JP2003342326A - Olefin copolymer bearing reactive group and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive low-molecular weight polyethylene copolymer bearing both a reactive group and an aromatic group expected to be useful as a compatibilizer, a resin modifier and the like, and a method for efficiently manufacturing the reactive low-molecular weight polyethylene copolymer under mild polymerization conditions. <P>SOLUTION: The ethylene-based polymer is represented by the formula (wherein T<SP>1</SP>and T<SP>2</SP>are each a hydrogen atom, a group selected from an alkyl group and an alkenyl group and T<SP>1</SP>and T<SP>2</SP>may form a ring together; Y is a functional group having a double bond; Z is an aromatic group; and a, b, c and d are each a number of at least 0 that satisfy the weight average molecular weight of the polymer of at most 20,000), has a reactive group (Y) at least at one end of the main chain and an aromatic group (Z) and substituting groups (T<SP>1</SP>, T<SP>2</SP>) in the side chain, and has a weight-average molecular weight of at most 20,000. The polymer is manufactured using a catalyst comprising a specific transition metal compound. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive low molecular weight polyethylene copolymer having a reactive group at at least one polymer main chain terminal and an aromatic group at a side chain, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Relatively low molecular weight polymers having reactive groups are available in a variety of polymer structures, such as block polymers,
It is an important building block for building cross-linked polymers, branched polymers, comb polymers, star polymers and the like. Polymers having these unique structures are expected to be used as compatibilizers, resin modifiers, rubbers, thermoplastic elastomers, and the like. There is a demand for such a polymer and a method for efficiently producing the polymer.

Various methods are known for introducing a reactive functional group into polyethylene. For example, copolymerization of ethylene and a reactive comonomer by radical polymerization is known. However, this method requires high-temperature and high-pressure reaction conditions, and it is difficult to quantitatively introduce a functional group into a terminal. Also, a method of grafting a functional group to polyethylene as a post-reaction is known. This method involves a two-stage reaction of polymerization and a polymer reaction, so that it is costly and often involves side reactions such as decomposition of a polymer. Copolymerization of ethylene with a reactive comonomer with a transition metal catalyst is also known. However, it has not been possible to simultaneously achieve quantitative introduction of a functional group to the terminal, control of molecular weight, and copolymerizability with a reactive comonomer.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has a reactive substituent at at least one polymer chain terminal, and has an aromatic group. It is an object of the present invention to provide a reactive low molecular weight polyethylene copolymer having a group in a side chain and to efficiently produce the reactive low molecular weight polyethylene copolymer under mild polymerization conditions. Aromatic group is an alkyl group,
An aromatic group whose nucleus is substituted with a reactive group such as a halogenated alkyl group, a silyl group, a hydroxy group, an amino group, a vinyl group, an allyl group, or a halogen atom. Another object of the present invention is to provide a reactive low molecular weight polyethylene copolymer having a reactive group and a method for producing the same.

[0005]

Means for Solving the Problems A first aspect of the present invention is a polymer having a reactive group (Y) at at least one polymer main chain terminal, which is represented by the following general formula (1): An ethylene polymer having an aromatic group (Z) and a substituent (T ¹ , T ² ) in a side chain and having a weight average molecular weight of 20,000 or less.

[0006]

Embedded image In the general formula (1), T ¹ and T ² represent a group selected from a hydrogen atom, an alkyl group and an alkenyl group, and T ¹ and T ² may form a ring with each other. Y represents a functional group having a double bond. Examples of such a functional group Y include a vinyl group, a vinylene group, and a vinylidene group. The amount (P) of the reactive group Y at the terminal position of the polymer main chain can be determined, for example, by a proton nuclear magnetic resonance spectrum (NMR) as described later.
Is determined by the following equation (Equation 1) based on the peak area of the polymer, and is usually 70 mol% or more, preferably 90 mol% or more from the viewpoint of the efficiency of the post-polymerization reaction. In the following description, the P value may be called an introduction rate. P = (pS _V / S _Me ) × 100 (Equation 1) In Formula 1, S _V indicates an NMR peak area attributable to all protons contained in the reactive group Y, and S _Me indicates all methyls. The NMR peak area due to the group is shown. The coefficient p is 1 for a vinyl group and 1.5 for a vinylene group or a vinylidene group.

[0007] Z represents an aromatic group. In general, when an aromatic group is introduced into a polymer side chain, the polymer itself exhibits properties not obtainable with a polyolefin, and when the aromatic group is a group whose nucleus is substituted with a functional group, There is an advantage that the degree of freedom of denaturation can be increased. As the aromatic group, a nucleus-substituted phenyl group represented by the following general formula (4) is preferable from the viewpoint of reactivity of a post-polymerization reaction.

[0008]

Embedded image In the general formula (4), * indicates a bonding point to a polymer side chain, and R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a silyl group, a hydroxyl group, an amino group, An arbitrary group selected from an amino group, an allyl group, a vinyl group, a vinylene group, a vinylidene group, and a halogen in which one or two hydrogen atoms are substituted with a hydrogen group. n represents an integer of 1 to 5, and when n is 2 or more, Rs may be the same or different from each other, and may form a ring with each other. Aromatic group Z
As the phenyl group, p-
Preferable are a bromophenyl group, a p-chlorophenyl group, a p-methylphenyl group, a p-bromomethylphenyl group, and a p-chloromethylphenyl group.

The weight average molecular weight (Mw) of the ethylene polymer represented by the general formula (1) determined by gel permeation (GPC) analysis is 20,000 or less. Such a molecular weight can be widely used for compatibilizers, resin modifiers, rubbers, thermoplastic elastomers, and the like.

In the general formula (1), a, b, c and d are
It represents a number of 0 or more that satisfies the Mw of the ethylene polymer of the present invention of 20,000 or less. a, b, c and d can be arbitrarily adjusted depending on the production conditions of the ethylene-based polymer, particularly the charged ratio of the raw material olefins. Generally, when it is desired to impart properties close to polystyrene to the olefin polymer of the present invention, or when further modified and used.
An olefin polymer having a relatively high value of b is used. Although it depends on the form of Z, a value is usually 0 to 0.1.
0, b value is 0.02-0.80, c value is 0.20
0.98, preferably a value is 0 to 0.04, b
The value is 0.05 to 0.40, and the c value is 0.60 to 0.9.
5

A second aspect of the present invention is that ethylene and, if necessary, C 3-20 in the presence of a catalyst comprising a transition metal compound represented by the following general formula (2) or (3):
A method for producing the ethylene-based polymer according to any one of claims 1 to 3 from the α-olefin of (1). Hereinafter, the transition metal compound [A] represented by the general formula (2) and the transition metal compound [B] represented by the general formula (3) will be described, and then a method for producing an ethylene polymer will be described. An α-olefin having an aromatic group having 8 to 20 carbon atoms, which is used as a raw material, will be described.

Transition metal compound [A] The transition metal compound [A] is a compound represented by the following general formula (2).

[0013]

Embedded image In the general formula (2), R ^{1 to} R ³ represent 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring , and one of the radicals R ¹ to R ³ which is included in any one of the ligands, binding group or with one of the radicals R ¹ to R ³ contained in other ligands A single bond may be formed. As the substituent R ¹ , primary or secondary
It is preferably an alkyl group of a lower class, specifically, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a benzyl group, a nucleus having a nucleus, or an aryl group having 6 to 15 carbon atoms. Include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Isopropyl group, isobutyl group, 1-methylpropyl group, 1-ethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, 2-norbornyl group,
Benzyl and phenyl are preferred.

N is a number that satisfies the valence of M ¹ , and M ¹ is Ti, Zr or Hf, preferably Zr.
X represents a hydrogen atom, a halogen 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, or a silicon-containing residue. 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 as or different from each other; A ring may be formed.

Specific examples of the transition metal compound [A] include bis [N- (3-t-butylsalicylidene) methylaminato] zirconium dichloride and bis [N- (3-t-butylsalicylidene). Den) ethylaminato] zirconium dichloride, bis [N- (3-t-butylsalicylidene) propylaminato] zirconium dichloride, bis [N- (3-t-butylsalicylidene) hexylaminato] zirconium dichloride , Bis [N- (3-t-butylsalicylidene) cyclohexylaminato] zirconium dichloride, bis [N- (3-t-butylsalicylidene) cyclopentylaminato] zirconium dichloride, bis [N- (3- t-butylsalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N- (3-t-butylsalicylidene) benzylaminate] zirconium dichloride, Scan [N
-(3-cumylsalicylidene) methylaminate] zirconium dichloride, bis [N- (3-cumylsalicylidene) ethylaminate] zirconium dichloride, bis [N-
(3-cumylsalicylidene) propylaminate] zirconium dichloride, bis [N- (3-cumylsalicylidene) hexylaminate] zirconium dichloride, bis [N
-(3-cumylsalicylidene) cyclohexyl aminate]
Zirconium dichloride, bis [N- (3-cumylsalicylidene) cyclopentylaminate] zirconium dichloride, bis [N- (3-cumylsalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N- (3-
Cumylsalicylidene) benzylaminate] zirconium dichloride, bis [N- (3-t-butyl-5-methoxysalicylidene) methylaminate] zirconium dichloride, bis [N- (3-t-butyl-5- Methoxysalicylidene) ethylaminate] zirconium dichloride, bis [N-
(3-t-butyl-5-methoxysalicylidene) propylaminate] zirconium dichloride, bis [N- (3-t-butyl
-5-Methoxysalicylidene) hexylaminato] zirconium dichloride, bis [N- (3-t-butyl-5-methoxysalicylidene) cyclohexylaminato] zirconium dichloride, bis [N- (3-t-butyl -5-methoxysalicylidene) cyclopentylaminate] zirconium dichloride, bis [N- (3-t-butyl-5-methoxysalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N- ( (3-t-butyl-5-methoxysalicylidene)
Benzylaminate] zirconium dichloride, bis [N- (3-cumyl-5-methoxysalicylidene) methylaminate] zirconium dichloride, bis [N- (3-cumyl5-
Methoxysalicylidene) ethylaminate] zirconium dichloride, bis [N- (3-cumyl5-methoxysalicylidene) propylaminate] zirconium dichloride,
Bis [N- (3-cumyl5-methoxysalicylidene) hexylaminato] zirconium dichloride, bis [N- (3-cumyl5-methoxysalicylidene) cyclohexylaminato] zirconium dichloride, bis [N- (3 -Cumyl 5-methoxysalicylidene) cyclopentylaminate] zirconium dichloride, bis [N- (3-cumyl5-methoxysalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N- (3- Cumyl 5-methoxysalicylidene) benzylaminato] zirconium dichloride, bis [N- (3-adamantylsalicylidene) methylaminate] zirconium dichloride, bis [N- (3-adamantylsalicylidene) ethylaminate] Zirconium dichloride, bis [N- (3-adamantylsalicylidene) propylaminate] zirconium dichloride, Scan [N-
(3-adamantylsalicylidene) hexylaminate] zirconium dichloride, bis [N- (3-adamantylsalicylidene) cyclohexylaminate] zirconium dichloride, bis [N- (3-adamantylsalicylidene) cyclopentylaminate] Zirconium dichloride, bis [N- (3-adamantylsalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N- (3-adamantylsalicylidene) benzylaminate] zirconium dichloride, bis [N- (3-Adamantyl-5-methoxysalicylidene) methylaminate] zirconium dichloride, bis [N- (3-adamantyl-5-methoxysalicylidene) ethylaminate] zirconium dichloride, bis [N- (3-adamantyl) -5-methoxysalicylidene) propylaminate] zirconium dichloride , Bis [N- (3- adamantyl-5-methoxy-butylsalicylidene) hexyl amino Inert] zirconium dichloride, bis [N-
(3-adamantyl-5-methoxysalicylidene) cyclohexylaminate] zirconium dichloride, bis [N-
(3-adamantyl-5-methoxysalicylidene) cyclopentylaminate] zirconium dichloride, bis [N-
(3-adamantyl-5-methoxysalicylidene) -2-norbornylaminate] zirconium dichloride, bis [N-
(3-adamantyl-5-methoxysalicylidene) benzylaminate] zirconium dichloride.
Further, zirconium in these transition metal compounds may be replaced with titanium or hafnium.

Transition metal compound [B] The transition metal compound [B] is a compound represented by the following general formula (3).

[0017]

Embedded image In the general formula (3), M ² is Fe or Co, and R ⁴ is
Shows 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. . Specific examples of R ⁴ include an aryl group, an amino group, a pyridyl group, and a pyrrolyl group, and more specifically, a phenyl group, a 2,6-dimethylphenyl group, and a 2,6-diisopropylphenyl group. , 2-t-
Butylphenyl group, N, N-diphenylamino group, N,
Examples include an N-dimethylamino group, an N-methyl-N-phenylamino group, a 2,5-dimethylpyrrolyl group, and the like.

N is a number satisfying the valence of M ² , and X
Represents a hydrogen atom, a halogen 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, and 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 are linked to each other to form a ring. May be formed.

Specific transition metal compounds [B] include:
2,6-diacetylpyridinebis (N, N-diphenylhydrazone) iron dichloride, 2,6-diacetylpyridinebis (N, N-dimethylhydrazone) iron dichloride, 2,6-diacetylpyridinebis (N-methyl-N- Phenylhydrazone) iron dichloride, 2,6-diacetylpyridinebis (2,5-dimethylpyrrolyl) iron dichloride, 2,6-diacetylpyridinebis (2,6-dimethylphenyl) iron dichloride, 2,6-diacetylpyridinebis (2,6-diisopropylphenyl) iron dichloride, 2,6-diacetylpyridinebis (2-t-butylphenyl) iron dichloride, 2,6-diacetylpyridinebis (N, N-diphenylhydrazone) cobalt dichloride, 2,6 -Diacetylpyridinebis (N, N-
Dimethylhydrazone) cobalt dichloride, 2,6-diacetylpyridinebis (N-methyl-N-phenylhydrazone) cobalt dichloride, 2,6-diacetylpyridinebis (2,5-dimethylpyrrolyl) cobalt dichloride, 2,6-diacetyl Pyridinebis (2,6-dimethylphenyl) cobalt dichloride, 2,6-diacetylpyridinebis (2,6-diisopropylphenyl) cobalt dichloride, 2,6-diacetylpyridinebis (2-t-butylphenyl) cobalt dichloride, etc. No.

Process for Producing Ethylene Polymer The olefin polymer according to the present invention has the general formula (2)
Or the transition metal compound [B] represented by the general formula (3) may be polymerized alone, or [C] [C-1] an organometallic compound [C -2] An organic aluminum oxy compound and at least one compound selected from compounds that react with the [C-3] transition metal compound (A) to form an ion pair may be used as the olefin polymerization catalyst. Hereinafter, the components [C-1], [C-2] and [C-3] will be described.

[C-1] Organometallic Compounds The [C-1] organometallic compounds used as required in the present invention include, specifically, the following Periodic Table Groups 1 and 2 and Groups 12 and 13. Group organometallic compounds are used.

[0022] In [C-1a] formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0023] [C-1b] In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal belonging to Group 1 of the periodic table and aluminum.

[C-1c] Formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

Examples of the organoaluminum compound belonging to the above [C-1a] include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

More specifically, the organoaluminum compounds belonging to [C-1a] include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri-n-alkyl aluminum such as aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y, z
Is a positive number and z ≧ 2x. ) And the like; trialkenyl aluminum such as triisoprenyl aluminum; alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide Dialkylaluminum alkoxides, such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide, etc .; partially alkoxylated alkyl aluminums having an average composition represented by ^Ra _2.5 Al (OR ^b ) _0.5, etc. ; Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) Ethylaluminum bis (2,6-di -t- butyl-4-methyl phenoxide), diisobutylaluminum (2,6
Dialkylaluminium aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride Dialkylaluminum halides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; alkyls such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkylaluminums such as aluminum dihalide; diethylaluminum Dialkylaluminum hydrides such as aluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxychloride, butylaluminum Partially alkoxylated and halogenated alkylaluminums such as butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

Further, compounds similar to [C-1a] can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ A
1N (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Compounds belonging to the above [C-1b] include Li
_{Al (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like. In addition, as the [C-1] organometallic compound, 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, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

Further, a compound which forms the above-mentioned 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.

[C-1] Among the organometallic compounds, an organoaluminum compound is preferred. The [C-1] organometallic compounds as described above are used alone or in combination of two or more.

[C-2] Organoaluminum oxy compound The [C-2] organoaluminum oxy compound used as required in the present invention may be a conventionally known aluminoxane, and JP-A-2-78687. And a benzene-insoluble organoaluminum oxy compound as exemplified in (1).

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, primary chloride
A method in which an organoaluminum compound such as trialkylaluminum is added to a suspension of a hydrocarbon medium such as cerium hydrate, and the adsorbed water or water of crystallization reacts with the organoaluminum compound. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) Decane, benzene, organoaluminum compounds such as trialkylaluminum in a medium such as toluene,
A method of reacting an organic tin oxide such as dimethyl tin oxide and dibutyl tin oxide.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the aforementioned [C-1a]
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound has an Al component soluble in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, that is, And those which are insoluble or hardly soluble in benzene are preferred.

As the organic aluminum oxy compound,
An organic aluminum oxy compound containing boron represented by the following general formula (5) can also be given.

[0039]

Embedded image In the formula, R ⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁸ may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy compound containing boron represented by the general formula (5) is represented by the following general formula (5)
a) reacting the alkylboronic acid represented by a) with R ⁷ —B (OH) ₂ (5a) (wherein R ⁷ represents the same group as described above) under an inert gas atmosphere; It can be produced by reacting in a solvent at a temperature of -80C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (5a) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid are those described in (B-1a) above.
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more. The above [C-2] organoaluminum oxy compounds are used alone or in combination of two or more.

[C-3] Transition metal compound [A] or [B]
A compound that forms an ion pair by reacting with a compound [C-3] (hereinafter referred to as an “ionized ionic compound”) that forms an ion pair by reacting with a transition metal compound [A] used as necessary in the present invention. May be called).
01950, JP-A-1-50203, JP-A-3-179005, JP-A-3-179006
JP, JP-A-3-207703, JP-A-3-2703
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP 07704, USP-5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, BR ₃
(R is a phenyl group which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group or fluorine.), For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionized ionic compound include a compound represented by the following general formula (6).

[0047]

Embedded image In the formula, R ⁹⁺ includes H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, and the like.

R ^{10 to} R ¹³ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ⁹⁺ is a carbonium cation,
Ammonium cations and the like are preferable, and triphenylcarbonium cation, N, N-dimethylanilinium cation and N, N-diethylanilinium cation are particularly preferable.

Examples of the ionized ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m'-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-
Butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron and tri (n-butyl) ammonium tetra (o-tolyl) boron.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N, 2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionized ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenyl Carbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compounds represented by the following formula (7) or (8), and the like can also be mentioned.

[0057]

Embedded image

[0058]

Embedded image

Specific examples of the borane compound include, for example,
Decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium ) Ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl)
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl -1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The heteropoly compound has an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin,
It is composed of one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, and salts of these acids, for example, metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.

The above [C-3] ionized ionic compounds are used alone or in combination of two or more. When the above-mentioned transition metal compound [A] or [B] is used as a catalyst for olefin polymerization, an organoaluminum oxy compound such as methylaluminoxane may be used as a promoter component.
When used in combination with [B-2], it exhibits very high polymerization activity for olefins.

The olefin polymerization catalyst used in the present invention comprises the above-mentioned transition metal compound [A] or [B],
Organometallic compounds [C-1], Organoaluminum oxy compounds
[C-2] and at least one compound [C] (hereinafter sometimes referred to as “component [C]”) selected from the ionized ionic compound [C-3] and, if necessary, the following carrier [ D] and / or an organic compound [E] as described below.

[D] Carrier The [D] carrier optionally used in the present invention may be an inorganic or inorganic carrier.
Or an organic compound in the form of granules or fine particles
It is solid. Among them, the inorganic compounds include porous oxide
Materials, inorganic halides, clays, clay minerals and porous acids
As a compound, specifically, SiO_Two, Al_TwoO_Three, MgO, ZrO, Ti
O_Two, B_TwoO _Three, CaO, ZnO, BaO, ThO_TwoOr these
Uses composites or mixtures containing, e.g., natural or synthetic
Zeolite, SiO_Two-MgO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-
V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-Use MgO etc.
Can be. Of these, SiO_TwoAnd / or Al_TwoO_ThreeTo
Those having a main component are preferred.

The above inorganic oxide is composed of 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 , KN
It may contain carbonate, sulfate, nitrate and oxide components such as O ₃ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a porous oxide vary depending on the kind and the production method, but the carrier preferably used has a particle size of 10 to 300 μm, preferably 20 to 200 μm.
μm, the specific surface area is in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may optionally be 100-100.
It is used after firing at 0 ° C, preferably 150 to 700 ° C.

As inorganic halides, MgCl ₂ , MgB
r ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, after dissolving inorganic chlorides in a solvent such as alcohol, those obtained by precipitating these into fine particles with a precipitant can also be used.

Clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used.

As the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, and ionic crystalline compounds having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. Compounds and the like can be exemplified.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, Nacrite, dickite, halloysite, and the like.Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HP
_{O 4) 2, α-Zr} (KPO 4) 2 · 3H 2 O, α-Ti (HPO 4) 2, α-Ti (H
AsO ₄ ) ₂・ H ₂ O, α-Sn (HPO ₄ ) ₂・ H ₂ O, γ-Zr (HPO ₄ ) ₂ ,
Crystalline acidic salts of polyvalent metals such as γ-Ti (HPO ₄ ) ₂ and γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O are exemplified.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of at least 20 mm in radius measured by mercury porosimetry and having a pore volume of at least 0.1 cc / g.
Those having 0.3 to 5 cc / g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of a pore radius of 20 to 3 × 10 ⁴ Å.

The volume of pores having a radius of 20 ° or more is 0.1 cc /
When a material smaller than g is used as a carrier, a high polymerization activity tends to be hardly obtained. Clay and clay minerals are also preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. Acid treatment removes impurities on the surface, Al in the crystal structure,
The surface area is increased by eluting cations such as Fe and Mg. 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 substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by utilizing the ion-exchange property and exchanging the exchangeable ion between the layers with another large bulky ion. Such a bulky ion plays a role of a support for supporting the layered structure, and is usually called a pillar. Introducing another substance between layers of the layered compound in this way is called intercalation. TiC is used as the intercalating guest compound.
l _4, cationic inorganic compound such as _{ZrCl 4, Ti (OR) 4} , Zr (O
Metal alkoxides such as R) ₄ , PO (OR) ₃ , B (OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ^{2 +} ,
And metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. When intercalating these compounds, they were obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ . A polymer, a colloidal inorganic compound such as SiO ₂ or the like can also be allowed to coexist. Examples of the pillars include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

The clay, the clay mineral, and the ion-exchangeable layered compound may be used as they are, or may be used after performing a treatment such as ball milling or sieving. Further, it may be used after water is newly added and adsorbed or subjected to heat dehydration treatment. Further, they may be used alone or in combination of two or more.

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

The organic compound has a particle size of 10 to 300.
Granular or particulate solids in the range of μm are mentioned. Specifically, ethylene, propylene, 1-butene,
Α- having 2 to 14 carbon atoms such as 4-methyl-1-pentene
Examples thereof include (co) polymers produced mainly with olefins, vinylcyclohexane, (co) polymers produced mainly with styrene, and modified products thereof.

[E] Organic Compound Component In the present invention, the (E) organic compound component is used, if necessary, for the purpose of improving polymerization performance and physical properties of the produced polymer. Such organic compounds include, for example, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and phenolic compounds, those represented by R ¹⁴ —OH are usually used.
Here, R ¹⁴ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. As the alcohols, those in which R ¹⁴ is a halogenated hydrocarbon are preferred. Further, as the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, R is usually^Fifteen-COO
The one represented by H is used. R ^FifteenRepresents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halo group having 1 to 50 carbon atoms.
Genated hydrocarbon groups are preferred.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P-OR, phosphates having a P ＝ O bond, and phosphine oxide compounds are preferably used.
As the sulfonate, those represented by the following general formula (8) are used.

[0081]

Embedded image

In the formula, M is an element belonging to Groups 1 to 14 of the periodic table. R ¹⁶ is a hydrogen atom, 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. m is an integer of 1 to 7, and n
Is 1 ≦ n ≦ 7.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) A method in which the transition metal compound [A] or [B] is added alone to the polymerization vessel. (2) A method in which the transition metal compound [A] or [B] and the component [C] are added to the polymerization vessel in any order. (3) A method in which the catalyst component in which the transition metal compound [A] or [B] is supported on the carrier [D] and the component [C] are added to the polymerization reactor in any order. (4) a catalyst component in which the component [C] is supported on a carrier [D];
A method in which the transition metal compound [A] or [B] is added to the polymerization vessel in an arbitrary order. (5) A method in which a catalyst component in which a transition metal compound [A] or [B] and a component [C] are supported on a carrier [D] is added to a polymerization reactor.

In each of the above methods (2) to (5),
At least two or more of the catalyst components may be in contact with each other in advance. (4) wherein the component [C] is supported,
In each method of (5), the unsupported component [C] may be added in an arbitrary order, if necessary. In this case, the components [C] may be the same or different.

The component [D] is a solid catalyst component carrying the transition metal compound [A] or [B]. The component [D] is the transition metal compound [A] or [B] and the component [C]. The olefin may be preliminarily polymerized in the solid catalyst component on which is carried, or a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and the olefin itself is used as a solvent. You can also.

When an olefin polymer is produced using the olefin polymerization catalyst as described above, the transition metal compound [A] or [B] is usually added in an amount of 10 ^-12 to 10 ^-2 per liter of reaction volume. Mole, preferably 10 ^-10 to 10 ^-3 mole.

When component [C-1] is used, component [C-1]
And the molar ratio [[C-1] / M] of the transition metal atom (M) in the transition metal compound [A] or [B] is usually 0.01 to
It is used in an amount such that it is 100,000, preferably 0.05 to 50,000. When the component [C-2] is used, the molar ratio of the aluminum atom in the component [C-2] to the transition metal atom (M) in the transition metal compound [A] [[C-2] /
M] is usually 10 to 500,000, preferably 20 to 1
It is used in such an amount as to be 00000. When the component [C-3] is used, the molar ratio of the component [C-3] to the transition metal atom (M) in the transition metal compound [A] or [B] [[C-3] / M Is usually used in an amount of 1 to 10, preferably 1 to 5.

When the component [E] is used, when the component [C] is the component [C-1], the molar ratio [E] / [C-1] is usually from 0.01 to 10, preferably from 10 to 10. When the component [C] is the component [C-2] in such an amount as to be 0.1 to 5, the molar ratio [E] / [C-2] is usually 0.001 to 2, preferably 0. .
Component [C] is added to component [C-3] in such an amount as to be 005 to 1.
In this case, the molar ratio [E] / [C-3] is usually 0.01 to 1
It is used in an amount such that it becomes 0, preferably 0.1 to 5.

The polymerization temperature of the olefin polymer using such an olefin polymerization catalyst is usually -40 to 40.
+ 200 ° C, preferably in the range of 0 to + 100 ° C.
The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. it can. Further, the polymerization can be performed in two or more stages under different reaction conditions.

The molecular weight of the obtained ethylene copolymer is as follows:
It can be adjusted by controlling the monomer / catalyst ratio and the polymerization time.

Α-O having an aromatic group having 8 to 20 carbon atoms
Refining The α-olefin having an aromatic group having 8 to 20 carbon atoms includes an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-
Mono- or polyalkylstyrenes such as dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; halogenated alkylstyrenes such as p-bromomethylstyrene, p-chloromethylstyrene, p-trifluoromethylstyrene Bases; silylstyrenes such as p-trimethylsilylstyrene and p-triethylsilylstyrene; aromatic hydroxyl-containing styrenes such as p-hydroxystyrene; aliphatic hydroxyl-containing styrenes such as p-methylolstyrene; p- (N- Amino group-containing styrenes such as methylamino) styrene; double bond-containing styrenes such as p-allylstyrene and divinylbenzene; p-chlorostyrene, p-bromostyrene, p-fluorostyrene, pentafluorostyrene, o-fluoro Styrene, o-chlorostyrene, o-bromostyrene, 2,4,6-trifur Examples thereof include halogen-substituted styrenes such as orostyrene. These olefins can be used alone or in combination of two or more.

In the present invention, it is also possible to proceed with the polymerization in the presence of the following third olefin. Such olefins include propylene, 1-butene, 2-
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, Linear or branched α-olefins having 2 to 20 carbon atoms such as 1-hexadecene, 1-octadecene and 1-eicosene; cyclopentene, cycloheptene, norbornene,
5-methyl-2-norbornene, tetracyclododecene, 2-
A cyclic olefin having 3 to 20 carbon atoms such as methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; As an olefin of
Also included are vinylcyclohexane, dienes or polyenes. Examples of the diene or polyene include cyclic or chain compounds having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. Specifically, 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, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-
Methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like can be mentioned.

The olefin polymer has a weight average molecular weight of 20,000 or less, preferably 10,000 or less. Moreover, Mw / Mn is usually 1.1 to 4.5, preferably 1.5 to 3.0.

The weight-average molecular weight, number-average molecular weight and Mw / Mn (Mw; weight-average molecular weight, Mn; number-average molecular weight) were determined by using GPC (gel permeation chromatography) after dissolving in an orthodichlorobenzene solvent.
Measured at 140 ° C.

[0097]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The structure of the polymer obtained in the example was 270 MH
z, ¹ H- and ¹³ C-NMR (JEOL GSH-270
Type), GPC (Waters, alliance 2000) and the like. The introduction ratio of the terminal vinyl group was determined from ¹ H-NMR based on the integral ratio of the terminal vinyl group to the terminal methyl group {A (vinyl) / A (CH ₃ )} × 100. Hereinafter, specific examples will be described.

[Example 1] Internal volume 2 sufficiently purged with nitrogen
A 50 mL glass reactor was charged with 40 mL of toluene and 10 mL of distilled styrene, and the liquid and gas phases were saturated with ethylene. After the temperature was raised to 50 ° C., 1.0 mmol of methylaluminoxane in terms of aluminum atom was added, followed by 1.7 mg of zirconium complex bis [N- (3-t-butylsalicylidene) -n-hexylaminate] zirconium dichloride. The polymerization was started. Under normal pressure ethylene gas atmosphere (gas flow rate 100L / h),
After reacting for 1 minute, the supply of ethylene was stopped, and the polymerization was stopped by adding a small amount of methanol. After termination of the polymerization, the reaction product was poured into 600 mL of methanol to precipitate the entire amount of the polymer, and the polymer was recovered by filtration. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 1.03 g of a polymer was obtained. The polymerization activity per 1 mmol of zirconium was 517 g, and the styrene content of the polymer was 6.7 mol.
1% and weight average molecular weight of 10,100.

Example 2 In Example 1, the added zirconium complex was changed to 1.5 mg of bis [N- (3-tert-butylsalicylidene) -2-norbornylaminate] zirconium dichloride. Was similarly polymerized to obtain 0.25 g of a polymer. 1 mmol zirconium
The polymerization activity per unit was 125 g, the styrene content of the polymer was 5.2 mol%, the weight average molecular weight was 4,000, and the terminal vinyl group introduction ratio was 72%.

Example 3 In Example 1, the added zirconium complex was bis [N- (3-t-butylsalicylidene) anilinato] zirconium dichloride (1.4 mg).
Polymerization was carried out in the same manner, except that the polymer was changed to 0.1.
30 g were obtained. The polymerization activity per 1 mmol of zirconium was 150 g, the styrene content of the polymer was 2.2 mol%, the weight average molecular weight was 5,500, and the terminal vinyl group introduction ratio was 100%.

Example 4 In Example 1, the zirconium complex to be added was bis [N- (3-cumylsalicylidene) methylaminate] zirconium dichloride 1.4.
Polymerization was carried out in the same manner except that the amount was changed to mg, and 0.81 g of a polymer was obtained. The polymerization activity per 1 mmol of zirconium was 406 g, the styrene content of the polymer was 13.3 mol%,
Number average molecular weight 4,100, terminal vinyl group introduction rate 92%
Met.

Example 5 In Example 1, the zirconium complex to be added was bis [N- (3-t-butylsalicylidene) methylaminate] zirconium dichloride.
Polymerization was carried out in the same manner except that the polymerization time was changed to 2 mg and the polymerization time to 120 minutes, to obtain 0.30 g of a polymer. The polymerization activity per 1 mmol of zirconium was 38 g, the styrene content of the polymer was 24 mol%, the number average molecular weight was 5,200, and the terminal vinyl group introduction rate was 94%.

Example 6 In Example 1, the zirconium complex to be added was bis [N- (3-cumylsalicylidene) methylaminate] zirconium dichloride 1.6.
The polymerization was carried out in the same manner except that the polymerization time was changed to 10 mg, and 2.40 g of a polymer was obtained. Zirconium 1m
The polymerization activity per mol was 7,200 g, the styrene content of the polymer was 2.7 mol%, the number average molecular weight was 2,600, and the terminal vinyl group introduction rate was 70%.

[0104]

The polyethylene copolymer according to the present invention has a functional group such as a vinyl group at a terminal at a high introduction rate,
The side chain has a wide range of reactive substituents. The method for producing the copolymer according to the present invention can efficiently produce the copolymer under mild conditions.

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 4J100 AA02P AA03R AA04R AA05R                       AA07R AA09R AA15R AA16R                       AA17R AA18R AA19R AA20R                       AA21R AB02Q AB04Q AB07Q                       AB08Q AB09Q AB10Q AB15Q                       AB16Q AR04R AR05R AR09R                       AR11R AR22R AR25R AS01R                       AS02R AS03R AS04R AS11R                       AS21R BA03Q BA30Q BA72Q                       BB01Q BB03Q BB18Q CA04                       CA05 CA27 CA31 DA01 FA10                       HA35 HA62 HC09 JA15                 4J128 AA01 AB00 AB01 AC01 AC08                       AC26 AC46 AC47 AE02 AE05                       AF03 BA00A BA00B BA01B                       BB00A BB00B BB01B BC01B                       BC05B BC06B BC12B BC15B                       BC16B BC17B BC19B BC24B                       BC25B BC27B BC28B BC29B                       EA01 EB01 EB02 EB12 EB15                       EB21 EC02 EC04 GA01 GA26                       GB01

Claims (4)

[Claims] [Claim 1] A compound represented by the following general formula (1), which has a reactive group (Y) at at least one main chain terminal and an aromatic group (Z) and a substituent ( An ethylene polymer having a weight average molecular weight of 20,000 or less having T ¹ and T ² ). Embedded image (Wherein, T ¹ and T ² are a hydrogen atom, a group selected from alkyl and alkenyl groups, T ¹ and T ² are good .Y be taken together, form a ring functional group having a double bond , Z represents an aromatic group, and a, b, c, and d each represent a number of 0 or more that satisfies the weight average molecular weight of the polymer of 20,000 or less.) 2. The ethylene polymer according to claim 1, wherein Y is at least one reactive group selected from a vinyl group, a vinylene group and a vinylidene group. 3. The ethylene polymer according to claim 1, wherein Z is a phenyl group or a nucleus-substituted phenyl group. 4. In the presence of a catalyst comprising a transition metal compound [A] represented by the following general formula (2) or a transition metal compound [B] represented by the following general formula (3), ethylene and C 8 -C 8 are present. From α-olefins having 20 aromatic groups,
A method for producing the ethylene-based polymer according to claim 1. Embedded image (Wherein, R ^{1 to} R ³ represent 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, a phosphorus-containing group, and a silicon-containing group. Group, a germanium-containing group or a tin-containing group,
Two or more of these may be linked to each other to form a ring, and R ^{1 to} R contained in any one of the ligands
^And one of R ¹ to R ¹ contained in another ligand.
May form a bonding group or a single bond between one group of ^3, n is a number satisfying the valence of M ^1, M ¹ is Ti, Zr or Hf, X is 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 group, germanium 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 connected to each other to form a ring May be. ) (Wherein, M ² is Fe or Co, and R ⁴ is 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, Represents a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, n is a number satisfying the valence of M ² , X is a hydrogen atom, a halogen atom, a 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 group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be connected to each other to form a ring. )