JP2005298747A - Olefin polymerization catalyst component and process for producing olefin polymer - Google Patents

Abstract

（式中、Ｒ¹はそれぞれ独立に水素原子、置換されていてもよい炭素原子数１〜１０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基又は置換されていてもよい炭素原子数６〜２０のアリール基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜２０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基等、を示す。ｎは１〜４の整数を示す。）で示されるフェノール化合物と、周期表第８−１０族の遷移金属を含む遷移金属化合物とを組合わせてなることを特徴とするオレフィン重合触媒成分。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst.
SOLUTION: Formula (1)

(In the formula, each R ¹ is independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or substituted. A preferable aryl group having 6 to 20 carbon atoms, wherein R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, An aralkyl group having 7 to 20 carbon atoms which may be substituted, etc., n represents an integer of 1 to 4, and a transition metal of Group 8-10 of the periodic table. An olefin polymerization catalyst component comprising a combination with a transition metal compound.
[Selection figure] None

Description

  The present invention relates to a novel olefin polymerization catalyst component and a method for producing an olefin polymer using the same.

Catalysts using Group 10 transition metal compounds in the periodic table are known to be useful as olefin polymerization catalysts (see, for example, Non-Patent Document 1). For example, nickel and palladium compounds coordinated with diimine There is known a catalyst system using a catalyst (see, for example, Patent Document 1).
WO96 / 23010 Chem. Rev. 2000, 110, 1169-1203

  Under such circumstances, development of a catalyst for producing a novel easily prepared olefin polymer using a late transition metal compound typified by Group 10 has been desired.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel late-cycle metal catalyst and have reached the present invention.

（式中、Ｒ¹はそれぞれ独立に水素原子、置換されていてもよい炭素原子数１〜１０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基又は置換されていてもよい炭素原子数６〜２０のアリール基を示し、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、ハロゲン原子、置換されていてもよい炭素原子数１〜２０のアルキル基、置換されていてもよい炭素原子数７〜２０のアラルキル基、置換されていてもよい炭素原子数６〜２０のアリール基、置換されていてもよい炭素原子数１〜２０のアルコキシ基、置換されていてもよい炭素原子数７〜２０のアラルキルオキシ基、置換されていてもよい炭素原子数６〜２０のアリールオキシ基、置換されていてもよい炭素原子数１〜２０の炭化水素で２置換されたアミノ基又は置換されていてもよい炭素原子数１〜２０の炭化水素で置換されたシリル基を示す。ｎは１〜４の整数を示す。）
で示されるフェノール化合物と、周期表第８−１０族の遷移金属を含む遷移金属化合物とを組合わせてなることを特徴とするオレフィン重合触媒成分、及びこれを用いることを特徴とするオレフィン重合体の製造方法に関する。 That is, the present invention provides the formula (1)

(In the formula, each R ¹ is independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or substituted. A preferable aryl group having 6 to 20 carbon atoms, wherein R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, Optionally substituted aralkyl group having 7-20 carbon atoms, optionally substituted aryl group having 6-20 carbon atoms, optionally substituted alkoxy group having 1-20 carbon atoms, substituted Aralkyloxy group having 7 to 20 carbon atoms, optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted hydrocarbon having 1 to 20 carbon atoms A Shows the amino group or substituted good having 1 to 20 carbon atoms be the hydrocarbon-substituted silyl group .n is an integer of 1-4.)
An olefin polymerization catalyst component characterized by combining a phenol compound represented by the above and a transition metal compound containing a transition metal of Group 8-10 of the periodic table, and an olefin polymer using the same It relates to the manufacturing method.

The present invention provides a novel late-cycle metal catalyst that is useful for the production of olefin polymers.

Hereinafter, the present invention will be described in detail.
In the phenol compound represented by the formula (1), specific examples of the optionally substituted alkyl group having 1 to 10 carbon atoms in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl Groups, and substituents in which these groups are substituted with halogen atoms, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons or silyl groups substituted with hydrocarbons, and specific examples thereof include , Fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl , Pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, trichloromethyl group, methoxymethyl group, phenoxymethyl group, dimethylamino Examples thereof include a methyl group and a trimethylsilylmethyl group.

Among the optionally substituted alkyl groups having 1 to 10 carbon atoms, preferred examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an amyl group, and the like, more preferably a methyl group, a tert- A butyl group etc. are mentioned.

Specific examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include benzyl group, naphthylmethyl group, anthracenylmethyl group, diphenyl Examples include methyl groups and those groups substituted with halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons, or silyl groups substituted with hydrocarbons. Specific examples of the aralkyl group having 7 to 20 carbon atoms which may be used include (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, ( 2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) Nyl) methyl group, (3,4-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) (Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2, 3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) Methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n- Pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (Fluorophenyl) methyl group, (difluorophenyl) methyl group, (pentafluorophenyl) methyl group, (chlorophenyl) methyl group, (methoxyphenyl) methyl group, (phenoxyphenyl) methyl group, (dimethylaminophenyl) methyl group, (Trimethylsilylphenyl) methyl group and the like are exemplified, and preferred examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms include benzyl group.

Specific examples of the optionally substituted aryl group having 6 to 20 carbon atoms in R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a phenyl group, a naphthyl group, an anthracenyl group and the like, and these Examples in which the group is substituted with a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon, a silyl group substituted with a hydrocarbon, etc. Are 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl Group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3 , 4 5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n -Octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,5-difluorophenyl group, Pentafluorophenyl group, 4-chlorophenyl group, 2-hydroxyphenyl group, 2 Hydroxy-4-methyl-6-tert-butylphenyl group, 2-hydroxy-6-tert-butylphenyl group, 2-hydroxy-4-chloro-6-tert-butylphenyl group, 2-hydroxy-4-methoxy- 6-tert-butylphenyl group, 2-hydroxynaphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-phenoxyphenyl group, 4-dimethylaminophenyl group, 4-trimethylsilylphenyl group As preferred examples of the optionally substituted aryl group having 6 to 20 carbon atoms, phenyl group, 2,3,5-trimethylphenyl group, 2,6-diisopropylphenyl group, 2-methoxy A phenyl group is mentioned.

Specific examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms in R ² , R ³ , R ⁴ and R ⁵ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n- Butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, and these Examples in which the group is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon or a silyl group substituted with a hydrocarbon, and specific examples thereof include fluoro Methoxy group, difluoromethoxy group, trifluoromethoxy group, fluoroethoxy group, difluoroethoxy group, trifluoroeth Xyl group, tetrafluoroethoxy group, pentafluoroethoxy group, perfluoropropoxy group, perfluorobutyloxy group, perfluoropentyloxy group, perfluorohexyloxy group, perfluorooctyloxy group, perfluorodecyloxy group, trichloromethyl Examples include an oxy group, a methoxymethoxy group, a phenoxymethoxy group, a dimethylaminomethoxy group, and a trimethylsilylmethoxy group. Preferable examples of the optionally substituted alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, and a tert-butoxy group.

Specific examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted in R ² , R ³ , R ⁴ and R ⁵ include benzyloxy group, naphthylmethoxy group, anthracenylmethoxy group, diphenylmethoxy Groups and these substituents are exemplified by halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, amino groups substituted with hydrocarbons or silyl groups substituted with hydrocarbons, etc. Specific examples thereof include (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethyl). Phenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4- Methylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (3,4,4) 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) Methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (N-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, n-pentylphenyl) methoxy group, (neopentylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-dodecylphenyl) methoxy Group, (fluorophenyl) methyl group, (difluorophenyl) methyl group, (pentafluorophenyl) methyl group, (chlorophenyl) methyl group, (methoxyphenyl) methyl group, (phenoxyphenyl) methyl group, (dimethylaminophenyl) methyl Group, (trimethylsilylphenyl) methyl group and the like. Preferred examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group.

Specific examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms in R ² , R ³ , R ⁴ and R ⁵ include a phenoxy group, a naphthoxy group, an anthracenoxy group, and these groups, Examples thereof include those substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group substituted with a hydrocarbon or a silyl group substituted with a hydrocarbon, and specific examples thereof include 2-methylphenoxy. Group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4- Dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylpheno Si group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5 -Tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group N-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 3,5-difluoropheno Si group, pentafluorophenoxy group, 4-chlorophenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group, 4-phenoxyphenoxy group, 4-dimethylaminophenoxy group, 4-trimethylsilylphenoxy group Etc. are exemplified. Preferable examples of the optionally substituted aryloxy group having 7 to 20 carbon atoms include a phenoxy group.

The amino group that is disubstituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ² , R ³ , R ^4, and R ⁵ is an amino group that is substituted with two hydrocarbon groups. As the hydrocarbon group here, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, C1-10 alkyl group such as amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, carbon atom such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group Examples include an aryl group of 6 to 20. Examples of the amino group substituted with a hydrocarbon having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec. -Butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenyl An amino group etc. are mentioned, Preferably a dimethylamino group, a diethylamino group, etc. are mentioned.

Examples of the hydrocarbon group in the silyl group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms in R ² , R ³ , R ⁴ and R ⁵ include a methyl group, an ethyl group, n- Propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, etc. And an aryl group having 6 to 20 carbon atoms such as an alkyl group having 1 to 10 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthracenyl group. Examples of the silyl group substituted with are monosubstituted silyl groups such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, and diethylsilyl group. Di-substituted silyl groups such as diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri- tert-butylsilyl group, tri-isobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, etc. Preferred examples of the silyl group substituted with an optionally substituted hydrocarbon having 1 to 20 carbon atoms include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group. Examples of the silyl group substituted with these hydrocarbons include those in which the hydrocarbon group is substituted with a halogen atom, for example, a fluorine atom.

Examples of the halogen atom in R ^{2, R} 3, ^{R 4} and ^{R 5,} for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom.

Specific examples of the phenol compound represented by the formula (1) include the following compounds, but are not limited thereto.

For example, the phenol compound represented by the formula (1) is a compound of Organic Journal of Chemistry (2000), 598 (1), 87, in which a biscarbonyl compound and an amine compound equivalent to twice the equivalent are heated using a Dean-Stark apparatus. It can manufacture according to the method of description.

Examples of the transition metal in the transition metal compound containing a transition metal of Group 8-10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum, preferably iron, cobalt. , Nickel and palladium, more preferably cobalt and nickel, and most preferably nickel.

The transition metal compound may have an anionic ligand. Examples of the anionic ligand include halogen, alkyl group, allyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group. Group, amino group, acyloxy group, sulfonoxy group, 1,3-diketonate group, borate group, phosphate group, antimonate group, etc., specifically, chlorine, bromine, iodine, methyl group, trimethylsilylmethyl group, Ethyl group, allyl group, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, benzyl group, methoxy group, ethoxy group, ethylenedioxy group, phenoxy group, 2-methylphenoxy group, 3-methyl Phenoxy group, 4-methylphenoxy group, 1,2-phenylenedioxy group, 1,1′-binaphthyl-2,2 ′ Dioxy group, benzyloxy group, dimethylamino group, diethylamino group, acetoxy group, trifluoroacetoxy group, benzoyloxy group, methanesulfonyloxy group, benzenesulfonyloxy group, 2-toluenesulfonyloxy group, 3-toluenesulfonyloxy group, 4-toluenesulfonyloxy group, acetylacetonate group, 1,3-diphenyl-1,3-propanedionate group, 3-methyl-2,4-pentanedionate group, tetrafluoroborate group, tetraphenylborate group, Examples include tetra (pentafluorophenyl) borate group, hexafluorophosphate group, hexafluoroantimonate group, preferably chlorine, bromine, acetylacetonate group, 3-methyl-2,4-pentanedionate group, ,further Mashiku is acetyl acetonate group.

The transition metal compound may also have a neutral ligand.

Examples of such a neutral ligand include molecules having a neutral functional group such as ether, sulfide, amine, phosphine, olefin, and nitrile, and also having a plurality of coordination functional groups in the molecule. Specifically, dimethyl ether, diethyl ether, methyl tert-butyl ether, furan, tetrahydrofuran, dimethoxyethane, dimethoxyethane, dimethyl sulfide, diethyl sulfide, methyl tert-butyl sulfide, thiophene, tetrahydrothiophene, ethylenedithiol dimethyl Sulfide, ethylenedithiol diethylsulfide, trimethylamine, triethylamine, triphenylamine, tricyclohexylamine, pyridine, 2,2'-bipyridine, ethylenediamine, tetramethyl Ruethylenediamine, tetraethylethylenediamine, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, bis (diphenylphosphino) methane, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) ) Binaphthyl, ethylene, propylene, butene, butadiene, octene, octadiene, cyclohexene, cyclohexadiene, norbornene, norbornadiene, benzonitrile, acetonitrile and the like.

Specific examples of such transition metal compounds include iron dichloride, iron trichloride, iron (II) acetate, triisopropoxy iron, dimesityl iron, iron (II) acetylacetonate, iron (III) acetylacetonate, bis ( Trifluoroacetoxy) iron, tris (trifluoroacetoxy) iron, iron (II) hexafluoroacetylacetonate

Ruthenium dichloride, ruthenium trichloride, tetrakis (triphenylphosphine) ruthenium dihydride, ruthenium (III) acetylacetonate, ruthenium dichloride (cyclooctadiene)

Cobalt dichloride, cobalt (II) acetate, dimesityl cobalt, trimesityl cobalt, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, bis (trifluoroacetoxy) cobalt, tris (trifluoroacetoxy) cobalt Bis (tris [trimethylsilyl] methyl) cobalt, tris (triphenylphosphine) cobalt methyl

Nickel dichloride, nickel acetate (II), nickel (II) acetylacetonate, allyl nickel chloride, nickel (0) dicyclooctadiene, tetrakis (triphenylphosphine) nickel, bis (triphenylphosphine) phenylnickel chloride, bis (Trimethylsilylmethyl) nickel dipyridine, dimethylnickel tetramethylethylenediamine, dibromonickel dimethoxyethane, bis (trifluoroacetoxy) nickel, bis (hexafluoroacetylacetonate) nickel

Palladium (II) acetate, tris (dibenzylideneacetone) bispalladium, palladium (II) acetylacetonate, (cyclooctadiene) methylpalladium chloride, (cyclooctene) methylpalladium chloride, (cyclooctadiene) methylpalladium triflate, allyl Palladium chloride, dimethylpalladium tetramethylethylenediamine, tetrakis (acetonitrile) palladium bis (tetrafluoroborate)

Bis (ethylenediamine) platinum (II) chloride, cyclooctadiene platinum (II) bromide, cyclooctadiene platinum (II) chloride, bis (benzonitrile) platinum (II) chloride, bis (pyridine) platinum (II) chloride, bis (Triphenylphosphine) platinum (II) chloride, dimethylplatinum (cyclooctadiene), dicyclopentadiene platinum (II) chloride, etc. are exemplified, preferably cobalt compound, nickel compound, more preferably nickel (II) acetylacetonate It is.

The polymerization catalyst component used in the present invention is a combination of a phenol compound represented by the formula (1) and a transition metal compound containing a transition metal of Group 8-10 of the periodic table, and usually both are mixed. It is prepared by.

The molar ratio of the phenol compound represented by the formula (1) and the transition metal compound containing a transition metal of Group 8-10 of the periodic table is not particularly limited, but is preferably in the range of 1: 0.1 to 1:10, more preferably Is in the range of 1: 0.3 to 1: 3.

The polymerization catalyst component is usually prepared in a solvent. Examples of such solvents include aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, hexamethylphosphoric. Amido solvents such as amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Preferably, it is toluene. These solvents are used alone or in combination of two or more, and the amount of the solvent used is not particularly limited.

The obtained reaction mixture is concentrated to precipitate a solid, and in some cases, the polymerization catalyst component can be taken out by a technique such as recrystallization purification, but it can also be used for polymerization without taking it out.

The polymerization catalyst component thus prepared can be used for polymerization by reacting with an activated cocatalyst, and examples of the activated cocatalyst include compounds commonly used such as zinc compounds, aluminum compounds, and boron compounds.

Preferred activating cocatalysts include aluminum compounds and non-aluminum compounds that form ion pairs in pairs with transition metals. By reacting a single or combined compound with a polymerization catalyst component, polymerization can be achieved. Can be used.

A non-aluminum compound that forms an ion pair by pairing with a polymerization catalyst component, an aluminum compound, and a transition metal can be charged and used in any order at the time of polymerization. The reaction product obtained can also be used.

Examples of the aluminum compound used in the present invention include known organoaluminum compounds, for example, compounds represented by the following formulas (A1), (A2), and (A3), and aluminate compounds. Can be used in combination.
(A1): an organoaluminum compound represented by the formula E1 a Al (Z) 3-a,
(A2): a cyclic aluminoxane having a structure represented by the formula {-Al (E2) -O-} b;
(A3): a linear aluminoxane having a structure represented by the formula E3 {-Al (E3) -O-} c Al (E3) 2 (wherein E1 to E3 are the same or different and have 1 to 8 is a hydrocarbon group, Z is the same or different and represents a hydrogen atom or a halogen atom, a is 1, 2 or 3, b is an integer of 2 or more, and c is an integer of 1 or more.)

Specific examples of the organoaluminum compound (A1) represented by the formula E1 a Al (Z) 3-a include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum Dialkylaluminum chlorides such as chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethyl Aluminum high Examples thereof include dialkylaluminum hydrides such as dride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

A cyclic aluminoxane (A2) having a structure represented by the formula {-Al (E2) -O-} b or a structure represented by the formula E3 {-Al (E3) -O-} c Al (E3) 2 Specific examples of E2 and E3 in the linear aluminoxane (A3) include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group and neopentyl group. can do. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E2 or E3 is a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40. Specific examples thereof include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), butylaluminoxane (BAO) and the like.

The above aluminoxane can be obtained from commercial products or prepared by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to produce according to a well-known method. For example, a solution in which trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is made by contacting with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact with the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

Examples of aluminate compounds that can be used in the present invention include triphenylcarbenium tetrakis (pentafluorophenyl) aluminate and triphenylcarbenium tris (2,2 ′, 2 ″ -nanofluorobiphenyl) fluoroaluminate. And triphenylcarbenium tetrakis (pentafluorophenoxy) aluminate.

Non-aluminum compounds that form an ion pair by pairing with a transition metal include compounds that are bulky and / or have an electroattractive substituent and have an anionic atom paired with a transition metal. Examples of such atoms include boron atoms. For example, compounds represented by the following formulas (B1), (B2), and (B3) can be used, and they can be used alone or in combination of two or more. be able to.
(B1) a boron compound represented by the formula BQ1 Q2 Q3,
(B2) a boron compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-
(B3) A boron compound represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-.

In the boron compound (B1) represented by the formula BQ1 Q2 Q3, B is a boron atom in a trivalent valence state, Q1 to Q3 are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carbon number of 1 -20 halogenated hydrocarbon groups, silyl groups substituted with 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms or disubstituted with hydrocarbons having 1 to 20 carbon atoms An amino group, which may be the same or different. Preferred examples of Q1 to Q3 include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of (B1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, and tris. (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like are preferable, but tris (pentafluorophenyl) is preferable. For example, borane.

In the boron compound (B2) represented by the formula Z + (BQ1 Q2 Q3 Q4)-, Z + is an inorganic or organic cation, B is a boron atom in a trivalent valence state, and Q1 to Q4 are The same thing as Q1-Q3 in said (B1) is mentioned.

As a specific example of a compound represented by the formula Z + (BQ1 Q2 Q3 Q4)-, an inorganic cation Z + includes a ferrocenium cation, an alkyl-substituted ferrocenium cation, a silver cation, and the like. Examples of the cation Z + include triphenylmethyl cation. (BQ1 Q2 Q3 Q4)-includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) Examples include borate.

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

In the boron compound (B3) represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-, L is a neutral Lewis base, (LH) + is a Bronsted acid, B is a boron atom in a trivalent valence state, and Q1 to Q4 are the same as Q1 to Q3 in (B1) above.

Specific examples of the compound represented by the formula (LH) + (BQ1 Q2 Q3 Q4)-include Bronsted acid (LH) + include trialkyl-substituted ammonium, N, N-dialkylaniline. Ni, dialkylammonium, triarylphosphonium and the like, and (BQ1 Q2 Q3 Q4)-include the same as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium Tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4 , 6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl Borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethyl) Phenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. Preferably, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, etc. Is mentioned.

The boron compound used in the present invention similarly includes a boron compound containing two or more boron atoms in the molecule via a crosslinking group. Examples of the crosslinking group include an optionally substituted phenylene group and a heterocyclic ring such as imidazole. Specific examples thereof include bis (triphenylcarbenium) [2,3,5,6-tetrafluorophenylene-1 , 4-bis [tris (pentafluorophenyl) borate]], lithium imidazole-bis (tris (pentafluorophenyl) borane) adduct, triethylammonium imidazole-bis (tris (pentafluorophenyl) borane) adduct, etc. It is done.

The amount of each catalyst component used is such that the molar ratio of the compound (A) [the (A1)-(A3) is collectively referred to as (A)] / the transition metal in the polymerization catalyst component is 0.1 to 10,000. Preferably, each component is used so that the molar ratio of the transition metal in the compound (B) / polymerization catalyst component is 0.01-100, preferably 0.5-10. Is desirable.
Regarding the concentration when each catalyst component is used in a solution state, the transition metal in the polymerization catalyst component is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the compound (A) is In terms of Al atom, 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter, and compound (B) is 0.0001 to 5 mmol / liter, preferably 0.001. It is desirable to use each component so that it is in the range of ˜1 mmol / liter.

In the present invention, the monomer used for the polymerization may be any olefin or diolefin having 2 to 20 carbon atoms, and two or more types of monomers may be used at the same time. Such monomers are exemplified below, but the present invention is not limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 5-methyl-2-pentene-1, Vinylcyclohexene and the like are exemplified. Examples of the diolefin compound include conjugated dienes and nonconjugated dienes of hydrocarbon compounds. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, 1 , 4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6 -Octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5 , 8-endomethylenehexahydronaphthalene and the like, and specific examples of the conjugated diene compound include 1,3 Butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, can be exemplified 1,3-cyclohexadiene and the like.
Specific examples of monomers constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and 5-ethylidene-2-norbornene. Combinations and the like are exemplified, but the present invention is not limited to the above compounds.

In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o -Chlorostyrene, p-chlorostyrene, α-methylstyrene, divinylbenzene and the like.

In the present invention, an olefin having a polar functional group can also be used as a monomer. Specific examples of the olefin having a polar functional group include acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, vinyl acetate, acrylonitrile, allyl alcohol, 5-norbornene-2-methanol, 5-norbornene-2-carboxylic Examples include acid, allylamine, acrylamide, 5-norbornene-2-carboxylic acid methyl ester, N, N-dimethylacrylamide and the like.

The polymerization method is not particularly limited. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride. Can be used for solvent polymerization, slurry polymerization, gas phase polymerization in a gaseous monomer, etc., and continuous polymerization or batch polymerization can be used.

The polymerization temperature can range from −50 ° C. to 200 ° C., but the range of about −20 ° C. to 100 ° C. is particularly preferable, and the polymerization pressure is preferably normal pressure to 6 MPa (60 kg / cm 2 G). In general, the polymerization time is appropriately selected depending on the kind of the target polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples. Moreover, the property of the polymer in an Example was measured with the following method.

[Molecular weight and molecular weight distribution]
It measured on condition of the following using RapidGPC (made by Symyx).
Liquid feeding device: (LC pump) manufactured by Gilson
Model305 (pump head 25.SC)
Column: manufactured by Polymer Laboratories (PL)
PLgel Mixed-B 10 μm
7.5mmφ × 300mm
Mobile phase: o-dichlorobenzene Dissolving solvent: 1,2,4-trichlorobenzene flow rate: 2 ml / min Column temperature: 160 ° C
Calibration curve: 8 standard samples of polystyrene (PS)
(Standard PS molecular weight) 5,000, 10,050, 28,500, 65,500
185,400, 483,000, 1,013,000, 3,390,000

[Melting point]
The measurement was performed under the following conditions using SAMMS (Sensor Array Modular System) (manufactured by Symyx).
Measurement mode: Melting temperature measurement by heat capacity spectroscopy Atmospheric gas: Vacuum condition (3.0 × 10 ^-4 Torr or less)
Temperature program: (start) room temperature
(Temperature increase rate) Approximately 50 ° C / min
(Hold) 200 ° C (0 min)

[Me branch]
Measurement was performed under the following conditions using IR (EQUINOX55 manufactured by Bruker).
Measurement mode: reflection transmission method (film creation on mirror surface)
Blank: Mirror surface (Air)
Measurement conditions: (Resolution) 2cm ^-1 , (Integration count) 128 times,
(Wavelength) 400-4000cm ^-1

配位子１の０．０２Mトルエン溶液、ビス（アセチルアセトナート）ニッケル（ＩＩ）０．０２Mトルエン溶液を０．３ｍｌずつバイアル瓶にサンプリングし、室温で２分間混合させた。
オートクレーブに窒素下で、トルエン５．０ｍＬを仕込み、４０℃で安定させた後、エチレンを０．６０ＭＰａまで加圧し安定させた。ここに、MMAO（０．２５Ｍ、１００μｍｏｌ）、上記に記載の重合触媒成分溶液（ニッケル濃度０．０１Ｍ、３μｍｏｌ）を加え、２分間重合した。重合の結果、分子量（Ｍｗ）＝１３００のポリマーをニッケル１ｍｏｌ当たり、1時間当たり、４．４×１０^５ｇ製造した。 [Example 1]
[Polymerization using ligand 1]

A 0.02M toluene solution of ligand 1 and a 0.02M toluene solution of bis (acetylacetonato) nickel (II) were sampled in 0.3 ml vials and mixed at room temperature for 2 minutes.
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. MMAO (0.25 M, 100 μmol) and the polymerization catalyst component solution described above (nickel concentration 0.01 M, 3 μmol) were added thereto, and polymerization was performed for 2 minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 1300 was produced at 4.4 × 10 ⁵ g per hour per 1 mol of nickel.

[Example 2]
Bis (acetylacetonato) nickel (II) to tris (acetylacetonato) cobalt (III), MMAO to triisobucil aluminum (0.25M, 40 μmol) and tris (pentafluorophenyl) borane (0.025M, 9 μmol) The procedure was the same as in Example 1 except that the polymerization time was changed to 3 hours. As a result of the polymerization, a polymer having a molecular weight (Mw) = 2100 was produced at 5.6 × 10 ³ g per hour per 1 mol of cobalt.

Claims (10)

Formula (1)

(In the formula, each R ¹ is independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or substituted. A preferable aryl group having 6 to 20 carbon atoms, wherein R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, Optionally substituted aralkyl group having 7-20 carbon atoms, optionally substituted aryl group having 6-20 carbon atoms, optionally substituted alkoxy group having 1-20 carbon atoms, substituted Aralkyloxy group having 7 to 20 carbon atoms, optionally substituted aryloxy group having 6 to 20 carbon atoms, and optionally substituted hydrocarbon having 1 to 20 carbon atoms A Shows the amino group or substituted good having 1 to 20 carbon atoms be the hydrocarbon-substituted silyl group .n is an integer of 1-4.)
An olefin polymerization catalyst component comprising a combination of a phenol compound represented by the above and a transition metal compound containing a transition metal of Group 8-10 of the periodic table. The olefin polymerization catalyst component according to claim 1, wherein n is 2 in the phenol compound represented by the formula (1). The olefin polymerization catalyst component according to claim 1 or 2, wherein the molar ratio of the phenol compound represented by formula (1) to the transition metal compound is in the range of 1: 0.3 to 1: 3. The olefin polymerization catalyst component according to any one of claims 1 to 3, wherein the transition metal compound is a nickel compound or a cobalt compound. The olefin polymerization catalyst component according to claim 4, wherein the nickel compound or the cobalt compound is a nickel compound having an acetylacetonate type anion or a cobalt compound having an acetylacetonate type anion. An olefin polymerization catalyst comprising the polymerization catalyst component according to any one of claims 1 to 5 in combination with an activated cocatalyst. The olefin polymerization catalyst according to claim 6, wherein the activated cocatalyst is an aluminum compound. The olefin polymerization catalyst according to claim 6, wherein the activated cocatalyst is a non-aluminum compound that forms an ion pair by pairing with an aluminum compound and / or a transition metal. The olefin polymerization catalyst according to claim 8, wherein the non-aluminum compound that forms an ion pair with the transition metal is a boron compound. An olefin polymer is produced using the olefin polymerization catalyst according to any one of claims 6 to 9, and a method for producing an olefin polymer.