JP2011137120A - NOVEL TRIARYL PHOSPHINE OR TRIARYL ARSINE COMPOUND, alpha-OLEFIN POLYMERIZATION CATALYST USING THE SAME, AND METHOD OF MANUFACTURING alpha-OLEFIN-(METH)ACRYLIC ACID COPOLYMER BY THE POLYMERIZATION CATALYST - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst component capable of manufacturing an α-olefin-(meth)acrylic acid copolymer excellent in mechanical and thermal physical properties, and applicable as a useful molding, without depending on a high-pressure radical method, and a method of manufacturing the copolymer using the same. <P>SOLUTION: This α-olefin polymerization catalyst is obtained by reacting a ligand selected from the group comprising triaryl phosphines or triaryl arsines, with a transition metal compounds of the eighth to tenth groups. The α-olefin-(meth)acrylic acid copolymer is manufactured using the polymerization catalyst. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel triarylphosphine or triarylarsine compound, an α-olefin polymerization catalyst using the compound, and a method for producing an α-olefin / (meth) acrylic acid copolymer using the polymerization catalyst. , Novel triarylphosphine or triarylarsine compounds having a substituent of hypophosphorous acid structure, α-olefin polymerization catalyst using them, and excellent mechanical and thermal properties by the polymerization catalyst, useful The present invention relates to a method for producing an α-olefin / (meth) acrylic acid copolymer that can be applied as a compact.

Conventionally, a copolymer of ethylene and a polar group-containing vinyl monomer such as vinyl acetate, (meth) acrylic acid or an ester has been produced by using a high-pressure radical method. It was difficult to obtain, and catalyst deactivation could not be avoided when using a Ziegler catalyst or a metallocene catalyst.
Recently, polar group-containing comonomer copolymerization by late transition metal complex catalysts has been energetically studied, and many of these have chelate ligands (Non-patent Document 1).

  Among these chelate ligand groups, many compounds having a phosphine ligand on one side of the chelate ligand have been reported, and on the other side of the chelate ligand, a phosphine ligand (Patent Document) 1), amine ligand (patent document 1), imine ligand (patent document 2), amide ligand (patent document 3), pyridine ligand (patent document 4), phenolate ligand (non-patent) Document 1), carboxylate ligand (Non-patent Document 2), sulfonate ligand (Non-patent Document 3, Patent Documents 5 to 10), phosphorate ligand (Patent Documents 5 to 10), alcoholate ligand ( A compound having Patent Document 11) has been reported. Of these, the group having a sulfonate ligand has attracted attention because it can copolymerize an olefin and a polar comonomer, and there have been many reports in recent years.

In contrast, a chelate compound having a phosphine ligand and a phosphinate ligand (hereinafter referred to as “phosphine phosphinate”) in the chelate ligand group is an example in which this is used as a polymerization catalyst. Has not been reported. There are very few synthesis report examples of phosphine phosphinate, and there are only synthesis report examples by Rieger (Non-patent Document 4).
In the examples of the synthesis of phosphine phosphinates so far, the aromatic ring on the trivalent phosphine is a phenyl group, that is, all hydrogen atoms, and is effective in improving the activity as a polymerization catalyst. There have been no reports on the synthesis of phosphine phosphinates having substituents in

JP-A-9-255713 WO9840420 Publication WO9830610 Publication WO9946271 Publication JP 2007-63280 A JP 2007-77395 A JP 2007-117991 A JP 2008-214628 A JP 2007-214629 A JP 2007-214630 A DE 3445090

M.M. Brookhart et al., Chem. Rev. 2000, 1169-1204. W. Keim, Stud. Surf. Sci. Catal. 1986, 25, 201. E. Drent et al. , Chem. Commun. 2002, 744. B. Rieger et al. Dalton Trans. , 2007, 272.

  In light of the background of the background art described above, the present invention is an α-olefin / (meth) acrylic acid type that is excellent in mechanical and thermal properties and can be applied as a useful molded body without using the high-pressure radical method. It is an object of the present invention to develop a catalyst component that can realize the production of a copolymer and a method for producing the copolymer that uses the catalyst component.

As a result of various searches for ligand compounds in the late transition metal complex catalyst with the aim of solving the above-described problems of the present invention, the present inventors have found that the phosphinate site in the triarylphosphine or triarylarsine compound. It has been found that the novel triarylphosphine or triarylarsine compound possessed functions as a component of the above-mentioned target polymerization catalyst, and the present invention has been realized.
That is, the compound forming the polymerization catalyst according to the present application is a phosphine (or arsine) phosphinate having a substituent at the ortho position of the aryl group on the trivalent phosphine, which is novel as a compound and applied as a catalyst Is also new.

  The triarylphosphine and triarylarsine compound having the specific structure are novel compounds constituting the first invention of the present invention, that is, a novel triarylphosphine represented by the following general formula (1) or Triarylarsine compounds. (The “present invention” means an invention group comprising the invention units of the following first to sixth inventions.)

(In General Formula (1), Y is phosphorus or arsenic, and Z is —P (R ¹⁵ ) (O) (OH).
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown. )

As the second invention of the present invention, an α-olefin polymerization catalyst obtained by reacting the compound of the first invention with a group 8-10 transition metal is disclosed.
As a third invention of the present invention, a metal complex represented by the following general formula (2) is disclosed.

(In general formula (2), Y is phosphorus or arsenic, Z ^{is, -P (R 15) (O} ) is O-.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown.

M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 carbon atom substituted with a halogen atom. Hydrocarbon group having 1 to 30 carbon atoms, hydrocarbon group having 1 to 30 carbon atoms substituted with alkoxy group, hydrocarbon group having 1 to 30 carbon atoms substituted with aryloxy group, alkoxy group having 1 to 30 carbon atoms, or carbon The substituent selected from the group which consists of a number 1-30 aryloxy group is shown.
B represents any ligand coordinated to M. A and B may be bonded to each other to form a ring. )

As the fourth invention of the present invention, an α-olefin polymerization catalyst containing the metal complex of the third invention is disclosed.
As a fifth invention of the present invention, an α-olefin polymerization catalyst in which the polymerization catalyst of the second or fourth invention further comprises a fine particle carrier is disclosed.
As a sixth invention of the present invention, an α-olefin and (meth) acrylic acid or ester are copolymerized in the presence of the α-olefin polymerization catalyst according to any of the second, fourth and fifth inventions. A method for producing an α-olefin / (meth) acrylic acid copolymer is disclosed.

In the present invention, an α-olefin / (meth) acrylic acid-based copolymer is produced by copolymerizing an α-olefin with (meth) acrylic acid or an ester in the presence of the polymerization catalyst according to the present invention. It became possible.
This olefin copolymer is excellent in mechanical and thermal properties and can be applied as a useful molded product. Specifically, the copolymer is a paint, printability, antistatic property, inorganic filler. Applicable to various uses such as film, sheet, adhesive resin, binder, compatibilizer, etc. by utilizing good properties in dispersibility, adhesion with other resins, compatibilizing ability with other resins, etc. It is.

The present invention relates to novel triarylphosphine and triarylarsine compounds having specific structures, catalysts in which these novel compounds are coordinated to specific metal elements, and α-olefin / (meth) acrylic acid systems using them. This relates to the production of a copolymer.
In the following, these novel compounds, polymerization catalysts, polymer components (monomer components), polymerization methods, and the like will be described in detail.

1. Triarylphosphine and triarylarsine compound In the polymerization catalyst of the present invention, a novel triarylphosphine or triarylarsine compound serving as a ligand for a specific metal element is represented by the following general formula (1).

(In General Formula (1), Y is phosphorus or arsenic, and Z is —P (R ¹⁵ ) (O) (OH).
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown. )

R ^{1 to} R ⁴ are ortho positions as viewed from the group 15 atom (phosphorus or arsenic), and are expected to be located in the axial direction of the central metal when complexed. This steric effect is considered to have influenced the improvement of the catalyst performance.
Therefore, it is necessary that at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted for other than a hydrogen atom. Preferably, at least one of R ¹ and R ² is other than a hydrogen atom, and at least one of R ³ and R ⁴ is other than a hydrogen atom. More preferably, ^one of R ¹ and R ² is a hydrogen atom, the other is other than a hydrogen atom, and one of R ³ and R ⁴ is a hydrogen atom and the other is other than a hydrogen atom.

The hydrocarbon group having 1 to 30 carbon atoms that is preferable as R ^{1 to} R ⁴ is more preferably a hydrocarbon group having 1 to 13 carbon atoms. Preferred specific examples are methyl group, ethyl group, 1-propyl group, 1 -Butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl- 2-phenylethyl, isopropyl, 1-dimethylpropyl, 1,1,2-trimethylpropyl, 1,1-diethylpropyl, 1-phenyl-2-propyl, isobutyl, 1,1-dimethyl Butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, 2-ethylhexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-propyl Tyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group , 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group , Phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, and p-ethylphenyl group.
Among these, more preferred substituents are isopropyl, isobutyl, and cyclohexyl, and particularly preferred is isopropyl.

The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom as R ^{1 to} R ⁴ is preferably a substituent in which the above hydrocarbon group having 1 to 30 carbon atoms is substituted with fluorine, chlorine, or bromine. There are specific preferred examples such as a trifluoromethyl group or a pentafluorophenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group as R ^{1 to} R ⁴ is preferably a methoxy group, an ethoxy group, an isopropoxy group, 1- A substituent substituted with a propoxy group, a 1-butoxy group, or a t-butoxy group. More preferably, it is a C1-C6 hydrocarbon group substituted by a methoxy group or an ethoxy group, and specifically includes 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- ( Phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, 1- (dimethylaminomethyl) ethyl group, 1- (diethylaminomethyl) ethyl group, di (methoxymethyl) methyl group , Di (ethoxymethyl) methyl group, and di (phenoxymethyl) methyl group. Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (ethoxymethyl) ethyl group.

The hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group as R ^{1 to} R ⁴ is preferably a phenoxy group, a 4-methylphenoxy group, a 4-methoxy group. It is a substituent substituted with a phenoxy group, a 2,6-dimethylphenoxy group, or a 2,6-di-t-butylphenoxy group. More preferred is a C1-C6 hydrocarbon group substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferred is a 1- (phenoxymethyl) ethyl group or 1- (2,6- Dimethylphenoxy group methyl) ethyl group.

The alkoxy group having 1 to 30 carbon atoms as R ^{1 to} R ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms. Preferred specific examples are methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1 -Butoxy group, t-butoxy group and the like. Among these, a more preferred substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and particularly preferably a methoxy group.

The aryloxy group having 6 to 30 carbon atoms as R ^{1 to} R ⁴ is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples thereof include a phenoxy group, a 4-methylphenoxy group, and a 4-methoxyphenoxy group. 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

Among these preferable groups as R ^{1 to} R ⁴ , an isopropyl group, an isobutyl group, and a cyclohexyl group are particularly preferable, and an isopropyl group is most preferable.

R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.

  Since these substituents are substituents at a site relatively distant from the central metal at the time of complex formation, any substituent that does not adversely affect the complex formation of the phosphine phosphinate ligand may be used. Compared to the steric effects of these substituents, the electronic effect is considered to affect the catalyst performance, and electron donating substituents are preferred. These substituents may be the same or different.

Preferred halogen atoms as R ^{5 to} R ¹⁴ include fluorine, chlorine, bromine and the like.

Preferred examples of the hydrocarbon group having 1 to 30 carbon atoms as R ^{5 to} R ¹⁴ include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group.
Here, examples of the alkyl group and the cycloalkyl group include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1 -Nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2- Ethylhexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cycl Pentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo [ 2.2.2] octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, and 5-decyl group.
Among these, preferred substituents are a methyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, a cinnamyl group, and a styryl group, and a cyclohexenyl group is preferable.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group. Examples of the substituent that can be present in the aromatic ring of these aryl groups include an alkyl group, an aryl group, a fused aryl group, and a phenylcyclohexyl group. Group, phenylbutenyl group, tolyl group, xylyl group, p-ethylphenyl group, pentafluorophenyl group. Among these, preferred substituents are a phenyl group and a pentafluorophenyl group.

The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom as R ^{5 to} R ¹⁴ is preferably a substitution in which the aforementioned hydrocarbon group having 1 to 30 carbon atoms is substituted with a halogen atom such as fluorine, chlorine or bromine. It is a group.
The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group as R ^{5 to} R ¹⁴ is preferably a methoxy group, an ethoxy group, an isopropoxy group, or 1-propoxy group. Or a substituent substituted with a 1-butoxy group or a t-butoxy group. More preferably, it is a C1-C6 hydrocarbon group substituted by a methoxy group or an ethoxy group, and specifically includes 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- ( Phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, 1- (dimethylaminomethyl) ethyl group, 1- (diethylaminomethyl) ethyl group, di (methoxymethyl) methyl group , Di (ethoxymethyl) methyl group, and di (phenoxymethyl) methyl group. Particularly preferred are 1- (methoxymethyl) ethyl group and 1- (ethoxymethyl) ethyl group.

The alkoxy group having 1 to 30 carbon atoms as R ^{5 to} R ¹⁴ is preferably an alkoxy group having 1 to 6 carbon atoms. Preferred specific examples are methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1 -Butoxy group, t-butoxy group and the like. Among these, a more preferred substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and particularly preferred is a methoxy group.

The aryloxy group having 6 to 30 carbon atoms as R ^{5 to} R ¹⁴ is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples thereof are phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group. 2,6-dimethylphenoxy group and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.

  The silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms is preferably a silyl group having 3 to 18 carbon atoms. Preferred specific examples include trimethylsilyl group, dimethylphenylsilyl group, diphenylmethylphenylsilyl group, Phenylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tripropylsilyl group, dimethylisopropylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, tributylsilyl group, trihexylsilyl group, cyclohexyldimethylsilyl group, tri A benzylsilyl group is mentioned. Particularly preferred are a trimethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylphenylsilyl group, and a triphenylsilyl group.

Among these preferred groups as R ^{5 to} R ¹⁴ , more preferred are a hydrogen atom, a methyl group, and an isopropyl group, and particularly preferred is a hydrogen atom.

R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown.

The hydrocarbon group having 1 to 30 carbon atoms as R ¹⁵ is preferably a hydrocarbon group having 1 to 13 carbon atoms. Preferred specific examples are methyl group, ethyl group, 1-propyl group, 1-butyl group, 1 -Pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group , Isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group, 1,1-dimethylbutyl group, 2- Pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-propylheptyl group, 2-octyl group Tyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group , Exo-norbornyl group, endo-norbornyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group, allyl group, phenyl Group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, p-ethylphenyl group and the like.
Among these, more preferred substituents are a methyl group, an ethyl group, an allyl group, and a phenyl group, and particularly preferred is a phenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group as R ¹⁵ is preferably a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, or the above-described hydrocarbon group having 1 to 30 carbon atoms, Examples thereof include a substituent substituted with a 1-butoxy group, a t-butoxy group, and the like. Particularly preferred are 4-methoxyphenyl group and 2,6-dimethoxyphenyl group.

The hydrocarbon group having 7 to 30 carbon atoms, which is substituted with an aryloxy group as R ¹⁵ , is preferably a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, the above-described hydrocarbon group having 1 to 30 carbon atoms, Examples thereof include a substituent substituted with a 2,6-dimethylphenoxy group or a 2,6-di-t-butylphenoxy group. More preferred is a C1-C6 hydrocarbon group substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferred is a 1- (phenoxymethyl) ethyl group or 1- (2,6- Dimethylphenoxy group methyl) ethyl group.

The alkoxy group having 1 to 30 carbon atoms as R ¹⁵ is preferably an alkoxy group having 1 to 6 carbon atoms, and preferred specific examples are methoxy group, ethoxy group, isopropoxy group, 1-propoxy group, 1-butoxy group. , T-butoxy group, and phenoxy group. Among these, a more preferable substituent is a methoxy group, an ethoxy group, or a phenoxy group, and a phenoxy group is particularly preferable.

The aryloxy group having 6 to 30 carbon atoms as R ¹⁵ is preferably an aryloxy group having 6 to 12 carbon atoms. Preferred specific examples include phenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 2, Examples include 6-dimethylphenoxy group and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a phenoxy group is particularly preferable.
Among these preferred groups as R ¹⁵ , more preferred are a methyl group, an ethyl group, an allyl group, a phenyl group, and a phenoxy group, and particularly preferred is a phenyl group.

2. Synthesis of Polymerization Catalyst The polymerization catalyst of the present invention comprises a novel triarylphosphine or triarylarsine compound represented by the general formula (1) and a group 8 to 10 (long period type; Fe, Co, Ni, Pd, etc.) An α-olefin polymerization catalyst obtained by reacting with a transition metal compound.
The synthesis of the catalyst composition is generally carried out by contacting a group 8-10 transition metal compound and a ligand in a solution or slurry.

  The transition metal compound is preferably a Group 10 transition metal compound, and is bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, palladium sulfate, palladium acetate, bis (allyl palladium chloride), palladium chloride, bromide. Palladium, (cyclooctadiene) palladium (methyl) chloride, dimethyl (tetramethylethylenediamine) palladium, bis (cyclooctadiene) nickel, nickel chloride, nickel bromide, (tetramethylethylenediamine) nickel (methyl) chloride, dimethyl (tetra It is synthesized using (methylethylenediamine) nickel, (cyclooctadiene) nickel (methyl) chloride, or the like.

The complexing reaction may be performed in a reactor used for copolymerization with an α-olefin, or may be performed in a container separate from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation. Furthermore, it can be carried out in the presence of a porous carrier described later.
Moreover, the catalyst composition of this invention may be used individually by 1 type, and may use multiple types of catalyst composition together. Particularly, for the purpose of widening the molecular weight distribution and the comonomer content distribution, the combined use of such a plurality of catalyst compositions is useful.

  The metal complex formed by reacting the triarylphosphine or triarylarsine compound represented by the general formula (1) with the group 8-10 transition metal compound is represented by the following general formula (2). It's okay.

(In general formula (2), Y is phosphorus or arsenic, Z ^{is, -P (R 15) (O} ) is O-.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown.

M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 carbon atom substituted with a halogen atom. A hydrocarbon group having -30 hydrocarbons, a hydrocarbon group having 2-30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7-30 carbon atoms substituted with an aryloxy group, an alkoxy group having 1-30 carbon atoms, or carbon The substituent selected from the group which consists of several 6-30 aryloxy groups is shown.
B represents any ligand coordinated to M. A and B may be bonded to each other to form a ring. )

Here, Y, Z, and R ^{1 to} R ¹⁵ are the same as the substituents in the triarylphosphine or triarylarsine compound represented by the general formula (1).
M represents a transition metal belonging to Groups 8 to 10, but Fe, Co, Ni, Pd, Pt and lanthanide are preferable, and Ni and Pd are more preferable.

The alkyl group as A is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a trifluoromethyl group, an acyl group, and an acetoxy group.
The aryl group as A is preferably an aryl group having 6 to 13 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a phenacyl group, and a pentafluorophenyl group. Particularly preferred substituents include a hydrogen atom, a methyl group and a phenyl group.

B is any ligand coordinated to M. Such a ligand is a hydrocarbon compound having 1 to 20 carbon atoms having oxygen, nitrogen, phosphorus, and sulfur as atoms capable of coordination bonding.
Specific ligands include phosphines, pyridine derivatives, piperidine derivatives, alkyl ether derivatives, aryl ether derivatives, alkyl aryl ether derivatives, ketones, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, Aliphatic esters, aromatic esters, amines and the like can be mentioned. Preferred are ketones, cyclic ethers, phosphines, and pyridine derivatives, and particularly preferred are acetone, tetrahydrofuran, pyridine, lutidine, and tripyridine. Phenylphosphine.

3. Fine particle carrier As the fine particle carrier used in the present invention, any fine particle carrier can be used as long as the gist of the present invention is not impaired.
In general, inorganic oxides and polymer carriers can be preferably used. Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture thereof, and SiO ₂ —Al ₂ O _3. , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O ₃ and other mixed oxides can also be used, and inorganic silicates, polyethylene, polypropylene, polystyrene, Carriers such as polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polyester, polyamide, and polyimide can also be used.
Among these carriers, a carrier made of an inorganic oxide is preferably used. Also preferably, an ion-exchange layered silicate is used, and still more preferably a smectite group.

As the ion-exchange layered silicate, clay, clay mineral, zeolite, diatomaceous earth, or the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, sericite and sea chlorite and other mica minerals, attapulgite, sepiolite, pigolite, bentonite, wood Examples include knot clay, gyrome clay, hysingelite, pyrophyllite, and ryokdee stones. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

  Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Examples include smectites, such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Smectite such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, Adult saponite, synthetic taeniolite.

These fine particle carriers may be used as they are, but acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti Salt treatment such as (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ may be performed. In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system, and the treatment may be performed, or shape control such as pulverization and granulation and drying treatment may be performed.
There are no particular restrictions on the particle size of these fine particle carriers, and any particle can be used, but the average particle size is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm.

  The fine particle carrier can be used after being treated with an organoaluminum compound. The organoaluminum compound used here has a substituent selected from an alkyl group having 1 to 20 carbon atoms, a halogen, hydrogen, an alkoxy group, or an amino group. Among these substituents, a C1-C20 alkyl group, hydrogen, and a C1-C20 alkoxy group are preferable, More preferably, it is a C1-C20 alkyl group. A plurality of substituents may be the same or different, and the organoaluminum compound may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride are preferable. More preferably, it is a trialkylaluminum having 1 to 8 carbon atoms.

4). Use Mode of Polymerization Catalyst The triarylphosphine or triarylarsine compound, the group 8-10 transition metal compound, and the particulate carrier can be contacted in any order. When contacting, each component may be brought into contact with a solid, or may be brought into contact with a solvent slurry or a uniform solution. The contact order of each component is, for example, as follows.
(1) A method in which a triarylphosphine or a triarylarsine compound and a Group 8-10 transition metal compound are brought into contact with each other, and then a fine particle carrier is brought into contact therewith.
(2) A method of contacting a group 8-10 transition metal compound after contacting a triarylphosphine or triarylarsine compound with a fine particle carrier.
(3) A method in which a triarylphosphine or a triarylarsine compound is contacted after contacting a Group 8-10 transition metal compound and a fine particle carrier.
Among these contact methods, (1) is preferable. Further, after bringing the fine particle carrier into contact with another catalyst component, it can be washed with a solvent that is not reactive with the catalyst component. As the solvent, hydrocarbon solvents and halogenated hydrocarbons are preferable.

The triarylphosphine or triarylarsine compound is usually used in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol, with respect to 1 g of the fine particle carrier.
The temperature at which each component is brought into contact may be any temperature as long as it is not higher than the boiling point of the solvent, but is preferably from room temperature to not higher than the boiling point of the solvent.
The contacted catalyst component can be used for polymerization evaluation as it is, but can also be dried and stored in a solid state. Furthermore, prepolymerization described below can also be performed.

The contacted catalyst component may be prepolymerized in the presence of an olefin in the polymerization tank or outside the polymerization tank. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Preferred are olefins having 2 or 3 carbon atoms.
The olefin can be supplied by any method such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

5. Monomers used Examples of the monomer used for the production of the copolymer include (a) α-olefin, (b) (meth) acrylic acid or ester, and (c) other olefins described below. Each monomer component may be used alone or in combination.

(A) α-Olefin One of the monomers used in the present invention is an α-olefin represented by the general formula CH ₂ ═CHR ¹⁶ (hereinafter sometimes referred to as “component (a)”). Here, R ¹⁶ is hydrogen or an alkyl group having 1 to 20 carbon atoms. Of these, preferred component (a) include α- olefins having ^{R 16} having 1 to 10 carbon atoms. More preferable component (a) includes ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, and 4-methyl-1-pentene. Particularly preferred component (a) is ethylene.

(B) (Meth) acrylic acid or ester Another one of the monomers used in the present invention is (meth) acrylic acid represented by the general formula CH ₂ ═C (R ¹⁷ ) CO ₂ (R ¹⁸ ), Alternatively, it is a (meth) acrylic acid ester (hereinafter sometimes referred to as “component (b)”). Here, R ¹⁷ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may have a branch, a ring, and / or an unsaturated bond. R ¹⁸ is hydrogen or an alkyl group having 1 to 30 carbon atoms. Further, it may contain a hetero atom at any position within R ¹⁸ .

Preferable (b) component includes (meth) acrylic acid ester having 1 to 5 carbon atoms R ¹⁷ and (meth) acrylic acid. More preferable component (b) includes methacrylic acid ester in which R ¹⁷ is a methyl group, acrylic acid ester in which R ¹⁷ is hydrogen, and (meth) acrylic acid.
As more preferable component (b), methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate , Cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, acrylic acid Etc. A particularly preferred component (b) is methyl acrylate.

(C) Other Olefin Another one of the monomers that may be used in the present invention is another olefin (hereinafter referred to as “component (c)”).
Preferred examples of the component (c) include cyclic olefin monomers such as cyclopentene, cyclohexene, norbornene, and ethylidene norbornene, and styrene monomers such as p-methylstyrene. These skeletons include a hydroxyl group, an alkoxide group, and a carboxylic acid group. , May contain an ester group or an aldehyde group.

Norbornene-based olefins can be made by the Diels-Alder reaction ([4 + 2] cycloaddition) using cyclopentadiene. The dienophile used is, for example, diethyl azodicarboxylate, aldehyde, maleic anhydride, dihydrofuran, vinyl pyridine, alkyl acrylate or the above substituted olefins (TL Gilchrist, “Heterocyclic Chemistry”, 1985, 4. See chapter 3.3). These monomers can be represented by formulas (5a) to (5f). Here, R ¹⁹ is a hydrocarbon group having 1 to 30 carbon atoms, branched, may have a ring, or an unsaturated bond.

  Furthermore, the monomer specified in the component (a) may be a monomer having a hydroxyl group, an alkoxide group, a carboxylic acid group, an ester group, an aldehyde group, or the like. In addition, a diene derivative, maleic anhydride, vinyl acetate or the like is used. Is possible.

6). Copolymerization Reaction The copolymerization reaction in the present invention may be carried out by using a hydrocarbon solvent such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, a liquid such as a liquefied α-olefin, In the presence or absence of polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formylamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. Is called. Moreover, you may use the mixture of the liquid compound described here as a solvent. In addition, in order to obtain high polymerization activity and high molecular weight, the above-mentioned hydrocarbon solvent is more preferable.

In the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor or an additive having an action of stabilizing the produced copolymer is preferable. Examples of preferable additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction product of trimethylaluminum and BHT, reaction product of alkoxide of tetravalent titanium and BHT, etc. Can be used.
Further, as an additive, inorganic and / or organic fillers may be used and polymerization may be performed in the presence of these fillers.

In the present invention, the polymerization mode is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization using the liquefied monomer itself as a medium, gas phase polymerization carried out in the vaporized monomer, or polymer produced in a monomer liquefied at high temperature and high pressure High-pressure ionic polymerization in which at least a part of the polymer is dissolved is preferably used. Further, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used.
Unreacted monomers and media may be separated from the produced copolymer and recycled. In recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used to separate the produced copolymer from the unreacted monomer and medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.
There are no particular restrictions on the copolymerization temperature, copolymerization pressure, and copolymerization time, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0.00. It can be selected from the range of 1 minute to 10 hours, preferably 0.5 minutes to 7 hours, more preferably 1 minute to 6 hours.
In the present invention, the copolymerization is generally performed in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

There are no particular restrictions on the supply of catalyst and monomer to the copolymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to take a technique in which a predetermined amount of monomer is supplied to a copolymerization reactor in advance and a catalyst is supplied thereto. In this case, an additional monomer or an additional catalyst may be supplied to the copolymerization reactor. In the case of continuous polymerization, a method in which a predetermined amount of monomer and catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously can be employed.
Regarding the control of the copolymer composition, a method of controlling a copolymer by supplying a plurality of monomers to a reactor and changing the supply ratio thereof can be generally used. Other methods include controlling the copolymer composition using the difference in monomer reactivity ratio due to the difference in catalyst structure, and controlling the copolymer composition using the polymerization temperature dependence of the monomer reactivity ratio. .

A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method for controlling the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and a control of the ligand structure in the transition metal complex. For example, controlling the molecular weight.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl, etc. can be used. In addition, when the component (b) or (c) itself becomes a kind of chain transfer agent, the molecular weight can be adjusted by controlling the concentration of the component (b) or (c) and the ratio to the component (a). Is possible.
When the molecular weight is adjusted by controlling the ligand structure in the transition metal complex, bulky substituents are arranged around the metal M, or electron donation such as aryl groups and heteroatom-containing substituents is provided on the metal M. Generally, the tendency to improve the molecular weight can be utilized by arranging the sex groups so that they can interact with each other or introducing heteroatoms into the aforementioned R ^{18 to} R ¹⁹ .

  In the following, the present invention will be specifically described by way of examples to demonstrate the rationality and significance of the configuration of the present invention and the superiority over the prior art. The ligand structure used in the examples is shown in Chemical formula 6.

1. Evaluation method (1) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
(Measurement conditions) Model used: 150C manufactured by Waters Inc. Detector: MIRAN1A / IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Measurement temperature: 140 ° C. Solvent: Orthodichlorobenzene (ODCB) Column: AD806M manufactured by Showa Denko KK / S (3) Flow rate: 1.0 mL / min Injection volume: 0.2 mL
(Preparation of sample) A sample was prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)) at 140 ° C. It took about 1 hour to dissolve.
(Calculation of molecular weight) The standard polystyrene method was used, and the conversion from the retention capacity to the molecular weight was performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are brands manufactured by Tosoh Corporation, and are F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000.
A calibration curve was prepared by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each would be 0.5 mg / mL. The calibration curve used was a cubic equation obtained by approximation by the least square method. The following numerical values were used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

(2) Melting point (Tm)
Using a DSC6200 differential scanning calorimeter manufactured by Seiko Instruments Inc., the sheet-like sample piece was packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./min, and held for 5 minutes. Thereafter, the temperature was lowered to 20 ° C. at 10 ° C./min for crystallization, and then the temperature was raised to 200 ° C. at 10 ° C./min to obtain a melting curve.
The peak top temperature of the main endothermic peak in the final temperature increase step performed to obtain the melting curve was defined as the melting point Tm, and the peak area of the peak was defined as ΔHm.

(3) Comonomer content The comonomer content was determined by infrared absorption spectrum using a Shimadzu FTIR-8300 model prepared by producing a press plate of about 0.5 mm.
Comonomer content, and harmonic absorption of the carbonyl group in the vicinity of 3450 cm ^-1, was calculated based on the infrared absorption intensity ratio of olefin absorption around 4250cm ^-1. In the calculation, a calibration curve prepared by ¹³ C / NMR measurement was used.

2. Ligand synthesis The ligands obtained in the following synthesis examples were used. Unless otherwise specified in the following synthesis examples, the operation was performed in a purified nitrogen atmosphere, and the solvent used was dehydrated and deoxygenated.
Synthesis Example 1 Synthesis of Ligand (I)
To a solution of 1-iodo-2-bromo-benzene (10.0 g, 35.3 mmol) in anhydrous tetrahydrofuran (200 mL) was added a solution of isopropylmagnesium chloride in tetrahydrofuran (2.0 M, 17.6 mL, 35.3 mmol) at −30 ° C. And stirred at the same temperature for 2 hours. The reaction solution was cooled to −78 ° C., phosphorus trichloride (3.0 mL, 35.3 mmol) was added, and the mixture was stirred at −78 ° C. for 2 hours (reaction solution A).
To a solution of 1-bromo-2-isopropyl-benzene (17.6 g, 88.7 mmol) in anhydrous diethyl ether (200 mL), normal butyllithium hexane solution (2.5 M, 35.5 mL, 88.7 mmol) was added at 0 ° C. The solution was slowly added dropwise and stirred at room temperature for 2 hours. This solution was added dropwise to the previous reaction solution A at −30 ° C. and stirred overnight at room temperature. After distilling off the solvent, purification by flash silica gel column chromatography gave 1.5 g of white powder of (2-bromophenyl) [di (2-isopropylphenyl)] phosphine (yield 10%).

To a solution of (2-bromophenyl) [di (2-isopropylphenyl)] phosphine (0.5 g, 1.1 mmol) in anhydrous tetrahydrofuran (10 mL), a normal butyl lithium hexane solution (2.5 M, 0.7 mL, 1. 7 mmol) was added dropwise at −78 ° C., and the mixture was stirred at the same temperature for 1 hour. To this reaction solution, phenylphosphinic dichloride (0.3
A solution of 6 mL, 2.6 mmol) in anhydrous tetrahydrofuran (20 mL) was added at −78 ° C., and the mixture was stirred overnight at room temperature. Water was added, extracted with ethyl acetate (100 mL × 3), dried over sodium sulfate, and then the solvent was distilled off. Purification by flash silica gel column chromatography (dichloromethane / methanol = 100/1) gave 0.4 g of a white powder. By recrystallization from ethyl acetate, 0.1 g of a white target product was obtained (yield 17%).
1H NMR (CDCl3, ppm / d): 8.57 (br, 1 H), 8.12 (m, 1 H), 7.66 (dd, J = 7.2, 13.6 Hz, 2 H), 7.36 (m, 3 H), 7.3 -7.2 (m, 6 H), 6.99 (m, 3 H), 6.65 (br, 2 H), 3.09 (br, 2 H), 0.90 (d, J = 8.0 Hz, 12 H). 31P NMR (CDCl3 , ppm / d): 33.0 (d, J = 10.7 Hz), -30.9 (d, J = 11.7 Hz).

3. Polymerization 3-1. (Example 1: Ethylene polymerization)
25 μmoles of palladium bisdibenzylideneacetone and phosphine phosphinate ligands are weighed into a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) is added, and then this is treated with an ultrasonic vibrator for 10 minutes. Thus, a catalyst slurry was prepared. Next, the inside of the induction stirring stainless steel autoclave having an internal volume of 1 L was replaced with purified nitrogen, and purified toluene (700 mL) was introduced into the autoclave under a purified nitrogen atmosphere. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was kept at 80 ° C., and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 3 MPa.
After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, the obtained polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. 0.3 g, Mw: 25,000, Mw / Mn: 2.16, Tm: 132.6 ° C.

3-2. (Example 2: Copolymerization of ethylene / methacrylate)
100 μmoles of palladium bisdibenzylideneacetone and phosphine phosphinate ligands are weighed in a 30 mL flask sufficiently purged with nitrogen, and dehydrated toluene (10 mL) is added thereto, which is then treated with an ultrasonic vibrator for 10 minutes. Thus, a catalyst slurry was prepared. Next, the inside of the induction-stirring stainless steel autoclave with an internal volume of 1 L is replaced with purified nitrogen, and purified toluene (617 mL) and methyl acrylate (72 mL, adjusted so that the concentration during polymerization is 1 mol / L) are in a purified nitrogen atmosphere The autoclave was introduced below. The previously prepared catalyst solution was added, and polymerization was started at room temperature with an ethylene pressure of 3 MPa. During the reaction, the temperature was kept at 80 ° C., and ethylene was continuously supplied so that the partial pressure of ethylene was maintained at 3 MPa.
After the polymerization was completed, ethylene was purged, the autoclave was cooled to room temperature, the obtained polymer was reprecipitated using ethanol (1 L), and the precipitated polymer was filtered. Furthermore, the obtained solid polymer was dispersed in ethanol (1 L), 1N hydrochloric acid (20 ml) was added thereto, and the mixture was stirred for 60 minutes, and the polymer was filtered. The obtained solid polymer was washed with ethanol and dried under reduced pressure at 60 ° C. for 3 hours to finally recover the polymer. 1.0 g, Mw: 4,100, Mw / Mn: 1.9, Tm: 120.0 ° C.

By using the phosphine phosphinate-based polymerization catalyst of the present invention, the above-described examples are used to industrially produce a copolymer of α-olefin and (meth) acrylic acid or ester, which has been difficult to produce conventionally. It has been shown that it can be obtained.
Therefore, the rationality and significance of the configuration of the present invention and the superiority over the prior art are clearly demonstrated.

By using the polymerization catalyst according to the present invention, a copolymer of an α-olefin and (meth) acrylic acid or an ester can be obtained industrially.
The obtained copolymer is excellent in mechanical and thermal properties and can be applied as a useful molded article. Specifically, the copolymer of the present invention is utilized by utilizing good properties such as paintability, printability, antistatic properties, inorganic filler dispersibility, adhesiveness with other resins, and compatibilizing ability with other resins. Can be applied in various applications such as films, sheets, adhesive resins, binders, compatibilizers and the like.

Claims (6)

A triarylphosphine or triarylarsine compound represented by the following general formula (1).

(In General Formula (1), Y is phosphorus or arsenic, and Z is —P (R ¹⁵ ) (O) (OH).
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown. ) An α-olefin polymerization catalyst obtained by reacting the compound according to claim 1 with a group 8-10 transition metal compound. A metal complex represented by the following general formula (2).

(In general formula (2), Y is phosphorus or arsenic, Z ^{is, -P (R 15) (O} ) is O-.
R ^{1 to} R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or a carbon number 2 substituted with an alkoxy group. Substitution selected from the group consisting of hydrocarbon groups having 30 to 30 carbon atoms, hydrocarbon groups having 7 to 30 carbon atoms substituted with aryloxy groups, alkoxy groups having 1 to 30 carbon atoms, or aryloxy groups having 6 to 30 carbon atoms Indicates a group. At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is substituted other than a hydrogen atom.
R ^{5 to} R ¹⁴ are each independently substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, or an alkoxy group. Selected from the group consisting of a hydrocarbon group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a silyl group substituted with a hydrocarbon group having 1 to 30 carbon atoms Represents a substituted group.
R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group, The substituent selected from the group which consists of a 30 alkoxy group or a C6-C30 aryloxy group is shown.
M represents a metal atom selected from the group consisting of group 8-10 transition metals, and A represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or 1 carbon atom substituted with a halogen atom. A hydrocarbon group having -30 hydrocarbons, a hydrocarbon group having 2-30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7-30 carbon atoms substituted with an aryloxy group, an alkoxy group having 1-30 carbon atoms, or carbon The substituent selected from the group which consists of several 6-30 aryloxy groups is shown.
B represents any ligand coordinated to M. A and B may be bonded to each other to form a ring. ) The alpha olefin polymerization catalyst containing the metal complex of Claim 3. The α-olefin polymerization catalyst according to claim 2 or 4, further comprising a fine particle carrier. An α-olefin and (meth) acrylic acid or ester are copolymerized in the presence of the α-olefin polymerization catalyst according to claim 2, 4 or 5. A method for producing a (meth) acrylic acid copolymer.