JP2011231292A - Method for producing nonpolar-polar olefin copolymer, and nonpolar-polar olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonpolar-polar olefin copolymer exhibiting excellent properties; and to provide a method for producing the same under a mild polymerization condition and at a high efficiency.SOLUTION: The production method of a nonpolar-polar olefin copolymer includes copolymerizing a nonpolar olefin and a polar olefin in the presence of a catalyst for olefin polymerization comprising a transition metal compound (A) represented by formula (I), and at least one compound (B) selected from the group consisting of organometal compounds, organoaluminumoxy compounds, and compounds to react with the transition metal compound (A) to form an ion pair.

Description

  The present invention relates to a method for producing a copolymer of a nonpolar olefin and a polar olefin, and more particularly to a copolymer of an α-olefin and a specific polar olefin and a method for producing the copolymer.

  In general, an olefin polymer is excellent in mechanical properties and is used in various fields such as various molded product applications. However, in recent years, physical property requirements for olefin polymers have diversified, and olefin polymers having various properties are desired. As an olefin polymer satisfying such requirements, for example, a nonpolar-polar olefin copolymer obtained by copolymerizing a nonpolar olefin and a polar olefin is known. Introducing polar groups into nonpolar polyolefins is expected to improve mechanical properties such as strength and toughness, improve compatibility with other polar polymers, and improve adhesion, permeability, processability, and hydrophilicity. it can.

  As a method for producing a nonpolar-polar olefin copolymer obtained by copolymerizing a nonpolar olefin and a polar olefin, a radical polymerization method has been well known, for example, ethylene-vinyl acetate copolymer or ethylene-acrylic. Acid ertel copolymers and the like are produced by this method. When producing a nonpolar-polar olefin copolymer by radical polymerization, reaction conditions of high temperature and pressure are often required, and a method for obtaining a nonpolar-polar olefin copolymer under milder conditions is desired. It is rare. Japanese Patent Application Laid-Open No. 2004-51934 (Patent Document 1) discloses a method for polymerizing 1-hexene and methyl acrylate at a temperature close to room temperature by using a ruthenium complex. A polymer having a low content of polar monomers and showing the inherent properties of polyolefin has not been obtained.

On the other hand, as a method for obtaining a nonpolar-polar olefin copolymer under mild conditions, a method of copolymerizing a nonpolar olefin and a polar olefin by coordination polymerization using a transition metal complex catalyst in addition to radical polymerization has been reported. ing. For example, Brookhart et al. Have reported a method of obtaining a copolymer of a non-polar olefin such as ethylene and methyl acrylate under mild conditions using a diimine complex of palladium (Non-patent Documents 1 and 2). Grubbs et al. Reported copolymerization of norbornenes having a polar group and ethylene using a nickel complex (Non-patent Documents 3 and 4). In general, in olefin polymerization using these late-period metals, polymer chains are branched, and it is impossible to synthesize those having mechanical characteristics peculiar to linear polyolefins such as high strength and high crystallinity. Pugh et al. Succeeded in obtaining a linear ethylene-methyl acrylate copolymer by copolymerizing ethylene and methyl acrylate using a palladium catalyst generated in the system. The polymerization activity is extremely low (Non-patent Document 5). As an example using a pre-cycle metal, Japanese Patent Application Laid-Open No. 2003-231710 (Patent Document 2) discloses a copolymerization method of propylene and an allylamine having a silicon protecting group using a layered compound and a zirconium compound. (Patent Document 3) discloses a copolymerization method of 5-hexen-1-ol protected with propylene and an aluminum compound by a zirconium compound, both of which require a protective group for the polar monomer, and the former In this case, the polar group content of the obtained polymer is as low as about 0.68% by weight, which is not sufficient. In addition, in Japanese Patent Application Laid-Open No. 2002-155109 (Patent Document 4), the present applicant has proposed a method for producing a polar group-containing olefin copolymer obtained from a cyclic olefin and a polar olefin using a metallocene catalyst. However, since the polymerization requires an alkylaluminum compound having a polar olefin equivalent or more added, it is disadvantageous in terms of cost and a step of removing the alkylaluminum compound in the post-polymerization step is required. Further, the applicant of the present application is disclosed in
Non-polar olefin and polar olefin using transition metal compound having salicylaldoimine ligand having specific structure in Japanese Patent No. 80515 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2006-265541 (Patent Document 6) However, the polymerization activity and the amount of polar olefin incorporated are not sufficient.

  Under such circumstances, the emergence of nonpolar-polar olefin copolymers having excellent properties while exhibiting properties not found in conventional polyolefin copolymers, and production methods capable of producing them with high efficiency are emerging. It was desired.

JP 2004-051934 A JP 2003-231710 A JP 2002-201225 A JP 2002-155109 A JP 2002-080515 A JP 2006-265541 A

J. et al. Am. Chem. Soc. 1998, 120, 888 pages J. et al. Am. Chem. Soc. 1996, 118, 267 Organometallics 2004, 23, 5121 Science 2000, 287, 460 Chem. Commun. 2002, p.

  The present invention has been made in view of the prior art as described above, and provides a nonpolar-polar olefin copolymer having excellent properties and exhibiting properties not found in conventional polyolefin copolymers. The purpose is that. Another object of the present invention is to provide a method for producing these nonpolar-polar olefin copolymers under mild polymerization conditions and with high efficiency.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors can produce an excellent nonpolar-polar olefin copolymer by using a catalyst containing a transition metal compound having a specific structure. The present invention has been found, and further, an efficient production method has been found, and the present invention has been completed.

That is, the nonpolar-polar olefin copolymer according to the present invention and the production method thereof are:
A transition metal compound (A) represented by the following general formula (I):

(In the formula, M represents a transition metal atom of Group 4 or Group 5 of the periodic table, m represents an integer of ^{1 to 4} , R ^{1 to} R ⁴ may be the same or different from each other, hydrogen Indicates an atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group Two or more of these may be linked to each other to form a ring, and R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of primary or secondary carbon, carbon number 5 or more aliphatic hydrocarbon groups, aryl group-substituted alkyl groups, monocyclic or bicyclic alicyclic hydrocarbon groups and aromatic hydrocarbon groups are selected, and R ^{6 to} R ¹⁰ are the same or different from each other. May be a hydrogen atom, a halogen atom,
Hydrocarbon group, heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group,, R ⁶
One or more of ˜R ¹⁰ are silicon-containing groups, and two or more of these R ^{6 to} R ¹⁰ may be connected to each other to form a ring, and n satisfies the valence of M X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue A group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X May combine with each other to form a ring. )
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) an olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair. It is a method for producing a nonpolar-polar olefin copolymer, wherein a nonpolar olefin and a polar olefin are copolymerized in the presence.

In the transition metal compound (A) represented by the general formula (I), it is preferable that m is 2 and M is a titanium atom. Further, R ⁵ is preferably a phenyl group.

In the transition metal compound (A) represented by the general formula (I), the number of carbon atoms in the silicon-containing group contained in R ^{6 to} R ¹⁰ is preferably 4 or more.

  The nonpolar-polar olefin copolymer according to the present invention is obtained by the above-described method for producing a nonpolar-polar olefin copolymer.

According to the method for producing a nonpolar-polar olefin copolymer using a catalyst containing a transition metal compound having a specific structure in the present invention, an advantage that a polar monomer can be efficiently incorporated into the copolymer. There is. Moreover, according to the said manufacturing method, there exists an advantage that a nonpolar-polar olefin copolymer can be manufactured with high efficiency. The effect of the present invention is that, in the transition metal compound (A) represented by the general formula (I), (i) improved polymerization activity due to the three-dimensional bulkiness of the silicon-containing group, (ii) unique electrons in the silicon part This is thought to be due to the poisoning resistance and high polar comonomer uptake due to mechanical properties (high HOMO energy level, σ-π conjugate and σ ^* -π conjugate).

It is a figure which shows the relationship between the catalyst activity and the amount of polar olefin copolymerization in an Example and a comparative example.

  Hereinafter, each component of the catalyst for olefin polymerization used in the method for producing a nonpolar-polar olefin copolymer according to the present invention and a method for producing a nonpolar-polar olefin copolymer using the catalyst will be specifically described. .

The catalyst for olefin polymerization used in the method for producing the nonpolar-polar olefin copolymer according to the present invention,
(A) transition metal compound represented by the general formula (I), (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) transition metal compound ( And at least one compound selected from the group consisting of compounds that react with A) to form ion pairs.
[(A) Transition metal compound]
The transition metal compound (A) constituting the olefin polymerization catalyst used in the present invention is a compound represented by the following general formula (I).

(N... M here generally indicates coordination, but may or may not be coordinated in the present invention.)
In general formula (I), M represents a transition metal atom of Group 4 or Group 5 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably a Group 4 metal atom Specifically, titanium, zirconium, and hafnium are preferable, and titanium is more preferable.

  m represents an integer of 1 to 4, and is preferably 2.

In general formula (I), R ^{1 to} R ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably A linear or branched alkyl group having 1 to 20; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20, carbon atoms such as vinyl, allyl, isopropenyl, etc .; ethynyl, propargyl, etc. A linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., preferably 3 -20 cyclic saturated hydrocarbon group; carbon number such as cyclopentadienyl, indenyl, fluorenyl A cyclic unsaturated hydrocarbon group having ˜30; an aryl group having 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably 6-20; an aryl-substituted alkyl group such as benzyl; , Alkyl-substituted aryl groups such as isopropylphenyl, tert-butylphenyl, dimethylphenyl, and di-tert-butylphenyl.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl, etc. The halogenated hydrocarbon group of 1-30, Preferably 1-20 is mentioned.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Among these, the number of carbon atoms is 1-30, preferably 1-20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. A linear or branched alkyl group; a cyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl; Aryl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms, 1-30 carbon atoms, preferably 1-20 carbon atoms. Alkyl group or alkoxy group having 6 to 30 carbon atoms Preferably such substituted aryl group substituents, such as 6 to 20 aryl group or aryloxy group is 1-5 substituents is preferred.

  Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

  Examples of oxygen-containing groups include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, etc. Aryloxy groups; acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group; ester groups such as acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl; Is preferably exemplified.

  Examples of nitrogen-containing groups include amide groups such as acetamide, N-methylacetamide, and N-methylbenzamide; amino groups such as dimethylamino, ethylmethylamino, and diphenylamino; imide groups such as acetimide and benzimide; methylimino, ethylimino, and propylimino Preferred examples include imino groups such as butylimino and phenylimino; nitro groups.

  Sulfur-containing groups include alkylthio groups such as methylthio and ethylthio; arylthio groups such as phenylthio, methylphenylthio, and naltylthio; thioester groups such as acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl; methyl sulfonate, ethyl sulfonate, Preferred examples include sulfone ester groups such as phenyl sulfonate; sulfonamide groups such as phenyl sulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, such as methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups. , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group and the like are preferable. In particular, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group and tin-containing group include those obtained by substituting silicon of the silicon-containing group with germanium and tin.

In the general formula (I), R ^{1 to} R ⁴ are a hydrocarbon ring containing two or more groups, preferably adjacent groups connected to each other to form an alicyclic ring, an aromatic ring, or a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁴ may be linked. Further, when m is 2 or more, R ^{1 s} , R ^{2 s} , R ^{3 s} , and R ^{4 s} may be the same or different.

In general formula (I), R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of only primary or secondary carbon, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, A substituent selected from a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group is shown.

The hydrocarbon group having 1 to 4 carbon atoms composed of only primary or secondary carbon is 4 or less carbon atoms in which the carbon atom directly bonded to the phenoxy ring among the carbon atoms of R ⁵ is a primary or secondary carbon. A hydrocarbon group, specifically, a straight chain having 1 to 4, preferably 1 to 3, carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, etc. Or a branched alkyl group is mentioned.

The aliphatic hydrocarbon group having 5 or more carbon atoms is a hydrocarbon group in which the carbon atom directly bonded to the phenoxy ring among the carbon atoms of R ⁵ is not included in the ring structure, for example, 5 to 30 carbon atoms. Specifically, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and the like have 5 to 30 carbon atoms. , Preferably 5-20 linear or branched alkyl groups are mentioned.

  Specific examples of the aryl group-substituted alkyl group include benzyl, cumyl, 1-diphenylethyl, triphenylmethyl and the like.

  Examples of the monocyclic or bicyclic alicyclic hydrocarbon group include those having 3 to 30 carbon atoms. Specifically, a hydrocarbon group having a monocyclic alicyclic skeleton having 3 to 30, preferably 3 or 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl; .1.0] butyl, bicyclo [2.1.0] pentyl, norbornyl, bicyclo [2.2.2] octyl, spiro [2.2] pentyl, spiro [2.3] hexyl, etc. And a hydrocarbon group having a bicyclic alicyclic skeleton of 5-30, preferably 5-20.

  As an aromatic hydrocarbon group, a C6-C30 thing is mentioned, for example. Specific examples include phenyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranyl, phenanthryl and the like.

  A hydrocarbon group having 4 or less carbon atoms, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group consisting of only the primary or secondary carbon. An aromatic hydrocarbon group may have a hydrogen atom substituted with a halogen, such as trifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, bistrifluorophenyl, chlorophenyl And a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ⁵ is particularly preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms such as phenyl, naphthyl or anthranyl, preferably 6 to 20 or an aryl-substituted alkyl group such as benzyl, and methyl, ethyl, A linear or branched (secondary) alkyl group having 1 to 30, preferably 1 to 20, carbon atoms such as isopropyl, isobutyl, sec-butyl, neopentyl, etc., cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, etc., cyclic saturated hydrocarbons having 3 to 30, preferably 3 to 20 carbon atoms A group selected from the group is also preferred.

R ⁵ is particularly preferably an aromatic hydrocarbon group such as phenyl or naphthyl, an aryl-substituted alkyl group such as benzyl, and 3,5-difluorophenyl or 3,5-bistrifluoromethylphenyl substituted with these hydrogen atoms. Is preferable for the reason of improving the copolymerization performance because a wide coordination space can be taken. In addition, introduction of fluorine into a substituent is preferable because the cationic property of the active center is improved and the polymerization activity is improved from the electron-withdrawing property of the fluorine atom.

In general formula (I), R ^{6 to} R ¹⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. A group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring, R ^{6 to} R One or more of ¹⁰ are silicon-containing groups.

Among R ^{6 to} R ¹⁰ , a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group,
The substituents of the nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, and tin-containing group are the same as those exemplified for R ^{1 to} R ⁴ above. .

One or more of R ^{6 to} R ¹⁰ of the transition metal compound represented by the general formula (I) in the present invention is a silicon-containing group. In this case, (i) improvement in polymerization activity due to the three-dimensional bulkiness of the silicon-containing group, (ii) unique electronic properties of the silicon part (high HOMO energy level, σ-π conjugate and σ ^* -π conjugate) It exhibits the effects of poisoning resistance and high polar comonomer uptake.

  Specific examples of the silicon-containing group include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tributylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, isopropyldimethylsilyl, tert-butyldimethylsilyl, Hydrocarbon-substituted silyl groups such as tert-butyldiethylsilyl, tert-butyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; silyl-substituted silyl groups such as tristrimethylsilylsilyl; trimethylsilyl ether, triisopropylsilyl ether, tert-butyldiphenylsilyl Hydrocarbon-substituted silyl ether groups such as ether; alkoxy-substituted silyl groups such as trimethoxysilyl; bistrimethylsilyla Group, silicon-substituted amino groups such as bistriisopropylsilylamino group and bis-tert-butyldiphenylsilylamino group; silicon-substituted alkyl groups such as trimethylsilylmethyl and triisopropylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl and triisopropylsilylphenyl Group; etc. are preferred.

Next, the silicon-containing group in which one or more of R ^{6 to} R ¹⁰ described above are bonded will be described more specifically.

The silicon-containing group preferably has a total of 4 or more carbon atoms contained in the silicon-containing group bonded to R ^{6 to} R ¹⁰ in terms of the effect of improving the polymerization activity and the amount of polar monomer copolymerization. Among such silicon-containing groups, specific examples in which only one silicon-containing group has 4 or more carbon atoms include carbonization such as triisopropylsilyl group, tert-butyldimethylsilyl group, and tert-butyldiphenylsilyl group. A particularly preferred example is a hydrogen-substituted silyl group. Specific examples in which the total number of carbon atoms contained in two or more silicon-containing groups is 4 or more include 3,5-bistrimethylsilyl (wherein R ⁷ and R ⁹ are substituted with a trimethylsilyl group), 3,5- Bistriisopropylsilyl (a triisopropylsilyl group is substituted on R ⁷ and R ⁹ ) and the like are particularly preferred examples.

SHAPE \ * MERGEFORMAT Further, as the substitution position of the silicon-containing group, introduction into R ^{7 to} R ⁹ is particularly preferable from the viewpoint of improving the polymerization activity since the three-dimensional bulkiness of the silicon-containing group is further exhibited. Among these, particularly preferred examples of the substituent arrangement include R ⁸ substituted with a silyl group, R ⁷ and R ⁹ substituted with two silyl groups, and R ⁷ , R ⁸ and R ⁹ substituted with three silyl groups. Is mentioned.

In R ^{6 to} R ¹⁰ , two or more of these groups, preferably adjacent groups, are connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom or a silicon atom. These rings may further have a substituent.

In addition, when m is 2 or more, two groups out of the groups represented by R ^{6 to} R ¹⁰ may be linked. Further, when m is 2 or more, R ^{6 s} , R ^{7 s} , R ^{8 s} , R ^{9 s} , and R ^{10 s} may be the same or different.

  In the general formula (I), n is a number satisfying the valence of M, specifically 1 to 4, preferably 2.

  In general formula (I), X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, A heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group is shown.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl And aryl groups such as phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.

  Specific examples of the oxygen-containing group include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.

  Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate, Sulfonate groups such as p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene Sulfinate groups such as sulfinates; alkylthio groups; arylthio groups; sulfate groups; sulfide groups; polysulfide groups;

  Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino Arylamino groups or alkylarylamino groups such as: trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine Alkyl or arylamine groups such as (tppda).

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups and the like.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , ClO ₄ , and Sb.
Examples include chlorine-containing groups such as Cl ₆ and iodine-containing groups such as IO ₄ .

  Specific examples of the heterocyclic compound residue include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and the like. Examples include a group further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms in the heterocyclic compound residue.

  Specific examples of silicon-containing groups include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl;

  Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium.

  Specific examples of the tin-containing group include groups in which silicon in the silicon-containing group is substituted with tin.

  When n is 2 or more, a plurality of atoms or groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

  The bonding mode between X and transition metal atom M is not particularly limited, and examples of the bonding mode between X and transition metal atom M include a covalent bond, a coordination bond, an ionic bond, and a hydrogen bond.

Specific examples of the transition metal compound represented by the general formula (I) are shown below, but are not limited thereto. In the following examples, Ph is a phenyl group, ^t Bu is tert-
A butyl group, ⁱ Pr represents an isopropyl group, and Me represents a methyl group.

  In addition, the compound which replaced Ti metal with the other group 4 metal in the said exemplary compound can also be illustrated, for example, the compound which replaced Ti with Zr or Hf can also be illustrated.

  The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.

First, the ligand constituting the transition metal compound (A) is a salicylaldehyde compound, a primary amine compound represented by the following compound (II) (R ^{6 to} R ¹⁰ are as defined above) and It is obtained by reacting. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene solvent are preferable. The resulting solution is then stirred from room temperature under reflux conditions for about 1 to 48 hours to give the corresponding ligand in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed by Dean Stark, it is effective for the progress of the reaction.

  Next, the corresponding transition metal compound can be synthesized by reacting the ligand thus obtained with a transition metal-containing compound. Specifically, the synthesized ligand is dissolved in a solvent, and a base is reacted as necessary to prepare a phenoxide salt, which is then mixed with a metal compound such as a transition metal halogen compound and a transition metal alkyl compound at a low temperature. The mixture is stirred for about 1 to 48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those generally used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran, and hydrocarbon solvents such as toluene are preferably used. The base used in preparing the phenoxide salt is preferably a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. is not.

Depending on the properties of the compound, the transition metal compound (A) represented by the general formula (I) may be synthesized by directly reacting the ligand and the transition metal compound without going through phenoxide salt preparation. it can. Furthermore, for example, when any of R ^{1 to} R ¹⁰ is H, a substituent other than H can be introduced at any stage of the synthesis.

  Moreover, the reaction solution of a ligand and a transition metal compound can also be used for polymerization as it is without isolating the transition metal compound represented by the general formula (I).

  The above transition metal compounds (A) are used singly or in combination of two or more.

[(B-1) Organometallic compound]
As the (B-1) organometallic compound used in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table are used.
(B-1a) General formula R ^a _h Al (OR ^b ) _i H _j X _k
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and h represents 0 <H ≦ 3, i is 0 ≦ i <3, j is 0 ≦ j <3, k is a number of 0 ≦ k <3, and h + i + j + k = 3).
(B-1b) General formula M ² AlR ^a ₄
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Complex alkylated product with aluminum.
(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by:

  Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.

General formula R ^a _h Al (OR ^b ) _3-h
(In the formula, R ^a and R ^b may be the same or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and h is preferably 1.5 ≦ h ≦ An organoaluminum compound represented by the following formula:
General formula R ^a _h AlX _3-h
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and h is preferably 0 <h <3). Organoaluminum compounds,
General formula R ^a _h AlH _3-h
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and h is preferably 2 ≦ h <3),
General formula R ^a _h Al (OR ^b ) _i X _k
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and h represents 0 <H ≦ 3, i is a number satisfying 0 ≦ i <3, k is a number satisfying 0 ≦ k <3, and h + i + k = 3).
More specific examples of the organoaluminum compound belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum , Tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methyl Tri-branched alkyl aluminums such as xylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritylaluminum; diisobutylaluminum hydride Dialkylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide, etc .; alkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; ethylaluminum sesquiethoxy And alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide; R
^a partially alkoxylated alkylaluminum having an average composition represented by ^a _2.5 Al (OR ^b ) _0.5 ; diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), Ethylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-tert) Dialkylaluminum aryloxides such as -butyl-4-methylphenoxide); dialkyls such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Alkyl halides; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxychloride; Butyl aluminum butoxy chloride, ethyl , And the like partially alkoxylated and halogenated alkylaluminum such as Rumi um ethoxy bromide.

Moreover, the compound similar to (B-1a) can also be used, for example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

As the compound belonging to (B-1b),
Examples thereof include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound belonging to (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

  In addition, (B-1) organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used. (B-1) Among organometallic compounds, organoaluminum compounds are preferred. The above (B-1) organometallic compounds are used singly or in combination of two or more.
[(B-2) Organoaluminum oxy compound]
The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. Good. Specifically, compounds described as specific examples of (B-2) organoaluminum oxy compounds in JP-A No. 2004-331965 can also be cited in the present invention.

Said (B-2) organoaluminum oxy compound is used individually by 1 type or in combination of 2 or more types.

[(B-3) Compound that reacts with transition metal compound to form ion pair]
As the compound (B-3) used in the present invention to react with the transition metal compound (A) to form an ion pair (hereinafter referred to as “ionized ionic compound”), JP-A-1-501950, Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Specifically, compounds disclosed in Japanese Patent Application Laid-Open No. 2004-331965 as (B-3) a compound that forms an ion pair by reacting with a transition metal compound can also be exemplified in the present invention.

  Said (B-3) ionized ionic compound is used individually by 1 type or in combination of 2 or more types.

  Of these, compounds represented by the following general formula (III) are preferably used.

In the general formula (III), examples of R ¹¹ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{12 to} R ¹⁵ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.

  When an organoaluminum oxy compound (B-2) such as methylaluminoxane is used as the catalyst and promoter component, the transition metal compound according to the present invention exhibits better activity and higher copolymerizability with respect to the olefin compound. When an ionized ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having good activity and high molecular weight can be obtained.

Further, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) ionized ion. A support (E) to be described later can be used together with at least one compound selected from the active compounds, if necessary.
[(E) carrier]
The carrier (E) used as necessary in the present invention is an inorganic or organic compound and is a granular or fine particle solid.

  Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these, eg natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —T
_{iO 2, SiO 2 -V 2 O} 5, SiO 2 -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

Note that the inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , N
It may contain carbonates, sulfates, nitrates and oxide components such as a ₂ O, K ₂ O and Li ₂ O.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such carriers are
If necessary, it is baked at 100 to 1000 ° C, preferably 150 to 700 ° C.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. As disclosed in JP-A-2003-206310, the inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which a plurality of layers are stacked in parallel with each other with a weak binding force by ionic bonds or the like, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

  When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include TiCl ₄ , Zr
Cationic inorganic compounds such as Cl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O Examples thereof include metal hydroxide ions such as ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

  Examples of the organic compound carrier include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

The catalyst for olefin polymerization according to the present invention comprises the transition metal compound (A), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. A specific organic compound component (F), which will be described later, may be included as necessary together with at least one compound selected from the above, and optionally the carrier (E).
[(F) Organic compound component]
In the present invention, the organic compound component (F) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and phenolic compounds, those represented by R ¹⁶ —OH are usually used, wherein R ¹⁶ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms. A hydrocarbon group is shown. As the alcohol, R ¹⁶ is preferably a halogenated hydrocarbon. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ¹⁷ —COOH is usually used. R ¹⁷ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

  As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.

  As the sulfonate, those represented by the following general formula (IV) are used.

  In general formula (V), M is an atom selected from groups 1 to 14 of the periodic table.

R ¹⁸ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

  X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

  r is an integer of 1 to 7, and s is 1 ≦ s ≦ 7.

[Method for producing nonpolar-polar olefin copolymer]
In the method for producing a nonpolar-polar olefin copolymer according to the present invention, a copolymer can be obtained by copolymerizing a nonpolar olefin and a polar olefin in the presence of the olefin polymerization catalyst.

  The nonpolar olefin and polar olefin copolymerized by the manufacturing method of the nonpolar-polar olefin copolymer which concerns on this invention are illustrated below.

[Polar olefin]
The polar olefin in the present invention is a chain or cyclic unsaturated hydrocarbon having a polar group.

Specific examples of the chain unsaturated hydrocarbon having a polar group include acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, and 8-nonenoic acid. , 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentene Acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, ali Malonic acid, 2- (10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.2.1] -5-heptene- Unsaturated carboxylic acids such as 2,3-dicarboxylic acid, and metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt and calcium salt, and methyl ester and ethyl ester of these unsaturated carboxylic acids , N-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester and the like (if the unsaturated carboxylic acid is a dicarboxylic acid, mono Ester or diester), and amides of these unsaturated carboxylic acids Unsaturated carboxylic acid amides such as N, N-dimethylamide (in the case where the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide); for example, maleic anhydride, itaconic anhydride, Allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] -5-heptene-2, Unsaturated carboxylic acid anhydrides such as 3-dicarboxylic acid anhydride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; For example, vinyl chloride,
Halogenated olefins such as vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide; for example, allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyl Silylated olefins such as triisopropylsilane and allyltriphenylsilane; for example, acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5 Unsaturated nitriles such as heptene; for example, allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, Unsaturated alcohol compounds such as 12-tridecenol, and And unsaturated esters such as acetate, benzoate, propionate, caproate, caprate, laurate and stearate; substituted phenols such as vinylphenol and allylphenol; Unsaturated ethers such as ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene; for example, butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7- Unsaturated epoxides such as oxabicyclo [4.1.0] heptane; unsaturated aldehydes such as acrolein and undecenal, and their dimethyl acetal, diethyl aceto Unsaturated acetals such as tar; unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and their dimethyl acetal, diethyl Unsaturated acetals such as acetals; unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide; and unsaturated sulfoxides such as allyl phenyl sulfoxide; Unsaturated sulfones such as allyl phenyl sulfone; Unsaturated phosphines such as allyl diphenyl phosphine; And saturated phosphine oxides. Further, unsaturated hydrocarbons having the polar groups listed above, such as vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, methyl 4- (3-butenyloxy) benzoate, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 2-allylmethoxybenzene, 3-allylmethoxybenzene, 4-allylmethoxybenzene, 2-ethoxystyrene, 3-ethoxystyrene, 4-ethoxystyrene, allyl trifluoroacetate, o- Chlorostyrene, p-chlorostyrene, divinylbenzene, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) Ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane, etc. Is mentioned.

  As the cyclic unsaturated hydrocarbon having a polar group, the following general formula (V)

(In the formula (V), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{19 to} R ³⁶ and R ^a1 and R ^b1 are the same as or different from each other. May be a hydrogen atom or a hydrocarbon group, and R ^{33 to} R ³⁶ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle is a double bond And R ³³ and R ³⁴ , or R ³⁵ and R ³⁶ may form an alkylidene group.)
A cyclic olefin represented by the following general formula (VI)

(In the formula (VI), u1 and t are 0 or an integer of 1 or more, v1 and w1 are 0, 1 or 2, and R ^{37 to} R ⁵⁵ may be the same or different from each other, An aliphatic hydrocarbon group, an aromatic hydrocarbon group, a carbon atom to which R ⁴⁵ and R ⁴⁶ are bonded, and a carbon atom to which R ⁴⁹ is bonded or a carbon atom to which R ⁴⁷ is bonded May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when v1 = w1 = 0, R ⁵¹ and R ⁴⁸ or R ⁵¹ and R ⁵⁵ are bonded to each other to form a single ring Alternatively, a polycyclic aromatic ring may be formed.)
And the following general formula (VII)

(In formula (VII), R ⁵⁶ and R ⁵⁷ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and t1 is 1 ≦ t1 ≦ 18.)
One or more of the hydrogen atoms of the cyclic olefin represented by the formula is a polar group; for example, carboxyl group, nitrile group, hydroxyl group, ether group, epoxide, formyl group, ketone group, thioether group, sulfo group, phosphine, substituted silyl It is a cyclic polar olefin substituted with a group or the like. In the case of a polar cyclic olefin having a carboxyl group, metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt and calcium salt, and methyl ester, ethyl ester and n-propyl of these unsaturated carboxylic acids Unsaturated carboxylic acid esters such as ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester (in the case where the unsaturated carboxylic acid is a dicarboxylic acid, And amides of these unsaturated carboxylic acids, and unsaturated carboxylic acid amides such as N, N-dimethylamide (if the unsaturated carboxylic acid is a dicarboxylic acid, it is a monoamide). May also be a diamide); for example bicyclo [2.2 1] -5-heptene-2,3-unsaturated carboxylic acid anhydrides such as dicarboxylic acid anhydride. In the case of a polar cyclic olefin having a hydroxyl group, unsaturated esters such as acetic acid esters, benzoic acid esters, propionic acid esters, caproic acid esters, capric acid esters, lauric acid esters and stearic acid esters of these cyclic unsaturated alcohols should be mentioned. Can do. In the case of polar cyclic olefins having an aldehyde group, the unsaturated acetals such as dimethyl acetal and diethyl acetal should be mentioned. In the case of polar cyclic olefins having a ketone group, the unsaturated acetals such as dimethyl acetal and diethyl acetal should be mentioned Can do.

More specifically, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5,6-dimethylbicyclo [2.2.1] Hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-n-butylbicyclo [2.2 .1] hecyclo-2-ene, 5-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene and the like bicyclo [2.2. 1] hept-2-ene derivatives; tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, etc. Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative; tricyclo [
4.4.0.1 ^2,5 ] -3-undecene, tricyclo [4.4.0.1 ^2, 7-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene and the like ^{. 5} ] -3-undecene derivative; tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4
. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene, 8-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Hexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-stearyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 5,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4
. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-9-methyltetracyclo [4
. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11,12-dimethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,7,9-trimethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,7-dimethyl-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,11,12-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-11,1
2-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2,7,8,9-tetramethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-ethylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidenetetracyclocyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-n-propylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-isopropylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene, 8-isopropylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-bromotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene derivative; pentacyclo [6
. 5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,3-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 1,6-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 14,15-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, etc. pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene derivatives; pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-pentadecene, methyl-substituted pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . Pentacyclo [7 such as 0 ^8,13 ] -3-pentadecene
. 4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-pentadecene derivative; pentacyclo [6.5
. 1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] 4,10 penta cyclopentadiene octadecadienoic compounds such penta decadiene; pentacyclo [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-hexadecene, 10-methyl - pentacyclo [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-hexadecene, 10-ethyl - pentacyclo [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13 ] -3
-Hexadecene, 10,11-dimethyl-pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 .
0 ^8,13] -3-hexadecene, pentacyclo such [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-hexadecene derivatives; pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14 ] −
4-hexadecene, 1,3-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 1,6-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 15,16-dimethylpentacyclo [6.6.1.1 ^3,6 .
0 ^2,7 . 0 ^9,14] -4-hexadecene, pentacyclo such as [6.6.1.1 ^3,6. 0 ^2,7
. 0 ^9,14] -4-hexadecene derivatives; hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-methyl-hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-ethylhexanoate cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 11-isobutyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, 1,6,10-
Trimethyl-12-isobutylhexacyclo [6.6.1.1 ^3,6 . 11 ^0,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, hexacyclo such as [6.6.1.1 ^3,6. 1 ^10,13 . 0 ^2,7
. 0 ^9,14] -4-heptadecene derivatives; heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene and other heptacyclo-5-eicosene derivatives;
Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-eicosene, dimethyl-substituted heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^{11, 16]} -4-eicosene heptacyclo such as [8.7.0.1 ^3,6. 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16] -4-eicosene derivatives; heptacyclo [8.8.0.1 ^2,9. 1 ^4,7 . 1 ^11,18 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene , heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene , 14-methyl-heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene , trimethyl-substituted heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ]
Heptacyclo-5-heneicosene derivatives such as -5-heneicosene; octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 14-methyloctacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, 14-ethyloctacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 .
1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene and other octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene derivative; nonacyclo [10.
9.1.1 ^4,7 . 1 ^13,20 . 1 ^15,18 . 0 ^2,10 . 0 ^3,8 . 0 ^12,21 . 0 ^{14, 19]} -5-pentacosenoic, trimethyl replacement Nonashikuro [10.9.1.1 ^4,7. 1 ^13,20 . 1 ^15,18 . 0 ^2,10 .
0 ^3,8
. 0 ^12,21 . 0 ^{14, 19]} -5-pentacosenoic, Nonashikuro such as [10.9.1.1 ^4,7.
1 ^13,20 . 1 ^15,18 . 0 ^2,10 . 0 ^3,8 . 0 ^12,21 . 0 ^14,19] -5-pentacosene derivatives; Nonashikuro [10.10.1.1 ^5,8. 1 ^14,21 . 1 ^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic Nonashikuro such as [10.10.1.1 ^5,8. 1 ^14,21 . 1 ^16,19
. 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic derivatives; 5-phenyl - bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenyl [2.2.1] hept-2-ene, 5 -Benzyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene, 5- (ethylphenyl) -bicyclo [2.2.1] Hept-2-ene, 5- (isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 5- (biphenyl) -bicyclo [2.2.1] hept-2-ene, 5- ( β-naphthyl) -bicyclo [2.2.1] hept-2-ene, 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene, 5- (anthracenyl) -bicyclo [2 2.1] hept-2-ene, 5,6-diphenyl-bicyclo [2. .1] hept-2-ene, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a -Hexahydroanthracene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-Benzyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-tolyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (isopropylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-
Diphenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (β-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (α-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene, a compound obtained by further adding cyclopentadiene to (cyclopentadiene-acenaphthylene adduct), 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, 11,12-benzo - pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14] -4-hexadecene, 11-phenyl - hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 .
0 ^9,14] -4-heptadecene, 14,15-benzo - heptacyclo [8.7.0.1 ^2,9
. 1 ^4,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cycloeicocene, etc. Examples include cyclic polar olefins substituted with carboxyl group, nitrile group, hydroxyl group, ether group, epoxide, formyl group, ketone group, thioether group, sulfo group, phosphine, substituted silyl group, and the like.

  Of these, the polar olefin is any of unsaturated ethers, unsaturated carboxylic acid derivatives (particularly acid anhydrides, esters, amides), halogenated olefins, unsaturated alcohol compounds, and esters thereof. preferable. An aromatic compound having both an alkenyl group and an alkoxy group is also preferable. These polar olefins can be used alone or in combination of two or more.

[Non-polar olefin]
The nonpolar olefin, which is a constituent element of the nonpolar-polar olefin copolymer according to the present invention, is an unsaturated hydrocarbon consisting of only carbon atoms and hydrogen atoms. Specifically, ethylene, propylene, 1 -Butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene, 1-eicosene and the like linear or branched α-olefin having 2 to 20 carbon atoms; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 2-methyl 1,4,5,8-dimethano-1,2,3
, 4,4a, 5,8,8a-octahydronaphthalene and the like cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms; butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3 -Pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4 , 8-decatriene or the like having 4 to 30 carbon atoms, preferably 4 to 20 and having two or more double bonds in a cyclic or chain form Diene or polyene; mono- or polyalkyl styrene such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; Aromatic vinyl compounds; vinylcyclohexane; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

These nonpolar olefins can be used alone or in combination of two or more. As the nonpolar olefin, a linear or branched α-olefin having 2 to 20 carbon atoms or a cyclic olefin having 3 to 20 carbon atoms is preferable, and a linear or branched chain having 2 to 12 carbon atoms is preferable. An α-olefin or a cyclic olefin having 3 to 12 carbon atoms is more preferable, and ethylene, bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is particularly preferred.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

  Hereinafter, the conditions of the production method of the nonpolar-polar olefin copolymer in the present invention will be described in detail.

(Polymerization solvent)
As the solvent used in the liquid phase polymerization method, an inert solvent that is not subjected to the reaction during the polymerization reaction is used, and in particular, an inert hydrocarbon solvent is used. Specific examples of the inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. Moreover, the olefin itself used for reaction can also be used as a solvent.

(Catalyst concentration)
In the copolymerization of a nonpolar olefin and a polar olefin using the above-mentioned catalyst for olefin polymerization, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to It is used in such an amount that it becomes 10 ⁻³ mol.

  In the component (B-1), the molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) is usually 0.01 to 100, 000, preferably 0.05 to 50,000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) and transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.

  When the component (B) is the component (B-1), the component (F) has a molar ratio [(F) / (B-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (B) is the component (B-2), the molar ratio [(F) / (B-2)] is usually 0.001 to 2, preferably 0.005. When the component (B) is the component (B-3), the molar ratio [(F) / (B-3)] is usually 0.01 to 10, preferably 0.1. It is used as needed in such an amount that it becomes ˜5.

(Method of adding each component)
In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which the component (A) and the component (B) are supported on the carrier (C) is added to the polymerization vessel.
In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.
In the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.
The solid catalyst component in which the component (A) is supported on the carrier (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

(Polymerization temperature / Polymerization pressure)
Moreover, the polymerization temperature of the copolymerization of the nonpolar olefin and the polar olefin in the present invention is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 9.8 MPa (100 kg / cm ² ) (gauge pressure), preferably from normal pressure to 4.9 MPa (50
kg / cm ² ) (gauge pressure), and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

(Molecular weight adjustment)
The molecular weight of the resulting nonpolar-polar olefin copolymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) to be used.

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

In addition, the structure of the compound obtained in the synthesis example is 270 MHz ¹ H NMR (JEOL G
SH-270), FD-mass spectrometry (JEOL SX-102A) and the like.

The polar olefin content in the nonpolar-polar olefin copolymer was determined by ¹ H-NMR measurement using an ECX400P nuclear magnetic resonance apparatus manufactured by JEOL (measurement solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature). : 120 ° C). The weight average molecular weight, number average molecular weight, and molecular weight distribution were determined by GPC analysis (140 ° C., o-dichlorobenzene, polystyrene conversion) using Waters Alliance GPC2000.

  The complex compounds used in the comparison were synthesized by the methods disclosed in JP-A Nos. 2004-331965 and 2004-331966.

<1. Synthesis of ligand>
[Synthesis Example 1]
To a 100 mL reactor thoroughly dried and purged with nitrogen, 1.82 g (9.2 mmol) of compound 2-phenylsalicylaldehyde and 30 mL of toluene were charged. J. Am. Chem. Soc. 1998, 120, 213 pages, 10 mL of a toluene solution containing 1.52 g (9.2 mmol) of 4-trimethylsilylaniline synthesized by the method described in 213, and 0.0875 g of p-toluenesulfonic acid were added, and the mixture was stirred for 1 hour while heating under reflux. did. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 0.886 g (yield 21%) of the target compound represented by the following formula (a).

The obtained compound was analyzed by ¹ H NMR. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 0.29 (s, 9H, SiCH ₃ ), 7.02 (dd, 1H, J = 7.1 Hz, J = 7.1 Hz, Ar), 7.27 ( d, 2H, J
= 8.2 Hz, Ar), 7.33-7.48 (m, 5H, Ar), 7.56-7.59 (m, 2H, Ar), 7.64-7.67 (m, 2H, Ar), 8.71 (s, 1H, HC = N), 13.97 (s, 1H, OH)

[Synthesis Example 2]
To a 100 mL reactor thoroughly dried and purged with nitrogen, 0.186 g (0.938 mmol) of compound 2-phenylsalicylaldehyde and 20 mL of toluene were charged. Thereto was added 5 mL of a toluene solution containing 0.155 g (0.938 mmol) of 3-trimethylsilylaniline synthesized by the same method as in Synthesis Example 1, and the mixture was stirred for 5 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 0.257 g (yield 79%) of the desired product represented by the following formula (b).
Analysis by ¹ H NMR was performed. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 0.30 (s, 9H, SiCH ₃ ), 7.00-7.06 (m, 1H, Ar), 7.26-7.49 (m, 9H, Ar), 7.64-7.68 (m, 2H, Ar), 8.71 (s, 1H, HC = N), 14.08 (s, 1H, OH)

[Synthesis Example 3]
To a 100 mL reactor thoroughly dried and purged with nitrogen, 0.350 g (1.77 mmol) of compound 2-phenylsalicylaldehyde and 20 mL of toluene were charged. Thereto was added 5 mL of a toluene solution containing 0.441 g (1.77 mmol) of 4-triisopropylsilylaniline synthesized by the same method as in Synthesis Example 1, and 0.0337 g of p-toluenesulfonic acid was added. Stir for hours. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 0.257 g (yield 79%) of the target compound represented by the following formula (c).
Analysis by ¹ H NMR was performed. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 1.09 (d, 18H, CH ₃ ), 1.3
4-1.47 (m, 3H, CH), 7.01 (dd, 1H, J = 7.7 Hz, J = 7.7 Hz, Ar), 7.26-7.29 (m, 2H, Ar) , 7.34-7.48 (m, 5H, Ar), 7.53-7.56 (m, 2H, Ar), 7.64-7.68 (m, 2H, Ar), 8.72 ( s, 1H, HC = N), 14.00 (s, 1H, OH)

<2. Synthesis of transition metal compounds>
[Synthesis Example 4]
0.173 g (0.5 mmol) of the compound (a) obtained in Synthesis Example 1 was inserted into a 100 mL reactor sufficiently dried and purged with argon, and dissolved in 5 mL of dichloroethane. This solution was added dropwise to 10 mL of a dichloroethane solution containing 0.25 mL of titanium tetrachloride toluene solution (1.00 M, 0.25 mmol) cooled to −78 ° C. After completion of dropping, stirring was continued for 3 hours while slowly returning to room temperature.

After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 5 mL of methylene chloride, reprecipitated with 20 mL of diethyl ether, and the obtained solid was filtered through a glass filter. By drying under reduced pressure, 0.143 g (yield 71%) of a brown powder compound represented by the following formula (A) (hereinafter referred to as complex compound (d)) was obtained.
Analysis by ¹ H NMR, ¹³ C NMR, and FD-mass spectrometry was performed. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 0.186 (s, 18H, SiCH ₃ ), 6.83-6.89 (m, 6H, Ar), 6.97-7.00 (m, 4H, Ar), 7.07-7.10 (m, 2H, Ar), 7.38-7.56 (m, 8H, Ar), 7.80-7.84 (m, 4H, Ar), 7. 98 (s, 2H, HC = N)
¹³ C NMR (CDCl ₃ , 67.5 MHz): d-1.51, 121.37, 122.52, 124.65, 127.64, 128.09, 129.48, 129.86, 133.20, 133.64, 136.17, 136.54, 138.60, 152.26, 158.56, 165.21
FD-mass spectrometry (M +): m / z = 806

[Synthesis Example 5]
Into a 100 mL reactor sufficiently dried and purged with argon, 0.250 g (0.724 mmol) of the compound (b) obtained in Synthesis Example 2 was inserted and dissolved in 15 mL of dichloroethane. This solution was added dropwise to 10 mL of a dichloroethane solution containing 0.362 mL of a titanium tetrachloride toluene solution (1.00 M, 0.362 mmol) cooled to −78 ° C. After completion of dropping, stirring was continued for 3 hours while slowly returning to room temperature.

After evaporating the solvent of the reaction solution, the obtained solid was dissolved in 5 mL of methylene chloride, reprecipitated with 20 mL of diethyl ether and 15 mL of hexane, and the obtained solid was filtered through a glass filter. By drying under reduced pressure, 0.0945 g (yield 32%) of a brown powder compound represented by the following formula (e) (hereinafter referred to as complex compound (e)) was obtained.
Analysis by ¹ H NMR, ¹³ C NMR, and FD-mass spectrometry was performed. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 0.13 (s, 18H, SiCH ₃ ), 6.72-6.77 (m, 4H, Ar), 6.85-6.91 (m, 2H, Ar), 7.03-7.14 (m, 6H, Ar), 7.35-7.41 (m, 2H, Ar), 7.46-7.53 (m, 6H, Ar), 7. 75-7.78 (m, 4H, Ar), 8.02 (s, 2H, HC = N)
¹³ C NMR (CDCl ₃ , 67.5 MHz): d−1.15, 121.43, 124.54, 125.20, 125.23, 127.55, 128.05, 128.19, 129.58, 129.91, 131.35, 133.60, 136.15, 136.74, 140.72, 151.68, 158.66, 165.04
FD-mass spectrometry (M +): m / z = 806

[Synthesis Example 6]
In a 100 mL reactor sufficiently dried and purged with argon, 0.111 g (0.258 mmol) of the compound (c) obtained in Synthesis Example 3 was inserted and dissolved in 5 mL of dichloroethane. This solution was added dropwise to 5 mL of a dichloroethane solution containing 0.129 mL of a titanium tetrachloride toluene solution (1.00 M, 0.129 mmol) cooled to −78 ° C. After completion of dropping, stirring was continued for 15 hours while slowly returning to room temperature.

After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 5 mL of methylene chloride, reprecipitated with 10 mL of hexane, and the obtained solid was filtered through a glass filter. By drying under reduced pressure, 0.0836 g (yield 66%) of a brown powder compound represented by the following formula (f) (hereinafter referred to as complex compound (f)) was obtained.
Analysis by ¹ H NMR, ¹³ C NMR, and FD-mass spectrometry was performed. The results are shown below.
¹ H NMR (CDCl ₃ , 270 MHz): d 0.96 (d, 18 H, J = 8.1 Hz)
_{, CH 3), 0.98 (d} , 18H, J = 8.1Hz, CH 3), 1.21-1.35 (m, 6H, CH), 6.80-6.86 (dd, 2H, J = 8.1 Hz, J = 8.1 Hz, Ar), 699-7.12 (m, 10H, Ar), 7.40-7.56 (m, 8H, A)
r), 7.88-7.91 (m, 4H, Ar), 8.00 (s, 2H, HC = N)
¹³ C NMR (CDCl ₃ , 67.5 MHz): d 10.79, 18.53, 18.63, 121.49, 122.51, 124.51, 127.63, 128.19, 129.50, 129 .67, 133.69, 133.94, 135.09, 136.27, 136.90, 152.20, 158.70, 165.85
FD-mass spectrometry (M +): m / z = 974

[Example 1]
[Ethylene 4-allyl anisole copolymerization with complex compound (d)]
A glass autoclave with a paddle blade stirrer with an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, 31.5 mmol of 4-allyl anisole was added, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. It was. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the complex compound (d) was added to initiate polymerization. After reacting at 50 ° C. for 5 minutes in an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After termination of the polymerization, the reaction product was poured into a large amount of methanol / hydrochloric acid mixed solution to precipitate the whole amount of the polymer, and then filtered through a glass filter. The polymer was thoroughly washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.813 g of polymer. When this polymer was analyzed by ¹ H-NMR, the obtained polymer was an ethylene / 4-allylanisole copolymer containing 1.1 mol% of 4-allyl anisole in the polymer main chain. The polymerization activity and the analysis results of the obtained ethylene / allyl anisole copolymer are summarized in Table 1 and FIG.

[Example 2]
[Ethylene 4-allyl anisole copolymerization with complex compound (e)]
A glass autoclave with a paddle blade stirrer with an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, 31.5 mmol of 4-allyl anisole was added, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. It was. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the complex compound (e) was added to initiate polymerization. After reacting at 50 ° C. for 5 minutes in an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After termination of the polymerization, the reaction product was poured into a large amount of methanol / hydrochloric acid mixed solution to precipitate the whole amount of the polymer, and then filtered through a glass filter. The polymer was thoroughly washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.511 g of the polymer. When this polymer was analyzed by ¹ H-NMR, the obtained polymer was an ethylene / 4-allylanisole copolymer containing 1.1 mol% of 4-allyl anisole in the polymer main chain. The polymerization activity and the analysis results of the obtained ethylene / allyl anisole copolymer are summarized in Table 1 and FIG.

Example 3
[Ethylene 4-allyl anisole copolymerization with complex compound (f)]
A glass autoclave with a paddle blade stirrer with an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, 31.5 mmol of 4-allyl anisole was added, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. It was. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the complex compound (f) was added to initiate polymerization. After reacting at 50 ° C. for 5 minutes in an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol. After termination of the polymerization, the reaction product was poured into a large amount of methanol / hydrochloric acid mixed solution to precipitate the whole amount of the polymer, and then filtered through a glass filter. The polymer was sufficiently washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.69 g of a polymer. When this polymer was analyzed by ¹ H-NMR, the obtained polymer was an ethylene / 4-allyl anisole copolymer containing 1.3 mol% of 4-allyl anisole in the polymer main chain. The polymerization activity and the analysis results of the obtained ethylene / allyl anisole copolymer are summarized in Table 1 and FIG.

Example 4
[Preparation of Magnesium Chloride Solution (Preparation Solution 1)]
After suspending 95.2 g (1.0 mol) of anhydrous magnesium chloride as a catalyst component (A) in 442 ml of decane, 390.6 g (3.0 mol) of 2-ethylhexyl alcohol was added as a catalyst component (B). A homogeneous solution was obtained by reacting at 130 ° C. for 2 hours. Further, this solution was diluted with dehydrated toluene to obtain a preparation solution 1 having a magnesium concentration of 0.4M.

[Ethylene / 4-allylanisole copolymerization]
In a glass autoclave with a paddle blade stirrer with an internal volume of 500 mL sufficiently purged with nitrogen, 250 mL of purified toluene was placed, heated to 50 ° C., and the liquid phase and gas phase were saturated with ethylene at 100 L / hr of ethylene. Then, 4.0 mL of magnesium chloride solution (preparation solution 1) prepared earlier (magnesium content 1.6 mmol) and then 5.0 mL of 1.0 M triisobutylaluminum (TIBA) toluene solution (TIBA = 5.0 mmol) were added. Precipitation of the solid component was confirmed. After 3 minutes, 5.0 mL (31.5 mmol) of 4-allyl anisole was added as a polar olefin, and then 0.8 mL of 0.0025 M dehydrated toluene solution of the complex compound (f) as a catalyst component (A) 002 mmol) was added to initiate the polymerization. After polymerization for 5 minutes in an atmospheric pressure ethylene gas atmosphere, a small amount of isobutyl alcohol was added to terminate the polymerization. The reaction product was put into a large amount of methanol / hydrochloric acid mixed solution to precipitate the whole amount of polymer, and then filtered through a glass filter. The obtained polymer was vacuum-dried for 10 hours to obtain 1.415 g of a white polymer solid. When this polymer was analyzed by ¹ H-NMR, the obtained polymer was an ethylene / 4-allyl anisole copolymer containing 1.68 mol% of 4-allyl anisole in the polymer main chain. The polymerization activity and the analysis results of the obtained ethylene / allyl anisole copolymer are summarized in Table 1 and FIG.

[Comparative Example 1]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, 31.5 mmol of 4-allyl anisole was added, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the following complex compound (g) was added to initiate polymerization. After reacting at 50 ° C. for 5 minutes in an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of methanol.

After termination of the polymerization, the reaction product was poured into a large amount of methanol / hydrochloric acid mixed solution to precipitate the whole amount of the polymer, and then filtered through a glass filter. The polymer was thoroughly washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.982 g of polymer. This polymer was subjected to ¹ H-NMR
As a result, the obtained polymer was an ethylene / 4-allyl anisole copolymer in which 0.95 mol% of 4-allyl anisole was contained in the polymer main chain. The polymerization activity and the analysis results of the obtained ethylene / allyl anisole copolymer are summarized in Table 1 and FIG.

  Since the nonpolar-polar olefin copolymer in the present invention contains a polar group in the polymer, the hydrophilicity is improved. For this reason, it has excellent physical properties such as compatibility and adhesion with other polar polymers, so it has diversified in a wide range of product fields such as automobiles, electrical equipment parts, food packaging, beverages / cosmetics / medical containers, civil engineering, and agricultural materials. It is possible to provide a product that satisfies the requirements for polyolefin.

Claims (5)

A transition metal compound (A) represented by the following general formula (I):

(In the formula, M represents a transition metal atom of Group 4 or 5 of the periodic table,
m represents an integer of 1 to 4,
R ^{1 to} R ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
R ⁵ is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms composed of only primary or secondary carbon, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or bicyclic Selected from alicyclic hydrocarbon groups and aromatic hydrocarbon groups of
R ^{6 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, or a phosphorus-containing group. , A silicon-containing group, a germanium-containing group, or a tin-containing group, wherein one or more of R ^{6 to} R ¹⁰ are silicon-containing groups, and two or more of these R ^{6 to} R ¹⁰ are connected to each other. May form a ring,
n is a number that satisfies the valence of M;
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. To form a ring. )
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) an olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair. A method for producing a nonpolar-polar olefin copolymer, which comprises copolymerizing a nonpolar olefin and a polar olefin in the presence thereof.   The method for producing a nonpolar-polar olefin copolymer according to claim 1, wherein m is 2 and M is a titanium atom in the transition metal compound (A) represented by the general formula (I). In the transition metal compound (A) represented by formula (I), non-polar of claim 2 R ⁵ is a phenyl group - the production method of a polar olefin copolymer. In the transition metal compound (A) represented by the general formula (I), the silicon-containing group contained in R ^{6 to} R ¹⁰ has 4 or more carbon atoms. 2. A method for producing a nonpolar-polar olefin copolymer according to item 1.   The nonpolar-polar olefin copolymer obtained by the manufacturing method of the polar olefin copolymer of any one of Claims 1-4.

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