JP2005154629A - Catalyst for olefin polymerization and method for producing polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a copolymer in high activity under economical reaction conditions in copolymerization of ethylene with a polar monomer such as an acrylate. <P>SOLUTION: Polymerization of an olefin is carried out by using an activated cocatalyst selected from a specific transition metal compound having an azaferrocene or a phosphaferrocene structure and a diimine structure, compounds represented by the formulas (3) [HL<SP>3</SP>][B(Ar)<SB>4</SB>], (4) [EL<SP>4</SP><SB>u</SB>][B(Ar)<SB>4</SB>], (5) [D][B(Ar)<SB>4</SB>] and (6) B(Ar)<SB>3</SB>, AgSbF<SB>6</SB>, NaPF<SB>6</SB>, Na BF<SB>4</SB>and a modified clay compound, and a catalyst for olefin polymerization containing a halogenated alkylaluminum as its component. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst using a transition metal compound and an olefin polymerization method. Specifically, the present invention relates to a method for efficiently producing a polyolefin by using a transition metal compound having an azaferrocene or phosphaferrocene structure, an activation co-catalyst, and an alkylaluminum halide as constituent components of an olefin polymerization catalyst. .

  In recent years, the use of bidentate (N, N'-diaryl) diimine chelate-type nickel and palladium complexes as catalyst components has led to a number of branches that differ in structure from polyolefins that can be produced with conventional metallocene catalysts. It has been reported that a polyolefin having a structure containing can be produced (for example, see Patent Document 1). These complexes are activated by a Lewis acid compound and an alkylaluminum, and a method for use in olefin polymerization is disclosed (for example, see Patent Document 2). The nickel diimine complex is known to be effective as a copolymerization catalyst of ethylene and a polar vinyl monomer such as an acrylate ester (see, for example, Patent Document 3). However, these diimine-type complexes need to improve polymerization activity in order to obtain a polymer industrially, and polar vinyl monomer copolymerization requires a large amount of expensive boron promoter and boron additive, which is economical. It was not a preferable method.

  Moreover, it was shown that an azaferrocenylimine chelate type nickel complex is effective for ethylene polymerization (for example, refer patent document 4). However, the activity was not high with respect to copolymerization of polar monomers such as acrylic acid esters.

WO96 / 23010 Publication

Special Table 2000-515195 WO01 / 92342 JP 2002-255918 A

  An object of the present invention is to efficiently produce a polyolefin using a transition metal compound having an azaferrocene or phosphaferrocene structure or a transition metal compound having a diimine structure, an activation promoter, and an alkylaluminum halide as constituent components. It is to provide a use as a possible catalyst for olefin polymerization and a method for producing polyolefin using the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have conducted olefin polymerization of a transition metal compound having an azaferrocene or phosphaferrocene structure or a transition metal compound having a diimine structure, an activation promoter, and an alkylaluminum halide. It has been found that a polyolefin can be efficiently produced by using it as a constituent of a catalyst for use in production, and the present invention has been completed.

  The present invention is described in detail below.

  The transition metal compound which is a constituent component of the olefin polymerization catalyst of the present invention is represented by the following general formula (1). That is,

（ここで、Ｍ^１はＮｉ、Ｐｄ又はＳｍであり、Ｘ^１は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基を有するアミノ基、又は炭素数１〜２０の炭化水素基を有するスルホネート基を示す。Ａは窒素原子又はリン原子を示す。Ｒ^１は水素原子、炭素数１〜２０の炭化水素基、ハロゲン原子，ケイ素原子，窒素原子，酸素原子若しくは硫黄原子を含む炭素数１〜２０の炭化水素基、フェロセニル基、又は置換フェロセニル基を示し、Ｒ^２は水素原子、炭素数１〜２０の炭化水素基、ハロゲン原子を含む炭素数１〜２０の炭化水素基、フェロセニル基、又は置換フェロセニル基を示し、Ｒ^１とＲ^２が環を形成することもできる。Ｒ^３は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基を有するシリル基、又は窒素原子，酸素原子，ハロゲン原子若しくは硫黄原子を含む炭素数１〜２０の炭化水素基を示し、ｍが２以上の時、Ｒ^３は互いに同じでも異なっていてもよく、また隣接するＲ^３同士が結合して環を形成することもできる。Ｒ^４は水素原子、炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基を有するシリル基、又は窒素原子，リン原子，酸素原子，ハロゲン原子若しくは硫黄原子を含む炭素数１〜２０の炭化水素基を示し、ｎが２以上の時、Ｒ^４は互いに同じでも異なっていてもよく、また隣接するＲ^４同士が結合して環を形成することもできる。Ｒ^３とＲ^４は結合を有することもできる。ｍは１〜３の整数を示し、ｎは１〜５の整数を示す。Ｌ^１は配位結合性化合物であり、ハロゲン含有炭化水素、π電子、カルボニル酸素、エーテル、ニトリル、アミン、ホスフィンを示し、Ｘとの結合を有することもできる。ｑは１〜３の整数を示し、ｒは０〜３の整数を示す。）
で表される。

(Here, M ¹ is Ni, Pd or Sm, and X ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, or carbon. A sulfonate group having a hydrocarbon group of 1 to 20. A represents a nitrogen atom or a phosphorus atom, R ¹ represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogen atom, a silicon atom, a nitrogen atom, A C1-C20 hydrocarbon group containing an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group, wherein R ² is a hydrogen atom, a C1-C20 hydrocarbon group, or a halogen atom containing 1 carbon atom. Represents a hydrocarbon group, a ferrocenyl group or a substituted ferrocenyl group of ˜20, and R ¹ and R ² can also form a ring, R ³ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon A silyl group having 20 hydrocarbon groups, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, oxygen atom, halogen atom or sulfur atom, and when m is 2 or more, R ³ is the same or different from each other R ³ may be bonded to each other to form a ring, and R ⁴ has a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. A silyl group or a hydrocarbon group having 1 to 20 carbon atoms containing a nitrogen atom, phosphorus atom, oxygen atom, halogen atom or sulfur atom, and when n is 2 or more, R ⁴ may be the same or different from each other; In addition, adjacent R ⁴ may be bonded to form a ring, R ³ and R ⁴ may have a bond, m represents an integer of 1 to 3, and n represents an integer of 1 to 5. shown .L ¹ is a coordinate bond compound, halo -Containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine, and may have a bond with X. q represents an integer of 1 to 3, and r represents an integer of 0 to 3. .)
It is represented by

In the general formula (1), M ¹ is a transition metal atom selected from Ni, Pd or Sm, preferably Ni.

In general formula (1), X ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. And is preferably a halogen atom. Specific examples of the halogen atom for X ¹ are chlorine atom, bromine atom and iodine atom, preferably chlorine atom and bromine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a benzyl group, an allyl group, a phenyl group, an o-tolyl group, and the like. Specific examples of the amino group having a hydrocarbon group include methylamino group, dimethylamino group, isopropylamino group, diisopropylamino group, phenylamino group, diphenylamino group and the like. Examples of the sulfonate group having an organic group having 1 to 20 carbon atoms are a trifluoromethanesulfonate group, a p-toluenesulfonate group, and the like. q represents an integer of 1 to 3.

  A in the general formula (1) represents a nitrogen atom or a phosphorus atom, preferably a nitrogen atom.

R ¹ in the general formula (1) is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom, ferrocenyl Or a substituted ferrocenyl group, preferably a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ¹ include methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2-methylphenyl group, 2,4- Dimethylphenyl group, 2-isopropylphenyl group, 2,4-diisopropylphenyl group, 2-tert-butylphenyl group, mesityl group, 2-biphenyl group, 2- (4-tert-butylphenyl) phenyl group, 1-naphthyl Group, an adamantyl group and the like, preferably a 2-methylphenyl group, a 2-isopropylphenyl group, a 2-biphenyl group, and a 2- (4-tert-butylphenyl) phenyl group. Specific examples of the C1-C20 hydrocarbon group containing a halogen atom, silicon atom, nitrogen atom, oxygen atom or sulfur atom are 2- (trifluoromethyl) phenyl group, 2- (trichloromethyl) phenyl group, 2 -Methyl-4-chlorophenyl group, 2- (trimethylsilyl) phenyl group, 2,4-di (trimethylsilyl) phenyl group, 2- (dimethylaminomethyl) phenyl group, 2- (diphenylaminomethyl) phenyl group, 2-methyl -4-methoxyphenyl group, 2- (methoxymethyl) phenyl group, 2- (phenoxymethyl) phenyl group, 2- (methylthiomethyl) phenyl group, 2- (phenylthiomethyl) phenyl group, 8-hydroxysulfonyl-1 -Naphthyl group, 2-pyridyl group, 2-quinolyl group, etc., preferably 2- (trifluoromethyl) ) Phenyl group, 2- (trichloromethyl) phenyl group, 2-methyl-4-chlorophenyl group, 2- (trimethylsilyl) phenyl group, 2- (diphenylaminomethyl) phenyl group, 2- (methoxymethyl) phenyl group. . Specific examples of the substituted ferrocenyl group include a ferrocenyl group having a methyl ferrocenyl group, a dimethyl ferrocenyl group, a tert-butyl ferrocenyl group, and a pentamethylcyclopentadienyl (Cp ^* ) group. .

R ² in the general formula (1) represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, a ferrocenyl group, or a substituted ferrocenyl group, preferably hydrogen An atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2-methylphenyl group, naphthyl group and the like. Preferably, they are a methyl group and a phenyl group. Specific examples of the C1-C20 hydrocarbon group containing a halogen atom include a trifluoromethyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a difluoromethyl group, and the like, preferably trifluoro It is a methyl group. Specific examples of the substituted ferrocenyl group include a methyl ferrocenyl group, a dimethyl ferrocenyl group, and a tert-butyl ferrocenyl group.

R ¹ and R ² in the general formula (1) can be bonded to form a ring, and specific examples of the ring containing nitrogen include a pyridyl group and a quinolyl group.

R ³ in the general formula (1) is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom, an oxygen atom, a halogen atom or A C1-C20 hydrocarbon group containing a sulfur atom is shown, Preferably they are a hydrogen atom, a C1-C20 hydrocarbon group, and a C1-C20 hydrocarbon group containing an oxygen atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms are a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2-methylphenyl group, and the like. Specific examples of the silyl group having a hydrogen group include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group. Specific examples of the C1-C20 hydrocarbon group containing a nitrogen atom, an oxygen atom, a halogen atom or a sulfur atom include a chloromethyl group, a methoxymethyl group, a 4-methoxyphenyl group, a dimethylaminomethyl group, a formyl group, A methylthiomethyl group, a phenylthiomethyl group, and the like; m is an integer of 1 to 3, and when m is 2 or more, they may be the same or different from each other, and adjacent R ³ may be bonded to form a ring.

R ⁴ in the general formula (1) is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom, a phosphorus atom, an oxygen atom, a halogen atom or A hydrocarbon group having 1 to 20 carbon atoms containing a sulfur atom, preferably a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms containing a nitrogen atom, an oxygen atom or a halogen atom. . Specific examples of the hydrocarbon group having 1 to 20 carbon atoms of R ⁴ include a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2-methylphenyl group, and a 3,5-dimethylphenyl group. Specific examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms such as 4-tert-butylphenyl group include trimethylsilyl group, tert-butyldimethylsilyl group, and triphenylsilyl group. it can. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms including nitrogen atom, phosphorus atom, oxygen atom, halogen atom or sulfur atom include 3- (dimethylaminomethyl) phenyl group, dimethylaminomethyl group, diphenylaminomethyl group , Phenylmethylaminomethyl group, 3- (diphenylphosphino) phenyl group, 3- (dicyclohexylphosphino) phenyl group, di (tert-butylphosphino) methyl group, 4-methoxyphenyl group, 3- (methoxymethyl) Phenyl group, methoxymethyl group, 1- (methoxymethyl) ethyl group, 2- (methoxy) ethyl group, phenoxymethyl group, (2-methylphenoxy) methyl group, 4-fluorophenyl group, 2,3,4,5 , 6-pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,2 2-trifluoroethyl group, 2- (methylthio) phenyl group, can be preferably exemplified a phenylthiomethyl group and the like. n is an integer of 1 to 5, when n is 2 or more, each may be the same or different from each other, can also be bonded is adjacent R ⁴ together form a ring.

L ¹ in the general formula (1) is a halogen-containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine coordination compound, specifically, dichloromethane, dichloroethane, dichlorobenzene, pentafluoro. Benzene, ethylene, propylene, styrene, acetone, acetophenone, benzophenone, dimethyl ether, diethyl ether, dibutyl ether, acetonitrile, benzonitrile, trimethylamine, triethylamine, N, N-dimethylaniline, N-methyldiphenylamine, triphenylphosphine, tricyclohexylphosphine Etc. r shows the integer of 0-3.

X ¹ and L ¹ in the general formula (1) can have a bond, and specific examples in that case include π-allyl group, 1-methyl-π-allyl group, 2-methyl-π- An allyl group, 1-phenyl-π-allyl group, 2-methoxycarbonyl-π-allyl group, η ³ -benzyl group and the like can be mentioned. The transition metal compound having an azaferrocene or phosphaferrocene ligand represented by the general formula (1) has surface asymmetry, but can also be either a racemate or an optically active substance.

  The synthesis of the transition metal compound represented by the general formula (1) of the present invention can be performed using, for example, a method described in JP-A-2002-255918.

  The transition metal compound which is a constituent component of the olefin polymerization catalyst of the present invention is also represented by the following general formula (2). That is,

（ここで、Ｍ^２はＮｉ、Ｐｄ又はＳｍであり、Ｘ^２は水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０の炭化水素基を有するアミノ基、又は炭素数１〜２０の炭化水素基を有するスルホネート基を示す。Ｒ^５及びＲ^６は同一でも異なっていてもよく、水素原子、炭素数１〜２０の炭化水素基、又はハロゲン原子，ケイ素原子，窒素原子，酸素原子若しくは硫黄原子を含む炭素数１〜２０の炭化水素基を示し、Ｒ^７及びＲ^８は同一でも異なっていてもよく、水素原子、炭素数１〜２０の炭化水素基、又はハロゲン原子を含む炭素数１〜２０の炭化水素基を示し、Ｒ^７とＲ^８が環を形成することもできる。Ｒ^５とＲ^７若しくはＲ^６とＲ^８は結合し、環を形成することができる。Ｌ^２は配位結合性化合物であり、ハロゲン含有炭化水素、π電子、カルボニル酸素、エーテル、ニトリル、アミン、ホスフィンを示し、Ｘとの結合を有することもできる。ｓは１〜３の整数を示し、ｔは０〜３の整数を示す。）
一般式（２）中、Ｍ^２はＮｉ、Ｐｄ又はＳｍより選ばれる遷移金属原子であり、好ましくはＮｉである。

(Here, M ² is Ni, Pd or Sm, and X ² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, or carbon. A sulfonate group having a hydrocarbon group of 1 to 20. R ⁵ and R ⁶ may be the same or different and are a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogen atom, a silicon atom, or nitrogen; C 1-20 hydrocarbon group containing an atom, oxygen atom or sulfur atom, R ⁷ and R ⁸ may be the same or different, hydrogen atom, C 1-20 hydrocarbon group, or halogen A hydrocarbon group having 1 to 20 carbon atoms including an atom, and R ⁷ and R ⁸ can also form a ring, and R ⁵ and R ⁷ or R ⁶ and R ⁸ can be bonded to form a ring. L ² is a coordination bond compound, and C Rogen-containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine, and may have a bond with X. s represents an integer of 1 to 3, and t represents an integer of 0 to 3. .)
In the general formula (2), M ² is a transition metal atom selected from Ni, Pd or Sm, preferably Ni.

In the general formula (2), ^{X 2} is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a hydrocarbon group having 1 to 20 carbon atoms having a hydrocarbon group having 1 to 20 carbon atoms And is preferably a halogen atom. Specific examples of the halogen atom for X ² are chlorine atom, bromine atom and iodine atom, preferably chlorine atom and bromine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a benzyl group, an allyl group, a phenyl group, an o-tolyl group, and the like. Specific examples of the amino group having a hydrocarbon group include methylamino group, dimethylamino group, isopropylamino group, diisopropylamino group, phenylamino group, diphenylamino group and the like. Examples of the sulfonate group having an organic group having 1 to 20 carbon atoms are a trifluoromethanesulfonate group, a p-toluenesulfonate group, and the like. s shows the integer of 1-3.

R ⁵ and R ⁶ in the general formula (2) may be the same or different, and represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom. A hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a silicon atom, a nitrogen atom, an oxygen atom or a sulfur atom; It is. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, tert-butyl group, phenyl group, 2-methylphenyl group, 2,6-dimethylphenyl group, and 2-isopropylphenyl group. 2,6-diisopropylphenyl group, 2-tert-butylphenyl group, mesityl group, 2-biphenyl group, 2,6-bis (4-tert-butylphenyl) phenyl group, etc., preferably 2,6- A dimethylphenyl group, a 2,6-diisopropylphenyl group, and a 2,6-bis (4-tert-butylphenyl) phenyl group. Specific examples of the C1-C20 hydrocarbon group containing a halogen atom, silicon atom, nitrogen atom, oxygen atom or sulfur atom are 2- (trifluoromethyl) phenyl group, 2- (trichloromethyl) phenyl group, 2 , 6-bis (trifluoromethyl) phenyl group, 2-methyl-6-chlorophenyl group, 2- (trimethylsilyl) phenyl group, 2,6-di (trimethylsilyl) phenyl group, 2- (dimethylaminomethyl) phenyl group, 2- (diphenylaminomethyl) phenyl group, 2- (methoxymethyl) phenyl group, 2,6-dimethyl-4-methoxyphenyl group, 2- (phenoxymethyl) phenyl group, 2- (methylthiomethyl) phenyl group, 2 -(Phenylthiomethyl) phenyl group, etc., preferably 2,6-bis (trifluoromethyl) phenyl group 2- (trichloromethyl) phenyl group, 2-methyl-6-chlorophenyl group, a 2- (trimethylsilyl) phenyl group.

R ⁷ and R ⁸ in the general formula (2) may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom. , Preferably they are a hydrogen atom and a C1-C20 hydrocarbon group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, benzyl group, phenyl group, 2-methylphenyl group, naphthyl group and the like. Preferably, they are a methyl group and a phenyl group. Specific examples of the C1-C20 hydrocarbon group containing a halogen atom include a trifluoromethyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a difluoromethyl group, and the like, preferably trifluoro It is a methyl group. R ⁷ and R ⁸ can also form a ring, and specific examples include an acenaphthene ring and a cyclohexane ring. R ⁵ and R ⁷ or R ⁶ and R ⁸ can be bonded to form a ring. A specific example is a pyridine ring.

L ² in the general formula (2) is a halogen-containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine coordination bond compound, specifically dichloromethane, dichloroethane, pentafluorobenzene, ethylene Propylene, styrene, acetone, acetophenone, benzophenone, dimethyl ether, diethyl ether, acetonitrile, benzonitrile, trimethylamine, triethylamine, N, N-dimethylaniline, N-methyldiphenylamine, triphenylphosphine, tricyclohexylphosphine, and the like. t shows the integer of 0-3.

X ² and L ² in the general formula (2) can have a bond, and specific examples in that case include π-allyl group, 1-methyl-π-allyl group, 2-methyl-π- An allyl group, 1-phenyl-π-allyl group, 2-methoxycarbonyl-π-allyl group, η ³ -benzyl group and the like can be mentioned.

  The synthesis of the transition metal compound represented by the general formula (2) of the present invention can be performed using, for example, a method described in WO96 / 23010.

  The activation cocatalyst (B), which is one of the components of the olefin polymerization catalyst in the present invention, acts or reacts with the reaction product of the transition metal compound (A) and the alkylaluminum halide (C). This indicates a compound having a role of forming a polymerization active species capable of polymerizing an olefin. The activation co-catalyst (B) is a compound that provides a compound that, after forming a polymerization active species, coordinates weakly or interacts with the generated polymerization active species but does not react directly with the active species. Examples of the activation co-catalyst include, but are not limited to, an ionized ionic compound having a non-coordinating anion and a modified clay compound.

When the activation promoter (B) is an ionized ionic compound having a non-coordinating anion, when the general formula (1) is used as the transition metal compound (A), the structure is represented by the following general formula (3). Protonic acid represented, ionized ionic compound represented by general formula (4), carbocationic compound represented by general formula (5), Lewis acid represented by general formula (6), AgSbF ₆ , NaPF ₆ or it is preferable that the compound having the structure of any of NaBF _4. On the other hand, when the general formula (2) is used as the transition metal compound (A), the structure thereof is a protonic acid represented by the following general formula (3), an ionized ionic compound represented by the general formula (4), AgSbF _6. , A compound having a structure of NaPF ₆ or NaBF ₄ is desirable.

[HL ³ ] [B (Ar) ₄ ] (3)
[EL ⁴ _u ] [B (Ar) ₄ ] (4)
[D] [B (Ar) ₄ ] (5)
B (Ar) ₃ (6)
(Here, H is a proton, B is a boron atom or an aluminum atom. L ³ is a Lewis base, L ⁴ is a Lewis base or a cyclopentadienyl group. E is lithium, sodium, iron, or silver. And C is a carbonium cation or a tropylium cation, Ar is an aryl group having 6 to 20 carbon atoms, or a halogen-substituted aryl group having 6 to 20 carbon atoms, u is 0 to 0. (It is an integer of 2.)
Specific examples of the protonic acid represented by the general formula (3) include diethyloxonium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate, diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium. Tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) borate, hydroniumtetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Anilinium tetrakis (nonafluoro-2-biphenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentaph Orophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis ( Examples thereof include, but are not limited to, pentafluorophenyl) aluminate and tri-n-butylammonium tetrakis (pentafluorophenyl) aluminate.

  Specific examples of the ionized ionic compound represented by the general formula (4) include sodium tetrakis {3,5-bis (trifluoromethyl) phenyl} borate, lithium tetrakis (pentafluorophenyl) borate, lithium tetrakis (nonafluoro). -2-biphenyl) borate, lithium salts such as lithium tetrakis (pentafluorophenyl) aluminate, or ether complexes thereof, ferricinium tetrakis (pentafluorophenyl) borate, ferricinium tetrakis (pentafluorophenyl) aluminate, etc. Silver salts such as ferricinium salt, silver tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) aluminate can be exemplified, but are not limited thereto.

  Specific examples of the carbocationic compound represented by the general formula (5) include trityltetrakis (pentafluorophenyl) borate, trityltetrakis (nonafluoro-2-biphenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, Tropylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) aluminate, tris {3,5-di (trimethylsilyl) phenyl} methyl tetrakis (pentafluorophenyl) borate, tris {3,5-di (Triethylsilyl) phenyl} methyl tetrakis (pentafluorophenyl) borate and the like can be mentioned, but are not limited thereto.

  Specific examples of the Lewis acid represented by the general formula (6) include tris {3,5-bis (trifluoromethyl) phenyl} borane, tris (pentafluorophenyl) borane, tris (2,3,5). , 6-tetrafluorophenyl) borane, tris (2,3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tris ( (3,4,5-trifluorophenyl) aluminum and the like can be mentioned, but are not limited thereto.

  When the activation promoter (B), which is a constituent component of the olefin polymerization catalyst of the present invention, is a modified clay compound, the clay compound used preferably has a cation exchange ability. In addition, the clay compound used in the present invention is preferably subjected to chemical treatment such as treatment with an acid or alkali, salt treatment, and formation of a complex by treatment with an organic compound or an inorganic compound.

  Clay compounds include kaolin minerals such as kaolinite, dickite, and halloysite that exist in nature, smectites such as montmorillonite, hectorite, beidellite, saponite, teniolite, and soconite, mica such as muscovite, paragonite, and illite, and vermiculite. , Brittle mica such as margarite and clintnite, curb group such as donbasite, kukeite and clinochlore, sepiolite and palygorskite, and artificially synthesized clay compounds can be mentioned, but not limited thereto.

  Examples of the acid used for the chemical treatment include Bronsted acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid, and sodium hydroxide, potassium hydroxide, and calcium hydroxide are preferably used as the alkali. Compounds used in the salt treatment include ionic halides such as sodium chloride, potassium chloride, lithium chloride, magnesium chloride, aluminum chloride, iron chloride, and ammonium chloride; sulfates such as sodium sulfate, potassium sulfate, aluminum sulfate, and ammonium sulfate. Carbonates such as potassium carbonate, sodium carbonate and calcium carbonate; inorganic salts such as sodium phosphate, potassium phosphate, aluminum phosphate and ammonium phosphate; and sodium acetate, potassium acetate, potassium oxalate, citric acid; Examples thereof include organic acid salts such as sodium acid and sodium tartrate.

  Examples of organic compounds used to form organic complexes of clay compounds include onium salts, compounds that generate carbon cations such as trityl chloride and tropylium bromide, and complex compounds that generate metal complex cations such as ferrocenium salts. Is done. Examples of the inorganic compound used for forming the inorganic composite include metal hydroxides that generate hydroxide cations such as aluminum hydroxide, zirconium hydroxide, and chromium hydroxide.

  Among the modified clay compounds used in the present invention, particularly preferred is a modified clay compound which is a clay compound-organic ion complex obtained by exchanging a metal ion which is an exchangeable cation present in the clay compound with a specific organic cation component. is there. Specific examples of organic cations introduced into the modified clay compound include aliphatic ammonium cations such as butylammonium, hexylammonium, decylammonium, dodecylammonium, diamylammonium, tributylammonium, N, N-dimethyldecylammonium, and anilinium. N-methylanilinium, N, N-dimethylanilinium, N-ethylanilinium, N, N-diethylanilinium, benzylammonium, toluidinium, dibenzylammonium, tribenzylammonium, N, N, 2,4 Examples include ammonium ions such as aromatic ammonium cations such as 6-pentamethylanilinium, and oxonium ions such as dimethyloxonium and diethyloxonium. Not intended to be.

  In the olefin polymerization catalyst of the present invention, an alkylaluminum halide (C) is used together with the transition metal compound (A) and the activation promoter (B). The alkylaluminum halide (C) is preferably a compound that has a role of inactivating the component that becomes a catalyst poison present in the polymerization system and at the same time can form an alkyl body of a transition metal compound. Include diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diisobutylaluminum chloride, dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum fluoride, ethyl (methoxy) aluminum chloride, or 1,3-dichloro-1,3 -Halogenated alkylaluminoxanes such as diethylaluminoxane and 1,3-dichloro-1,3-diisopropylaluminoxane; Ride is preferred. The alkylaluminum halide (C) of the present invention can be used without any trouble even if it is prepared by simply mixing trialkylaluminum and aluminum trichloride at an arbitrary ratio.

  Although there is no restriction | limiting in the ratio of (A) component in this invention, (B) component, and (C) component, (B) component is a compound represented by General formula (3), (4) or (5). In this case, the molar ratio of the component (A) to the component (C) per metal atom is in the range of (component A) :( component C) = 1: 10 to 1: 10000, particularly 1:30 to 1: 1000. The molar ratio of the component (A) to the component (B) is preferably (component A) :( component B) = 0.5: 1 to 1: 200, particularly 1: 1 to 1:20. It is preferable to be in the range. When the component (B) is a modified clay compound, the molar ratio of the component (A) to the component (C) per metal atom is in the range of (component A) :( component C) = 1: 10 to 1: 10000. In particular, the ratio is preferably in the range of 1:50 to 1: 1000, and the weight ratio of the component (A) to the component (B) is (component A) :( component B) = 1: 1 to 1: 10000, In particular, the range of 1:10 to 1: 1000 is preferable.

  The olefins used for polymerization in the present invention are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene and other α-olefins, styrene and styrene derivatives, butadiene, 1,4 -Conjugated and nonconjugated dienes such as hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, cyclobutene, cyclopentene, cyclohexene, norbornene, Cyclic olefins such as 1,3-cyclohexadiene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid Α, β-unsaturated carboxylic acids such as, and their sodium salts, potassium , Metal salts such as lithium salt, zinc salt, magnesium salt, calcium salt, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, acrylic Α, β-unsaturated carboxylic acid esters such as acid (2-phenoxyethyl), methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, vinyl acetate, Vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, itaconate Unsaturated glycidyl esters such as glycidyl, vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, phenyl vinyl ketone, α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile, 1-phenylacrylonitrile, vinyl silane, allyl silane, allyl trichlorosilane, Silane compounds such as 7-octenyltrichlorosilane, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and vinyl acetate, ethylene and methyl acrylate, ethylene and 2 types like methyl methacrylate, ethylene and 7-octenyltrichlorosilane, ethylene and propylene and styrene, ethylene and 1-hexene and styrene, ethylene, propylene and ethylidene norbornene It is also possible to polymerize by mixing the above ingredients.

  The polymerization of the olefin in the present invention can be carried out either in the gas phase or in the liquid phase, and when it is carried out in the liquid phase, any solvent can be used as long as it is a commonly used organic solvent. Specifically, benzene, toluene, Examples include xylene, diisopropylbenzene, pentane, hexane, heptane, 2,2,2-trifluoroethanol, hexafluoroisopropyl alcohol, etc., and olefins such as propylene, 1-butene, 1-octene and 1-hexene as solvents. Can also be used.

  There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, monomer concentration, etc. when producing polyolefin using the method of the present invention, but the polymerization temperature is -10 to 300 ° C., and the polymerization time is 10 seconds. The polymerization pressure is preferably in the range of normal pressure to 300 MPa for -100 hours. It is also possible to adjust the molecular weight using hydrogen during polymerization. Polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The polyolefin obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  The catalyst for olefin polymerization comprising a transition metal compound having an azaferrocene or phosphaferrocene structure and a diimine structure, an activation co-catalyst, and an alkylaluminum halide according to the present invention can efficiently produce a polyolefin. is there. In particular, in the copolymerization of ethylene with a polar monomer such as an acrylic ester, a highly active copolymer can be produced under economical reaction conditions.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.

  For the synthesis of the transition metal compound represented by the general formula (1), the method described in JP-A-2002-255918 is used, and for the synthesis of the transition metal compound represented by the general formula (2), WO96 / 23010 is disclosed. The method described in 1 was used. The polymerization reaction was performed using a mechanical stirrer, a pressure gauge, and a 2 L SUS autoclave having a tube for press-fitting and introducing a catalyst component, or a 150 mL SUS autoclave with a pressure gauge containing a magnetic rotor. The solvent used for the polymerization was a solvent that had been deoxygenated and dehydrated by a known method. As the ethylene gas, a polymerization grade was used as it was.

  The GPC measurement of the polymer obtained by polymerization was performed under the following conditions.

Column; TSK gel GMHhr-H (20) HT × 3
Flow rate; 1.0 mL / min Concentration; 1.0 mg / mL
Column temperature: 140 ° C
Eluent: 1,2,4-trichlorobenzene Example 1
[Preparation of complex solution]
A 100 mL Schlenk flask was purged with nitrogen, and Complex 1a (4.9 μmol) and toluene (50 mL) shown in the following figure were added and stirred.

［エチレン重合］
２ＬのＳＵＳ製オートクレーブに、トルエン（５００ｍＬ）及びエチルアルミニウムセスキクロライド（東ソー・ファインケム（株）製、０．７５Ｍ、３．３ｍＬ、アルミニウム原子換算で４．９ｍｍｏｌ）を加えた。攪拌下、１ＭＰａのエチレンを充填した後、上記で得られた錯体溶液を室温で窒素圧入した。さらにジメチルアニリニウム・［テトラキス（ペンタフルオロフェニル）］ボレート（２８．７ｍｇ、３５．８μｍｏｌ）とトルエン（５０ｍＬ）からなる溶液を室温で窒素圧入し、５０℃に加熱した。１ＭＰａの圧力になるようにエチレンを連続的に供給しながら１時間重合を行った。イソプロピルアルコール／エタノールの混合物（商品名：エキネン）を圧入して反応をクエンチし、脱圧した。イソプロピルアルコール／エタノールをさらに投入し、ポリマーを析出させた。ろ過し、ポリマーをイソプロピルアルコール／エタノールで洗浄した。減圧乾燥し、固体の重合物２４．４ｇを得た。重合活性は５．０Ｋｇ／Ｎｉ・ｍｍｏｌ・ｈである。ＤＳＣによる融点は５０．２℃（ΔＨ＝２８．２ｊ／ｇ）であり、ＧＰＣ測定の結果、Ｍｗ＝９．８×１０^４、分子量分布（Ｍｗ／Ｍｎ）は３．８であった。

[Ethylene polymerization]
To a 2 L SUS autoclave, toluene (500 mL) and ethylaluminum sesquichloride (manufactured by Tosoh Finechem Co., Ltd., 0.75 M, 3.3 mL, 4.9 mmol in terms of aluminum atom) were added. After stirring, 1 MPa of ethylene was charged under stirring, and the complex solution obtained above was injected with nitrogen at room temperature. Further, a solution consisting of dimethylanilinium [tetrakis (pentafluorophenyl)] borate (28.7 mg, 35.8 μmol) and toluene (50 mL) was injected with nitrogen at room temperature and heated to 50 ° C. Polymerization was carried out for 1 hour while ethylene was continuously supplied to a pressure of 1 MPa. A mixture of isopropyl alcohol / ethanol (trade name: Echinen) was injected to quench the reaction, and the pressure was released. Further isopropyl alcohol / ethanol was added to precipitate the polymer. Filter and wash the polymer with isopropyl alcohol / ethanol. The solid was dried under reduced pressure to obtain 24.4 g of a solid polymer. The polymerization activity is 5.0 kg / Ni · mmol · h. The melting point by DSC was 50.2 ° C. (ΔH = 28.2 j / g), and as a result of GPC measurement, Mw = 9.8 × 10 ⁴ and molecular weight distribution (Mw / Mn) were 3.8.

Examples 2-4
The same operation as in Example 1 was repeated except that the reaction conditions shown in Table 1 were used. The results are shown in Table 1.

比較例１〜３
表２に示したアルキル化剤及び反応条件を用いた以外は実施例１と同じ操作を繰り返した。重合活性は低下した。結果を表２に示した。

Comparative Examples 1-3
The same operation as in Example 1 was repeated except that the alkylating agent and reaction conditions shown in Table 2 were used. Polymerization activity decreased. The results are shown in Table 2.

実施例５、６
下図の錯体（１ｂ）を用いた以外は実施例１と同様の操作を繰り返した。結果を表３に示した。

Examples 5 and 6
The same operation as in Example 1 was repeated except that the complex (1b) shown below was used. The results are shown in Table 3.

実施例７
下図の錯体（１ｃ）を用いた以外は実施例１と同様の操作を繰り返した。結果を表４に示した。

Example 7
The same operation as in Example 1 was repeated except that the complex (1c) shown below was used. The results are shown in Table 4.

実施例８〜１０
下図の錯体（１ｄ）あるいは（１ｅ）を用い、表５に示した反応条件を用いた以外は実施例１と同様の操作を繰り返した。結果を表５に示した。

Examples 8-10
Using the complex (1d) or (1e) shown below, the same operation as in Example 1 was repeated except that the reaction conditions shown in Table 5 were used. The results are shown in Table 5.

実施例１１
［錯体溶液の調製］
５０ｍＬのシュレンクフラスコを窒素置換し、下図で示される錯体１ｆ（６．５μｍｏｌ）及びトルエン（１５ｍＬ）を加え混合した。

Example 11
[Preparation of complex solution]
The 50 mL Schlenk flask was purged with nitrogen, and the complex 1f (6.5 μmol) and toluene (15 mL) shown in the figure below were added and mixed.

[Ethylene / acrylic acid (2-phenoxyethyl) copolymerization]
The complex solution obtained above was introduced into a 150 mL SUS autoclave using a cannula. After pressurizing with 0.1 MPa ethylene once, the pressure was released, and ethylaluminum sesquichloride (manufactured by Tosoh Finechem Co., Ltd., 0.75M, 0.44 mL, 0.66 mmol in terms of aluminum atoms) was added using a syringe. Further, a solution consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate (29.3 mg, 36.6 μmol) and toluene (15 mL) was added using a cannula. Acrylic acid (2-phenoxyethyl) (0.5 mL, 2.9 mmol) was added using a syringe and immediately pressurized with 4 MPa of ethylene to give vibration. The autoclave was removed from the ethylene line and immersed in an oil bath heated to 80 ° C. with stirring (internal pressure increased to 5.2 MPa). Polymerization was carried out at 80 ° C. for 20 hours under stirring. A decrease in internal pressure was observed over time. The obtained reaction liquid was poured into a mixture of isopropyl alcohol / ethanol (trade name: Echinen) with stirring. The obtained insoluble matter was filtered, and the solid was dried to obtain 7.30 g of a white solid. The melting points by DSC are 39.8 ° C. and 78.3 ° C. (ΔH = 48.7 j / g). As a result of GPC measurement, Mw = 2.7 × 10 ⁴ and molecular weight distribution (Mw / Mn) is 3.8. Met. The content of acrylic acid (2-phenoxyethyl) in the copolymer was 1.00% by weight from ¹ H-NMR (C ₂ D ₂ Cl ₄ , 120 ° C.). Identification of the formation of the copolymer by ¹ H-NMR was carried out according to WO 01/92342.

実施例１２〜１６
表６に示した錯体及び反応条件を用いた以外は実施例１１と同じ操作を繰り返した。結果を表６に示した。

Examples 12-16
The same operation as in Example 11 was repeated except that the complexes and reaction conditions shown in Table 6 were used. The results are shown in Table 6.

比較例４
表７に示したアルキル化剤及び反応条件を用いた以外は実施例１１と同じ操作を繰り返した。共重合活性は顕著に低下した。結果を表７に示した。

Comparative Example 4
The same operation as in Example 11 was repeated except that the alkylating agent and reaction conditions shown in Table 7 were used. The copolymerization activity was significantly reduced. The results are shown in Table 7.

実施例１７
［錯体溶液の調製］
１００ｍＬのシュレンクフラスコを窒素置換し、下図で示される錯体２ａ（４．６μｍｏｌ）及びトルエン（５０ｍＬ）を加え攪拌した。

Example 17
[Preparation of complex solution]
The 100 mL Schlenk flask was purged with nitrogen, and complex 2a (4.6 μmol) and toluene (50 mL) shown in the figure below were added and stirred.

［エチレン重合］
２ＬのＳＵＳ製オートクレーブに、トルエン（５００ｍＬ）及びエチルアルミニウムセスキクロライド（東ソー・ファインケム（株）製、０．７５Ｍ、０．６２ｍＬ、アルミニウム原子換算で０．９３ｍｍｏｌ）を加えた。攪拌下、１ＭＰａのエチレンを充填した後、上記で得られた錯体溶液を室温で窒素圧入した。さらにジメチルアニリニウム・［テトラキス（ペンタフルオロフェニル）］ボレート（１７．５ｍｇ、２１．８μｍｏｌ）とトルエン（５０ｍＬ）からなる溶液を室温で窒素圧入し、５０℃に加熱した。１ＭＰａの圧力になるようにエチレンを連続的に供給しながら１時間重合を行った。イソプロピルアルコール／エタノールの混合物（商品名：エキネン）を圧入して反応をクエンチし、脱圧した。イソプロピルアルコール／エタノールをさらに投入後ろ過し、ポリマーをイソプロピルアルコール／エタノールで洗浄した。減圧乾燥し、固体の重合物６４．２ｇを得た。重合活性は１４．０Ｋｇ／Ｎｉ・ｍｍｏｌ・ｈである。ＤＳＣによる融点は３３．０℃、１０５．０℃（ΔＨ＝１８．７ｊ／ｇ）であり、ＧＰＣ測定の結果、Ｍｗ＝２０×１０^４、分子量分布（Ｍｗ／Ｍｎ）は２．４であった。

[Ethylene polymerization]
To a 2 L SUS autoclave, toluene (500 mL) and ethylaluminum sesquichloride (manufactured by Tosoh Finechem Co., Ltd., 0.75 M, 0.62 mL, 0.93 mmol in terms of aluminum atom) were added. After stirring, 1 MPa of ethylene was charged under stirring, and the complex solution obtained above was injected with nitrogen at room temperature. Further, a solution consisting of dimethylanilinium [tetrakis (pentafluorophenyl)] borate (17.5 mg, 21.8 μmol) and toluene (50 mL) was injected with nitrogen at room temperature and heated to 50 ° C. Polymerization was carried out for 1 hour while ethylene was continuously supplied to a pressure of 1 MPa. A mixture of isopropyl alcohol / ethanol (trade name: Echinen) was injected to quench the reaction, and the pressure was released. Further isopropyl alcohol / ethanol was added, followed by filtration, and the polymer was washed with isopropyl alcohol / ethanol. The solid was dried under reduced pressure to obtain 64.2 g of a solid polymer. The polymerization activity is 14.0 Kg / Ni · mmol · h. The melting point by DSC was 33.0 ° C. and 105.0 ° C. (ΔH = 18.7 j / g), and as a result of GPC measurement, Mw = 20 × 10 ⁴ and molecular weight distribution (Mw / Mn) were 2.4. It was.

Examples 18-21
The same operation as in Example 17 was repeated except that the reaction conditions shown in Table 8 were used. The results are shown in Table 8.

比較例５
表９に示したアルキル化剤及び反応条件を用いた以外は実施例１７と同じ操作を繰り返した。重合活性は低下した。結果を表９に示した。

Comparative Example 5
The same operation as in Example 17 was repeated except that the alkylating agent and reaction conditions shown in Table 9 were used. Polymerization activity decreased. The results are shown in Table 9.

実施例２２
［錯体溶液の調製］
５０ｍＬのシュレンクフラスコを窒素置換し、錯体２ａ（６．７μｍｏｌ）及びトルエン（１５ｍＬ）を加え混合した。

Example 22
[Preparation of complex solution]
The 50 mL Schlenk flask was purged with nitrogen, and complex 2a (6.7 μmol) and toluene (15 mL) were added and mixed.

[Ethylene / acrylic acid (2-phenoxyethyl) copolymerization]
The complex solution obtained above was introduced into a 150 mL SUS autoclave using a cannula. After pressurizing with 0.1 MPa ethylene once, the pressure was released, and ethylaluminum sesquichloride (manufactured by Tosoh Finechem Co., Ltd., 0.75M, 0.45 mL, 0.67 mmol in terms of aluminum atom) was added using a syringe. Further, a solution consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate (27.2 mg, 34.0 μmol) and toluene (15 mL) was added using a cannula. Acrylic acid (2-phenoxyethyl) (0.5 mL, 2.9 mmol) was added using a syringe and immediately pressurized with 4 MPa of ethylene to give vibration. The autoclave was removed from the ethylene line and immersed in an oil bath heated to 80 ° C. with stirring (internal pressure increased to 4.9 MPa). Polymerization was carried out at 80 ° C. for 20 hours under stirring. A decrease in internal pressure was observed over time. The obtained reaction liquid was poured into a mixture of isopropyl alcohol / ethanol (trade name: Echinen) with stirring. The obtained insoluble matter was filtered, and the solid was dried to obtain 8.52 g of a white solid. The melting points by DSC are 63.1 ° C. and 89.1 ° C. (ΔH = 31.5 j / g). As a result of GPC measurement, Mw = 4.3 × 10 ⁴ and molecular weight distribution (Mw / Mn) is 2.6. Met. The content of acrylic acid (2-phenoxyethyl) in the copolymer was 1.00% by weight from ¹ H-NMR (C ₂ D ₂ Cl ₄ , 120 ° C.). Identification of the formation of the copolymer by ¹ H-NMR was carried out according to WO 01/92342.

Example 23
The same operation as in Example 22 was repeated except that the reaction conditions shown in Table 10 were used. The results are shown in Table 10.

比較例６、７
表１１に示したアルキル化剤及び反応条件を用いた以外は実施例２２と同じ操作を繰り返した。共重合活性は顕著に低下した。結果を表１１に示した。

Comparative Examples 6 and 7
The same operation as in Example 22 was repeated except that the alkylating agent and reaction conditions shown in Table 11 were used. The copolymerization activity was significantly reduced. The results are shown in Table 11.

Claims (3)

Activation promoter selected from transition metal compounds represented by the following general formula (1), compounds represented by the following general formulas (3) to (6), AgSbF ₆ , NaPF ₆ , NaBF ₄ or modified clay compounds, and halogen Olefin polymerization catalyst comprising alkylaluminum fluoride as a constituent.

(Here, M ¹ is Ni, Pd or Sm, and X ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, or carbon. A sulfonate group having a hydrocarbon group of 1 to 20. A represents a nitrogen atom or a phosphorus atom, R ¹ represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogen atom, a silicon atom, a nitrogen atom, A C1-C20 hydrocarbon group containing an oxygen atom or a sulfur atom, a ferrocenyl group, or a substituted ferrocenyl group, wherein R ² is a hydrogen atom, a C1-C20 hydrocarbon group, or a halogen atom containing 1 carbon atom. Represents a hydrocarbon group, a ferrocenyl group or a substituted ferrocenyl group of ˜20, and R ¹ and R ² can also form a ring, R ³ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon A silyl group having 20 hydrocarbon groups, or a hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom, oxygen atom, halogen atom or sulfur atom, and when m is 2 or more, R ³ is the same or different from each other R ³ may be bonded to each other to form a ring, and R ⁴ has a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. A silyl group or a hydrocarbon group having 1 to 20 carbon atoms containing a nitrogen atom, phosphorus atom, oxygen atom, halogen atom or sulfur atom, and when n is 2 or more, R ⁴ may be the same or different from each other; In addition, adjacent R ⁴ may be bonded to form a ring, R ³ and R ⁴ may have a bond, m represents an integer of 1 to 3, and n represents an integer of 1 to 5. shown .L ¹ is a coordinate bond compound, halo -Containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine, and may have a bond with X. q represents an integer of 1 to 3, and r represents an integer of 0 to 3. .)
[HL ³ ] [B (Ar) ₄ ] (3)
[EL ⁴ _u ] [B (Ar) ₄ ] (4)
[D] [B (Ar) ₄ ] (5)
B (Ar) ₃ (6)
(Here, H is a proton, B is a boron atom or an aluminum atom. L ³ is a Lewis base, L ⁴ is a Lewis base or a cyclopentadienyl group. E is lithium, sodium, iron, or silver. And C is a carbonium cation or tropylium cation, Ar is an aryl group having 6 to 20 carbon atoms or a halogen-substituted aryl group having 6 to 20 carbon atoms, u is 0 to 0. (It is an integer of 2.) Activation promoter selected from transition metal compounds represented by the following general formula (2), compounds represented by the following general formulas (3) to (4), AgSbF ₆ , NaPF ₆ , NaBF ₄ or modified clay compounds, and halogen Olefin polymerization catalyst comprising alkylaluminum fluoride as a constituent.

(Here, M ² is Ni, Pd or Sm, and X ² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an amino group having a hydrocarbon group having 1 to 20 carbon atoms, or carbon. A sulfonate group having a hydrocarbon group of 1 to 20. R ⁵ and R ⁶ may be the same or different and are a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogen atom, a silicon atom, or nitrogen; C 1-20 hydrocarbon group containing an atom, oxygen atom or sulfur atom, R ⁷ and R ⁸ may be the same or different, hydrogen atom, C 1-20 hydrocarbon group, or halogen R ⁷ and R ⁸ can also form a ring, and R ⁵ and R ⁷ or R ⁶ and R ⁸ can be bonded to form a ring. L ² is a coordination bond compound, and C Rogen-containing hydrocarbon, π electron, carbonyl oxygen, ether, nitrile, amine, phosphine, and may have a bond with X. s represents an integer of 1 to 3, and t represents an integer of 0 to 3. .)
[HL ³ ] [B (Ar) ₄ ] (3)
[EL ⁴ _u ] [B (Ar) ₄ ] (4)
(Here, H is a proton, B is a boron atom or an aluminum atom. L ³ is a Lewis base, L ⁴ is a Lewis base or a cyclopentadienyl group. E is lithium, sodium, iron, or silver. (Ar is an aryl group having 6 to 20 carbon atoms or a halogen-substituted aryl group having 6 to 20 carbon atoms. U is an integer of 0 to 2.) A method for producing a polyolefin, wherein olefin polymerization is carried out using the olefin polymerization catalyst according to claim 1.