, 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] in the above formula [5] 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 (pentafluorophenyl) [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, triphenyloxon Umum 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 + ... [6]
In the formula [6], 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 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 [6] [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 .
A is A ⁺ is the counter cation of the borate compound include the same as the A ⁺ in the formula [5].

  Specific examples of borane compounds 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-dicarbound decaborane, dodecahydride-1 1-methyl-2,7-dicarbaound decaborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) a Nmonium 1-trimethylsilyl-1-carbadecaborate, 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-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl -7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaound decaborate , Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundeborate, tri (n -butyl) ammonium undecahydride-4, 6 -dibromo-7 -carbandecaborate and other anionic salts; tri (n -butyl) ammonium bis (nonahydride-1, 3 -dicarbanonaborate) cobalt Acid salt (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-Dicarbaoundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelic acid (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n- (Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaun Decaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] Screw (Undekahide Id-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri ( and salts of metal carborane anions such as (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

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

(C-1) Organometallic Compound As the (C-1) organometallic compound used in the present invention, the following organometallic compounds are specifically 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 represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a metal of Group 2 or Group 12 of the Periodic Table represented by: Moreover, such an organometallic compound (C-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(C-2) Organoaluminum compound Forming a catalyst for olefin polymerization (C-2) The organoaluminum compound is, for example, an organoaluminum compound represented by the following general formula [7], represented by the following general formula [8] 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 ... [7]
(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, 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 [8]
(Wherein, ^{M 2} represents a Li, Na or K, ^{R a} is from 1 to 15 carbon atoms, preferably an. 1-4 hydrocarbon group) of the periodic table Group 1 metals represented by 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 [7] include compounds represented by the following general formula [9], [10], [11], or [12].

R ^a _m Al (OR ^b ) _3-m ... [9]
(In the formula, R ^a and R ^b may be the same as 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 ... [10]
(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 ... [11]
(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 ... [12]
(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 [9], [10], [11], or [12] include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, Tri-n-alkylaluminums such as pentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; 3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylal Tri-branched alkylaluminums such as nium and tri-2-ethylhexylaluminum; Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminums 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 isoprenylaluminum represented by the formula: isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide and the like Kill aluminum alkoxide; Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide; General formula R ^a _2.5 Al (OR ^b ) partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; 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) Alkyl aluminum aryloxides such as 4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethyl Alkyl aluminum sesquihalides such as aluminum sesquibromides; Partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkyls such as diethylaluminum hydride and dibutylaluminum hydride Aluminum hydride Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; partially alkoxy such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide And alkylated aluminum and the like.

A compound similar to the compound represented by the general formula [7] 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 [8] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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 [7] or the complex alkylated product of the Group 1 metal and aluminum represented by the general formula [8] may be used alone or 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-exchangeable 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, the α-olefin (M) having 6 to 20 carbon atoms is 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1 Examples thereof include α-olefins having 6 to 20, preferably 6 to 16, carbon atoms such as -undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. In the case of a copolymer, the olefin (M) having 6 to 20 carbon atoms and the α-olefin having 2 to 20 carbon atoms (excluding α-olefin (M)) as the main monomer are used. Use in combination. In this case, it is also within the scope of the present invention to use two or more different α-olefins having 2 to 20 carbon atoms (excluding the α-olefin (M)).

  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 include 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 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.

  In the present invention, the polymerization reaction can also be 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 ⁻⁹ to 10 ⁻³ mol / liter, preferably from 10 ⁻⁸ to 10 ⁻⁴ mol / liter.

  Component (B) is such that the molar ratio [(B) / M] of component (B) and transition metal atom (M) in component (A) is usually 1 to 50, preferably 1 to 20. Used in quantity.

  Component (C-1) has a molar ratio (C-1) / M] of component (C-1) to all transition metal atoms (M) in component (A) of usually 0.01 to 5000, preferably Is used in an amount of 0.05 to 2000. Component (C-2) has a molar ratio [(C-2) / M] of component (C-2) to all transition metal atoms (M) in component (A) of usually 100 to 25000, preferably The amount used is 500 to 10,000.

  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 carried out 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 content of the skeleton unit derived from the α-olefin (M) having 6 to 20 carbon atoms as the main monomer in the α-olefin (co) polymer obtained in the present invention is preferably 50 to 100 mol%. Is in the range of 55 to 100 mol%, and the content of the α-olefin component having 2 to 20 carbon atoms (excluding the α-olefin (M)) is 0 to 50 mol%, preferably 0. It is in the range of ˜45 mol%.

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 kinematic viscosity at 100 ° C. is in the range of 10 to 10,000 mm ² / S, preferably It is in the range of 15 to 5,000 mm ² / S, and more preferably in the range of ^{20 to} 3,000 mm ² / S.

  The polymerization temperature in this invention is 95-200 degreeC normally, Preferably it is 95-180 degreeC, Most preferably, it is the range of 95-160 degreeC.

  When the polymerization temperature is within the above range, the heat removal of the polymerization system is easy, and the heat removal apparatus can be miniaturized. Moreover, in the same heat removal apparatus, the heat removal efficiency is increased, so that productivity can be improved. Furthermore, since the polymerization is performed at a high temperature, even if the polymer concentration is increased, the solution viscosity is not so high and the stirring power can be reduced, and the polymerization can be performed at a high concentration, so that productivity is improved.

  Usually, when (co) polymerizing olefins, heat is removed by circulating a solvent or the like in order to stabilize the polymerization temperature. In the heat removal apparatus used here, if the amount of heat removal is the same, the heat transfer area can be reduced as the polymerization temperature is higher, and the effect varies depending on the selection of conditions such as the cooling medium. When a simple counter-current heat exchanger using water is used, when the polymerization temperature is 100 ° C., the required heat transfer area is about 2 minutes compared to when the polymerization temperature is 70 ° C. It is also possible to set to 1. When the polymerization temperature is increased in this manner, the necessary heat transfer area can be reduced and the heat removal apparatus can be reduced in size, so that the equipment cost can be reduced.

  When the polymerization temperature exceeds 200 ° C., the resulting polymer may be deteriorated, which is not preferable for use as a lubricating oil.

When producing an olefin (co) polymer having the above kinematic viscosity at a polymerization temperature of less than 95 ° C., it is necessary to lower the monomer concentration or increase the H ₂ partial pressure. When the monomer concentration is lowered, the catalytic activity and productivity are lowered. In order to increase the H ₂ pressure, it is necessary to increase the pressure resistance of the polymerization vessel, which increases the equipment cost.

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

Viscosity Characteristics The kinematic viscosity at 100 ° C. of the α-olefin (co) polymer was measured and calculated by the method described in JIS K2283.

Turbidity The turbidity of the α-olefin (co) polymer was measured as follows. A sample is taken in a 50 mm glass cell, left in a -20 ° C. constant temperature bath for 1 hour, and then left in a 20 ° C. constant temperature water bath for 1 hour, then the sample is taken out, and a Hitachi U-2001 spectrophotometer is used. Measurements were made. The measurement result was expressed as absorbance at a wavelength of 660 nm.

Heat test In order to evaluate the heat resistance of the α-olefin (co) polymer, a test was conducted as follows. 30 g of a sample was placed in a glass petri dish having a diameter of 40 mm, left in a circulating drier at 180 ° C. for 24 hours, then taken out and allowed to cool to room temperature. The total acid value of the sample before and after the test was measured by the method described in JIS K2501, and the increase in the total acid value was calculated. Further, the hue of the sample after the heat test was measured by the method described in ASTM D1209, and the precipitate was confirmed visually.

1000 ml of 1-decene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature in the system was raised to 100 ° C., and hydrogen was supplied to adjust the total pressure to 3 MPa-G. Then 0.4 mmol of triisobutylaluminum, 0.0005 mmol of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) 0.002 mmol of borate was injected with nitrogen, and the polymerization was started by setting the stirring speed to 400 rpm. Thereafter, by continuously supplying only hydrogen, the total pressure was kept at 3 MPa-G, and polymerization was carried out at 100 ° C. for 60 minutes. Polymerization was stopped by adding a small amount of methanol into the system. Under reduced pressure (1 mmHg) at 175 ° C., the solvent and unreacted 1-decene were distilled off from the polymer solution to obtain 647 g of a liquid polymer (1-decene polymer). The polymerization activity was 1290 kg / mmol-Zr · hr. As a result of analysis of the polymer, it was a transparent liquid polymer having a kinematic viscosity at 100 ° C. of 110 mm ² / s, a hue (APHA) of 20, and a turbidity of less than 0.001. Further, after the heat resistance test of the obtained liquid polymer, the hue (APHA) was 180, the total acid value increase was 0.96 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Tables 1 and 2.

[Reference Example 1]
In Example 1, the polymer solution after completion of polymerization was added to 300 ml of 1N hydrochloric acid and stirred, and after separating the organic layer with a separatory funnel, the organic layer was washed with water and 175 ° C. under reduced pressure (1 mmHg). A 1-decene polymer was produced in the same manner as in Example 1 except that the solvent and unreacted 1-decene were distilled off. The obtained liquid polymer had a hue (APHA) of 20, a turbidity of less than 0.001, and was a transparent liquid polymer. After the heat test, the hue (APHA) was 200, the total acid value increase was 1.21 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Table 2.

[Comparative Example 1]
In Example 1, the amount of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.003 mmol, and N, N-dimethylanilinium tetrakis (pentafluoro A 1-decene polymer was produced in the same manner as in Example 1 except that the phenyl) borate was changed to 0.9 mmol of MMAO-3A (manufactured by Tosoh Finechem). The obtained polymer was 598 g, and the polymerization activity was 199 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 98 mm ² / s, the hue (APHA) was 20, the turbidity was 0.037, and it was a translucent liquid polymer with white turbidity. Further, after the heat test, the hue (APHA) was 300, the total acid value increase was 1.01 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 2]
In Example 1, 600 ml of n-heptane and 400 ml of 1-decene were charged instead of 1000 ml of 1-decene, and the temperature in the subsequent system and the polymerization temperature were changed to 90 ° C. 1-decene polymer was produced. The obtained polymer was 193 g, and the polymerization activity was 386 kg / mmol-Zr · hr. As a result of analysis of the polymer, the kinematic viscosity at 100 ° C. was 108 mm ² / s, the hue (APHA) was 20, the turbidity was 0.030, and it was a translucent liquid polymer with white turbidity. Further, after the heat test, the hue (APHA) was 270, the total acid value was 1.16 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

1000 ml of 1-decene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature in the system was raised to 120 ° C., and hydrogen was supplied to make the total pressure 3 MPa-G. Then 0.4 mmol of triisobutylaluminum, 0.0005 mmol of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) 0.002 mmol of borate was injected with nitrogen, and the polymerization was started by setting the stirring speed to 400 rpm. Thereafter, only hydrogen was continuously supplied to keep the total pressure at 3 MPa-G, and polymerization was carried out at 120 ° C. for 60 minutes. Polymerization was stopped by adding a small amount of methanol into the system. The solvent and unreacted 1-decene were distilled off from the polymer solution at 175 ° C. under reduced pressure (1 mmHg) to obtain 642 g of a liquid polymer (1-decene polymer). The polymerization activity was 1280 kg / mmol-Zr · hr. As a result of polymer analysis, it was a transparent liquid polymer having a kinematic viscosity at 100 ° C. of 61 mm ² / s, a hue (APHA) of 15, and a turbidity of less than 0.001. Further, after the heat resistance test of the obtained liquid polymer, the hue (APHA) was 180, the total acid value increase was 1.03 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Tables 1 and 2.

[Comparative Example 3]
In Example 2, the amount of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.003 mmol, and N, N-dimethylanilinium tetrakis (pentafluoro A 1-decene polymer was produced in the same manner as in Example 2, except that the phenyl) borate was changed to 0.9 mmol of MMAO-3A (manufactured by Tosoh Finechem). The obtained polymer was 482 g, and the polymerization activity was 161 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 54 mm ² / s, the hue (APHA) was 25, the turbidity was 0.042, and it was a translucent liquid polymer with white turbidity. Further, after the heat test, the hue (APHA) was 400, the total acid value was 1.10 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 4]
In Example 2, the amount of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.0025 mmol, and N, N-dimethylanilinium tetrakis (pentafluoro A 1-decene polymer was produced in the same manner as in Example 2 except that the phenyl) borate was changed to 0.75 mmol of MAO (Albemarle). The obtained polymer was 547 g, and the polymerization activity was 219 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 60 mm ² / s, the hue (APHA) was 20, the turbidity was 0.036, and it was a translucent liquid polymer with white turbidity. Further, after the heat resistance test, the hue (APHA) was 280, the total acid value increase was 1.21 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 5]
In Example 2, instead of 1000 ml of 1-decene, 800 ml of n-heptane and 200 ml of 1-decene were charged, and then the temperature in the system and the polymerization temperature were changed to 90 ° C. in the same manner as in Example 2. 1-decene polymer was produced. The obtained polymer was 65 g, and the polymerization activity was 130 kg / mmol-Zr · hr. As a result of analysis of the polymer, the kinematic viscosity at 100 ° C. was 72 mm ² / s, the hue (APHA) was 25, the turbidity was 0.049, and it was a translucent liquid polymer with white turbidity. Further, after the heat resistance test, the hue (APHA) was 420, the total acid value increase was 1.20 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

1000 ml of 1-decene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature in the system was raised to 120 ° C., and hydrogen was supplied to make the total pressure 3 MPa-G. Then 0.4 mmol of triisobutylaluminum, 0.0005 mmol of di (p-chloro-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and N, N-dimethylanilinium tetrakis (penta Polymerization was initiated by injecting 0.002 mmol of fluorophenyl) borate with nitrogen and setting the stirring speed to 400 rpm. Thereafter, only hydrogen was continuously supplied to keep the total pressure at 3 MPa-G, and polymerization was carried out at 120 ° C. for 60 minutes. Polymerization was stopped by adding a small amount of methanol into the system. The solvent and unreacted 1-decene were distilled off from the polymer solution at 175 ° C. under reduced pressure (1 mmHg) to obtain 665 g of a liquid polymer (1-decene polymer). The polymerization activity was 1330 kg / mmol-Zr · hr. As a result of analysis of the polymer, it was a transparent liquid polymer having a kinematic viscosity at 100 ° C. of 84 mm ² / s, a hue (APHA) of 10, and a turbidity of less than 0.001. Further, after the heat resistance test of the obtained liquid polymer, the hue (APHA) was 150, the total acid value increase was 1.09 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Tables 1 and 2.

[Comparative Example 6]
In Example 3, the amount of di (p-chloro-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.003 mmol, and N, N-dimethylanilinium tetrakis ( A 1-decene polymer was produced in the same manner as in Example 3 except that the pentafluorophenyl) borate was changed to 0.9 mmol of MMAO-3A (manufactured by Tosoh Finechem). The obtained polymer was 465 g, and the polymerization activity was 155 kg / mmol-Zr · hr. As a result of analysis of the polymer, the kinematic viscosity at 100 ° C. was 78 mm ² / s, the hue (APHA) was 25, the turbidity was 0.040, and it was a translucent liquid polymer with white turbidity. Further, after the heat test, the hue (APHA) was 400, the total acid value increase was 1.25 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 7]
In Example 3, the amount of di (p-chloro-phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.0025 mmol, and N, N-dimethylanilinium tetrakis ( A 1-decene polymer was produced in the same manner as in Example 3 except that the pentafluorophenyl) borate was changed to 0.75 mmol of MAO (Albemarle). The obtained polymer was 520 g, and the polymerization activity was 208 kg / mmol-Zr · hr. As a result of analysis of the polymer, the kinematic viscosity at 100 ° C. was 76 mm ² / s, the hue (APHA) was 20, the turbidity was 0.038, and it was a translucent liquid polymer with white turbidity. Further, after the heat test, the hue (APHA) was 270, the total acid value was 1.16 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 8]
In Example 3, instead of 1000 ml of 1-decene, 800 ml of n-heptane and 200 ml of 1-decene were charged, and the temperature in the system and the polymerization temperature thereafter were changed to 90 ° C., as in Example 3. 1-decene polymer was produced. The obtained polymer was 61 g, and the polymerization activity was 122 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 90 mm ² / s, the hue (APHA) was 25, the turbidity was 0.045, and it was a translucent liquid polymer with white turbidity. Moreover, after the heat test, the hue (APHA) was 460, the total acid value increase was 1.04 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer, but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

1000 ml of 1-decene was charged into a 2 L stainless steel autoclave sufficiently purged with nitrogen, the temperature inside the system was raised to 140 ° C., and hydrogen was supplied to make the total pressure 3 MPa-G. Then 0.4 mmol of triisobutylaluminum, 0.0005 mmol of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) 0.002 mmol of borate was injected with nitrogen, and the polymerization was started by setting the stirring speed to 400 rpm. Thereafter, only hydrogen was continuously supplied to keep the total pressure at 3 MPa-G, and polymerization was carried out at 140 ° C. for 60 minutes. Polymerization was stopped by adding a small amount of methanol into the system. The solvent and unreacted 1-decene were distilled off from the polymer solution at 175 ° C. under reduced pressure (1 mmHg) to obtain 623 g of a liquid polymer (1-decene polymer). The polymerization activity was 1250 kg / mmol-Zr · hr. As a result of polymer analysis, it was a transparent liquid polymer having a kinematic viscosity at 100 ° C. of 30 mm ² / s, a hue (APHA) of 15, and a turbidity of less than 0.001. Further, after the heat resistance test of the obtained liquid polymer, the hue (APHA) was 140, the total acid value increase was 0.98 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Tables 1 and 2.

In Example 4, a 1-decene polymer was produced in the same manner as in Example 4 except that 450 ml of n-heptane and 550 ml of 1-decene were used instead of 1000 ml of 1-decene. As a result, 304 g of a liquid polymer (1-decene polymer) was obtained. The polymerization activity was 608 kg / mmol-Zr · hr. As a result of analysis of the polymer, it was a transparent liquid polymer having a kinematic viscosity at 100 ° C. of 20 mm ² / s, a hue (APHA) of 20, and a turbidity of less than 0.001. Further, after the heat resistance test of the obtained liquid polymer, the hue (APHA) was 150, the total acid value increase was 1.15 mgKOH / g, there was no precipitate, and there was no problem in practical use. The results are summarized in Tables 1 and 2.

[Comparative Example 9]
In Example 4, the amount of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.003 mmol, and N, N-dimethylanilinium tetrakis (pentafluoro A 1-decene polymer was produced in the same manner as in Example 4 except that the phenyl) borate was changed to 0.9 mmol of MMAO-3A (manufactured by Tosoh Finechem). The obtained polymer was 258 g, and the polymerization activity was 86 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 36 mm ² / s, the hue (APHA) was 30, the turbidity was 0.067, and it was a translucent liquid polymer with white turbidity. In addition, after the heat resistance test, the hue (APHA) was 500, and the total acid value increase was 1.24 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 10]
In Example 4, the amount of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was changed to 0.003 mmol, and N, N-dimethylanilinium tetrakis (pentafluoro A 1-decene polymer was produced in the same manner as in Example 4 except that the phenyl) borate was changed to 3.0 mmol of MMAO-3A (manufactured by Tosoh Finechem). The obtained polymer was 610 g, and the polymerization activity was 203 kg / mmol-Zr · hr. As a result of analysis of the polymer, it was a translucent liquid polymer having a kinematic viscosity at 100 ° C. of 28 mm ² / s, a hue (APHA) of 20, a turbidity of 0.035, and white turbidity. Further, after the heat test, the hue (APHA) was 300, the total acid value increase was 1.05 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 11]
In Example 4, 900 ml of n-heptane and 100 ml of 1-decene were charged instead of 1000 ml of 1-decene, and the temperature in the system and the polymerization temperature thereafter were changed to 90 ° C. 1-decene polymer was produced. The obtained polymer was 16 g, and the polymerization activity was 32 kg / mmol-Zr · hr. As a result of polymer analysis, it was a translucent liquid polymer having a kinematic viscosity at 100 ° C. of 44 mm ² / s, a hue (APHA) of 30, a turbidity of 0.085, and white turbidity. Further, after the heat test, the hue (APHA) was 480, the total acid value increase was 1.26 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 12]
In Example 4, instead of 1000 ml of 1-decene, 800 ml of n-heptane and 200 ml of 1-decene were charged and di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium. In the same manner as in Example 4 except that 0.0005 mmol of di (phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride was used instead of dichloride, 1- A decene polymer was produced. The obtained polymer was 15 g, and the polymerization activity was 30 kg / mmol-Zr · hr. As a result of polymer analysis, the kinematic viscosity at 100 ° C. was 30 mm ² / s, the hue (APHA) was 30, the turbidity was 0.088, and it was a translucent liquid polymer with white turbidity. Moreover, after the heat test, the hue (APHA) was 500, the total acid value was 1.08 mgKOH / g, and a gel-like precipitate was formed. This precipitate is not caused by oxidation of the polymer but is caused by low activity and no decalcification, and the formation of these precipitates is unsuitable for use as a lubricating oil or the like. The results are summarized in Tables 1 and 2.

[Comparative Example 13]
In Example 4, 700 ml of n-heptane and 300 ml of 1-decene were used instead of 1000 ml of 1-decene, and di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium. Instead of dichloride, 0.0005 mmol of di (methyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride was used, and the polymer solution after the polymerization was treated with 300 ml of 1N hydrochloric acid. The organic layer was separated with a separatory funnel, washed with water, and the solvent and unreacted 1-decene were distilled off under reduced pressure (1 mmHg) at 175 ° C. In the same manner as in Example 4, a 1-decene polymer was produced. The obtained polymer was 104 g, and the polymerization activity was 208 kg / mmol-Zr · hr. As a result of polymer analysis, it was a transparent liquid polymer with a kinematic viscosity at 100 ° C. of 26 mm ² / s, a hue (APHA) of 20, and a turbidity of less than 0.001. Further, after the heat resistance test, the hue (APHA) was 220, and the total acid value was 1.48 mgKOH / g, and a gel-like precipitate was formed. This precipitate is due to the oxidation of the polymer, and the formation of these precipitates is unsuitable for use as a lubricating oil. The results are summarized in Tables 1 and 2.

Claims (2)

(A) Group 4 transition metal compound represented by the following general formula [1],
(B) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair, and (C) (C-1) an organometallic compound containing a Group 2 or Group 12 metal in the periodic table, and,
(C-2) at least one compound selected from organoaluminum compounds,
Homopolymerization of an α-olefin (M) having 6 to 20 carbon atoms or an α-olefin having 6 to 20 carbon atoms as a main monomer in the presence of an olefin polymerization catalyst comprising A method of producing a homopolymer or a copolymer by (co) polymerization using (M) and an α-olefin having 2 to 20 carbon atoms (excluding the α-olefin (M)).

(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 and R ¹² are a hydrogen atom, a hydrocarbon group, a silicon-containing group. R ¹³ and R ¹⁴ may be the same or different from a hydrocarbon group, a halogen-containing carbon hydrogen group, a halogen atom, an oxygen-containing group, a nitrogen-containing group, or a silicon-containing group. Each of R ¹³ and R ¹⁴ may be the same or different, M is Ti, Zr or Hf, Y is a group 14 atom, and Q is a substituted aryl group having one or more substituents. Are selected from a halogen, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4.) 2. The production method according to claim 1, which is a homopolymer or copolymer having a kinematic viscosity at 100 ° C. in the range of 10 to 10,000 mm ² / S, measured according to JIS K2283. .