JP3129341B2 - Olefin copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based copolymer and a method for producing the same, and more particularly, to a method of introducing a reactive unsaturated group into a polyolefin chain, thereby improving adhesiveness and compatibility with other resins. The present invention relates to a novel high-strength olefin copolymer capable of obtaining an excellent polyolefin material and a method for efficiently producing the olefin copolymer.

[0002]

2. Description of the Related Art Conventionally, olefin polymers such as high-density polyethylene, isotactic polypropylene, and linear low-density polyethylene have been developed by utilizing various characteristics such as chemical stability, good mechanical properties, and processing characteristics. It has application fields in molded articles, films, sheets, fibers, synthetic paper and other various fields. In order to utilize these olefin polymers more highly, attempts have been made for many years to improve the performance by a copolymerization reaction, or to modify or impart functionality by a polymer reaction.

[0003] That is, a method by copolymerization of ethylene and a branched 1,4-diene is disclosed in Japanese Patent Application Laid-open No. Sho 56-30413. This method makes it possible to produce a copolymer having a 1,1-disubstituted olefin in the side chain (that is, having a pendant olefin) by using bifunctional olefins having different reactivities. But,
This pendant olefin has the disadvantage that it is susceptible to chemical reaction restrictions due to its branched structure. For example, it is extremely difficult to perform a graft reaction with a polar monomer, an olefin, or the like. Further, Polymer Bulltein 10, 109 (1983) discloses a similar copolymerization method. However, this method has an advantage that a gelation reaction is relatively unlikely to occur, but when a high concentration of unsaturated group is contained, a gel is substantially formed, which is not preferable.

A method based on copolymerization of an α-olefin and divinylbenzene is disclosed in Japanese Patent Application Laid-Open No. 1-118510.
It is disclosed in Japanese Patent Application Laid-Open No. 1-123811. However, since divinylbenzene has the same double bond in reactivity, it has a drawback that a cross-linking reaction occurs in the course of copolymerization with an α-olefin, and it is easily insoluble and infusible. Then, the conversion of divinylbenzene into a copolymer is low, and many divinylbenzene monomers remain in the copolymer. Therefore, when a graft reaction is subsequently performed, it is necessary to remove the monomers, which causes a problem in production. Furthermore, pendant olefins have the disadvantage that they become styrenic monomers and are restricted by the graft reaction of olefins and the like.

In the case of using ω-alkenyl styrene, an o-allyl-styrene system described in Kobunshi Kagaku Vol. 29, No. 328, 593 (1972) uses a conventional anionic polymerization catalyst or cationic polymerization catalyst. It has been reported that when o-allyl-styrene is homopolymerized using, a catalyst species develops structural selectivity. However, it is difficult to produce olefin copolymers with these catalyst systems. Japanese Patent Application Laid-Open No. Sho 62-95303 discloses a similar copolymer, which is a long-chain branched polyethylene copolymer having a low density because it is a high-pressure radical polymerization. . Therefore, there is a disadvantage that strength and elastic modulus are low. Thus, there is no satisfactory state of the art in the related art.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present inventors
Developed an olefin copolymer with excellent modifiable strength that solves the above-mentioned disadvantages of the prior art and has excellent adhesiveness and can obtain a polyolefin material with excellent compatibility with other resins. I did my utmost research. As a result, they have found that by introducing a reactive unsaturated group into a polyolefin chain under specific conditions, an olefin-based copolymer having the above-mentioned properties can be obtained. The present invention has been completed based on such findings.

[0007]

That is, the present invention provides a compound represented by the general formula (I):

[0008]

Embedded image

Wherein R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ and R ⁴ each represent A hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms. M is an integer of 0 to 4) and a repeating unit derived from an olefin, and a polyolefin length. An object of the present invention is to provide an olefin copolymer having no chain branch. In addition, the present invention relates to (A) a compound represented by the general formula (II):

[0010]

Embedded image

Wherein R ¹ , R ² , R ³ , R ⁴ and m
Is the same as above. A) a styrene-based monomer represented by formula (1) and an olefin (B), a catalyst comprising a transition metal compound and an aluminoxane as main components; a catalyst comprising a transition metal compound and a halogen-substituted organometallic compound as main components; And a method for producing an olefin-based copolymer having no long-chain branched polyolefin, characterized by copolymerizing in the presence of a catalyst containing a compound capable of forming an ionic complex as a main component. Things.

The olefin copolymer of the present invention has the above-mentioned properties.
Whether the olefin is a repeating unit represented by the general formula (I)
And a repeating unit derived therefrom. And the above
The repeating unit represented by the general formula (I) has the general formula
Derived from the styrenic monomer represented by the formula (II)
You. Styrene monomer represented by this general formula (II)
Is an α-olefin unit and a styrene unit in one molecule.
There is no particular limitation as long as it is a monomer present in
Various things can be used. Where the general formula
In (I) or (II), R¹Is a divalent carbon having 1 to 20 carbons
A hydride group, for example, an alkylene group having 1 to 20 carbon atoms,
Arylene group having 6 to 20 carbon atoms, alkyl having 7 to 20 carbon atoms
It represents an arylene group or an arylalkylene group. Ingredient
Physically, methylene, ethylene, propylene,
Tylene group, pentenylene group, hexylene group, phenylene
Group or tolylene group. Also, R ^TwoIs a haloge
Atom (eg chlorine, bromine, fluorine, iodine) or carbon number
1-8 monovalent hydrocarbon groups (eg, methyl, ethyl
Group, propyl group, butyl group, pentyl group, etc.
Groups such as saturated hydrocarbon groups or vinyl groups
An unsaturated hydrocarbon group), and m is an integer of 0 to 4.
And R^ThreeAnd R^FourAre a hydrogen atom and a halogen, respectively.
Atom (eg chlorine, bromine, fluorine, iodine) or carbon number 1
To 8 monovalent hydrocarbon groups (eg, methyl group, ethyl group,
For alkyl groups such as propyl, butyl, and pentyl
Unsaturation such as a typical saturated hydrocarbon group or vinyl group
(Japanese hydrocarbon group). Stille represented by general formula (II)
As the monomeric monomer, specifically, R in the general formula (II)
¹Is an alkylene group, for example, p- (2-pro
Phenyl) styrene, m- (2-propenyl) styrene, p
-(3-butenyl) styrene, m- (3-butenyl) styrene
, O- (3-butenyl) styrene, p- (4-pentenyl)
Le) styrene, m- (4-pentenyl) styrene, o- (4
-Pentenyl) styrene, p- (7-octenyl) styrene
, P- (1-methyl-3-butenyl) styrene, p- (2
-Methyl-3-butenyl) styrene, m- (2-methyl-
3-butenyl) styrene, o- (2-methyl-3-butenyl)
G) styrene, p- (3-methyl-3-butenyl) styrene
, P- (2-ethyl-3-butenyl) styrene, p- (2
-Ethyl-4-pentenyl) styrene, p- (3-butenyl)
) -Α-methylstyrene, m- (3-butenyl) -α-
Methylstyrene, o- (3-butenyl) -α-methylsty
Len and the like can be mentioned. Further, R in the general formula (II)
¹Is an arylene group, for example, 4-vinyl-
4 '-(3-butenyl) biphenyl, 4-vinyl-3'-
(3-butenyl) biphenyl, 4-vinyl-4 '-(4-
Pentenyl) biphenyl, 4-vinyl-2 '-(4-pen
(Tenyl) biphenyl, 4-vinyl-4 '-(2-methyl-
(3-butenyl) biphenyl and the like.

On the other hand, there are various types of repeating units derived from olefins in the present invention, but in general, repeating units derived from ethylene, α-olefin, halogen-substituted (α-) olefin, cyclic olefin, etc. Is a unit. Of the olefins, α-olefins usually have 3 to 20 carbon atoms, for example, propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; 1; 3-
Methylbutene-1; 4-phenylbutene-1; 3-methylpentene-1; 4-methylpentene-1; 3-methylhexene-1; 4-methylhexene-1; 5-methylhexene-1; 6-phenylhexene -1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1;
4,4-dimethylpentene-1; vinylcyclohexene; vinylcyclohexane and the like. The halogen-substituted (α-) olefin usually has 2 to 20 carbon atoms, for example, fluoroethylene;
1,1-difluoroethylene; trifluoroethylene;
Tetrafluoroethylene; 2-fluoropropene; 3-
Fluoropropene; hexafluoropropene; 3,4-
Dichlorobutene-1 and the like can be mentioned. And
The cyclic olefin usually has 3 to 20 carbon atoms, for example, cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene; 5,6-dimethylnorbornene; -Trimethylnorbornene, 5-
Ethyl norbornene, 5-propylnorbornene, 5-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene and the like.

The olefin-based copolymer of the present invention has no polyolefin long-chain branching (ie, is substantially linear) and contains a repeating unit represented by the general formula (I). The amount is from 10 ^{-6 to} 95 mol%, preferably from 10 ^-4 to 70 mol%, particularly preferably from 10 ^-4 to 50 mol%. However, it does not gel even at 5 mol% or more. Then, the reduced viscosity at a concentration of 0.05 g / dl measured at 135 ° C. in 1,2,4-trichlorobenzene is from 0.01 to 0.01 g / dl.
30 dl / g, preferably 0.1 to 20 dl / g. If the reduced viscosity is less than 0.01 dl / g, the mechanical strength becomes insufficient, which is not preferable. In addition, the reduced viscosity is 3
If it exceeds 0 dl / g, the moldability deteriorates, which is not preferable. The present invention has a great feature that a copolymer substantially free of gel can be obtained even when the content of the repeating unit represented by the general formula (I) exceeds 5 mol%. are doing. Therefore, the range of application when producing a graft copolymer using this copolymer is expanded.

[0015] The olefin copolymer of the present invention having such characteristics can be produced by various methods.
Among them, (A) a styrene-based monomer represented by the general formula (II) and (B) an olefin are used as a copolymer component, and (a) a transition metal compound, (b) an aluminoxane, c) halogen-substituted organometallic compounds,
(D) The present invention comprises a compound or the like which is capable of forming an ionic complex by reacting with the transition metal compound as a main component, and is copolymerized in the presence of a catalyst in which the (a) transition metal compound is combined with each other. An olefin copolymer can be produced efficiently. Here, a particularly effective catalyst is a catalyst mainly composed of a transition metal compound and an aluminoxane, or a catalyst mainly composed of a transition metal compound and a halogen-substituted organometallic compound, or reacting with the transition metal compound and the transition metal compound. And a catalyst containing a compound capable of forming an ionic complex as a main component.

[0016] Here, there are various transition metal compounds, preferably in the following general formula ^{(III) M 1 (R 5} ) n ··· (III) ( wherein, M ¹ is, IVB Group A metal belonging to the group V or VI such as vanadium, niobium, tantalum or chromium, wherein R ⁵ is a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms;
20 aryl groups, alkylaryl groups or arylalkyl groups; an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, an acetylacetonate group, a substituted acetylacetonate group, a substituent containing a silicon atom, or carbonyl; Ligands such as oxygen molecules, nitrogen molecules, Lewis bases, chain unsaturated hydrocarbons or cyclic unsaturated hydrocarbons,
A cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group, and when n is 2 or more, a plurality of R ⁵ may be the same or different. Here, n represents the valence of M ¹ , but may be more than that, and is usually an integer of 2 to 5. ) Is at least one compound selected from the transition metal compounds. Among these transition metal compounds, those in which M ¹ in the general formula (III) is titanium, zirconium, hafnium, vanadium or chromium are preferably used.

Here, among the compounds represented by R ⁵ in the general formula (III), the halogen atom is specifically a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group and a 2-ethylhexyl group; A methoxy group, an ethoxy group, a popoxy group, a butoxy group, a phenoxy group; an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group includes a phenyl group,
Tolyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing a silicon atom; dimethyl ether, diethyl ether as Lewis base , Ethers such as tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as benzonitrile, trimethylamine, triethylamine, tributylamine; N, N-dimethylaniline, pyridine; 2,2′-bipyridine , Phenanthroline and other amines; phosphines such as triethylphosphine and triphenylphosphine; and linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, -Hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene,
Examples thereof include cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group; a 1,2-dimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. Enyl group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group;
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. Further, the ligand of R ⁵ may form a crosslinked body by a covalent bond between the ligands. Examples of the crosslink by covalent bonding include methylene crosslink, dimethylmethylene crosslink, dimethylsilylene crosslink, dimethylgermylene crosslink, and dimethylstannylene crosslink.

[0018] Among the above general formula (III) transition metal compounds represented by Specific examples of the titanium compound M ¹ is titanium, tetramethoxy titanium, tetraethoxy titanium, tetra -n- butoxy, tetraisopropoxy Titanium, titanium tetrachloride, titanium trichloride, titanium dichloride, titanium hydride, cyclopentadienyl trimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, cyclopentadienyl tributyl titanium, methyl cyclopenta Dienyltrimethyltitanium; 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium Pentamethylcyclopentadienyltributyltitanium, cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopentadienylmethyltitanium dichloride, pentamethylcyclopentadienylethyltitanium dichloride, cyclopentadienyl Dimethyl titanium monochloride; cyclopentadienyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, penta Methylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitanium triethoxide,
Pentamethylcyclopentadienyl titanium tripropoxide, pentamethylcyclopentadienyl titanium tributoxide, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclo Pentadienylmethoxytitanium dichloride, cyclopentadienyldimethoxytitanium chloride,
Pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium, pentamethylcyclopentadienylmethyldiethoxytitanium, indenyltitaniumtrichloride, indenyltitaniumtrimethoxide, indenyltitaniumtriethoxide, indet Niltrimethyltitanium, indenyltribenzyltitanium and the like.

Further, among the transition metal compounds represented by the general formula (III), specific examples of the zirconium compound in which M ¹ is zirconium include dicyclopentadienyl zirconium dichloride, tetrabutoxy zirconium, zirconium hydride, Zirconium tetrachloride, tetraphenyl zirconium, cyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trimethoxide, cyclopentadienyl tribenzyl zirconium, pentamethylcyclopentadienyl tribenzyl zirconium, bisindenyl zirconium Dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxy zirconium chloride, triisopropoxy zirconium chloride, (pentamethy (Cyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium , (Cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium,
(Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl)
Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium,
(Trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl)
Trichloro zirconium, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) ) Dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis ( Methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethyldi Conium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclopentadienyl) hydride Methyl zirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl)
Dichlorozirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadiene Enil)
Dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium,
Isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl Zirconium, ethylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopencil (9-fluorenyl)
(Cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5- Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium and the like.

Similarly, specific examples of the hafnium compound in which M ¹ is hafnium include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, and pentamethyl Cyclopentadienyl tribenzyl hafnium, bisindenyl hafnium dichloride, hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxy hafnium chloride, triisopropoxy hafnium chloride, hafnium tetrachloride, dicyclopentadienyl hafnium dichloride, tetraethoxy hafnium, etc. Is mentioned. Similarly, specific examples of the vanadium compound in which M ¹ is vanadium include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate,
Vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium trichloride, And dicyclopentadienylmethyl vanadium.

Similarly, specific examples of the niobium compound in which M ¹ is niobium include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethylmethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium. Trichloride, pentabutoxyniobium and the like, and similarly, specific examples of the tantalum compound include:
Tantalum pentachloride, dichlorotrimethyl tantalum, dicyclopentadienyl tantalum trihydride, pentabutoxy niobium, etc. Similarly, specific examples of the chloro compound include chromium trichloride, tetrabutoxy chrome, tetramethyl chromium, dicyclo Examples thereof include pentadienyl chromium, dibenzene chromium, chromium acetate, chromium stearate, and chromyl chloride. In addition, the transition metal compound is a magnesium compound, an aluminum compound,
A supported catalyst supported on a carrier such as a silicon compound can also be used. Further, those in which the transition metal compound is modified with an electron donating compound can also be used.

Next, among the catalyst components, aluminoxane is a contact product obtained by contacting an organoaluminum compound with a condensing agent. Here, as the organic aluminum compound, usually, the general formula _{^{(IV) AlR 6 3 ··· (}} IV) ( wherein, R ⁶ is. Represents an alkyl group having 1 to 8 carbon atoms) an organoaluminum compound represented by the It is. Specific examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is most preferred.

As the condensing agent, water is typically mentioned. In addition, any condensing agent capable of condensing the above-mentioned trialkylaluminum, such as copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, etc. And the like.
Examples of the aluminoxane used in the present invention include a contact product of a trialkylaluminum represented by the general formula (IV) as an organoaluminum compound and water as a condensing agent. Specifically, the following general formula (V)

[0024]

Embedded image

(Wherein p represents the degree of polymerization, 0 to 50, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, preferably a methyl group.) The following general formula (VI)

[0026]

Embedded image

(Wherein q represents the degree of polymerization, 2 to 50, and R ⁷ is the same as described above), and a cyclic alkylaluminoxane having a repeating unit represented by the formula:

In general, a contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with an unreacted trialkylaluminum and various condensation products together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane. Are molecules in which these are intricately associated, and these are various products depending on the contact conditions between the trialkylaluminum and water as a condensing agent. The method of contacting the alkyl aluminum compound with water at this time is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and a method in which water is added later, and further contained in a metal salt or the like There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with an organoaluminum compound. The water contains amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite.
It may be contained up to about 0%. Although this reaction proceeds even without solvent, it is preferably carried out in a solvent. Suitable solvents include aliphatic hydrocarbons such as hexane, heptane and decane and aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned.

Aluminoxane (for example, alkylaluminoxane), which is a contact product of such an organoaluminum compound and a condensing agent, is subjected to the above-mentioned contact reaction. The filtrate is heat-treated at normal temperature or reduced pressure at a temperature of 30 to 200 ° C, preferably 40 to 150 ° C, for 20 minutes to 8 hours, preferably 30 minutes to 5 hours while distilling off the solvent. Is preferred. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. In general, when the temperature is lower than 30 ° C., no effect is exhibited, and when the temperature is higher than 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferable. And
Depending on the processing conditions of the heat treatment, the reaction product is obtained in the form of a colorless solid or solution. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution.

A preferred example of an aluminoxane, particularly an alkylaluminoxane, which is a contact product of an organoaluminum compound used as a catalyst component and a condensing agent is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on the CH ₃ ) bond is 50% or less. In other words, at room temperature of the above contact product, when observing the proton nuclear magnetic resonance ⁽¹ H-NMR) spectra in toluene solvent, methyl proton signal based on the "Al-CH _3" is tetramethylsilane (TMS) standard In the range of 1.0 to -0.5 ppm. Since the TMS proton signal (0 ppm) is in the methyl proton observation region based on “Al-CH ₃ ”, this “Al-C 3
The methyl proton signal based on “H ₃ ” was calculated as 2.35 ppm of the methyl proton signal of toluene based on TMS.
And the high magnetic field component (that is, -0.1 to -0.5 ppm)
) And other magnetic field components (i.e., 1.0 to -0.1 ppm), those having a high magnetic field component of 50% or less, preferably 45 to 5% of the whole are suitably used as catalyst components. Can be used.

Among the above-mentioned catalyst components, as the halogen-containing organometallic compound, a compound represented by the general formula (VII) (R ⁸ ) _t M ² (X) _it (VII) is used. In the general formula (VII), R ⁸ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a carbon atom. Number 7
-20 represents an aralkyl group. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples thereof include an n-butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. Also, M ²
Means lithium, sodium, potassium, magnesium,
Zinc, cadmium, aluminum, boron, gallium,
Indicates silicon or tin. Further, X represents a halogen atom, that is, a chlorine atom, a bromine atom, an iodine atom, or the like. And i is the valence of M ² , usually 2 to 5
And t is a real number satisfying 0 <t <i, and indicates various values. As the compound represented by the general formula (VII),
There are various things. Specifically, for example, alkyl halogeno magnesium compounds such as ethylchloromagnesium and ethyl bromomagnesium, alkyl halogenogallium compounds such as diethylchlorogallium and ethyldichlorogallium, alkylhalogenoborane compounds such as diethylchloroboron, tributylchlorotin, tributylchlorotin And alkylhalogenotin compounds such as phenylchlorotin. When M ² is aluminum, there are various compounds. Specifically, for example, diethylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, diisopropylaluminum monochloride,
Examples thereof include dialkylaluminum monohalides such as diisobutylaluminum monochloride and dioctylaluminum monochloride, and alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, and butylaluminum sesquichloride.

Further, among the catalyst components, the type of the compound capable of forming an ionic complex by reacting with the transition metal compound is not necessarily limited. Ritsuyo VB, VIB
A coordination complex compound comprising an anion bonded to an element selected from Group IV, Group VIIB, Group VIII, Group IB, Group IIB, Group IIIA, Group IVA and Group VA can be suitably used. That is, as the coordination complex compound that can be suitably used, general formula (VIII) or (IX) ([L ¹ -R ⁹ ] ^{u +} ) _v ([M ³ Z ¹ Z ² ... Z ^e ] _{^{(ef) -) w ··· (}} VIII) ( [L ^{2] u +)} _v ^{([M 4 Z 1 Z 2 ··· Z} e ] _{^{(ef) -) w ··· (}} IX) ( where, L ^{2 M 5, R 10 R 11 M} 6, R 12 3 C or R ¹³
It is an M ^6. Wherein L ¹ is a Lewis base, M ³ and M ⁴ are VB, VIB, VIIB, VIII, IB and II of the periodic table, respectively.
An element selected from group B, IIIA, IVA and V, M ⁵
And M ⁶ are groups IIIB, IV, V, VI of the periodic table, respectively.
An element selected from the group B, VIIB, VIII, I, IB, IIA, IIB, and VIIA, and Z ^{1 to} Z ^e each represent a hydrogen atom, a dialkylamino group, an alkoxy group,
Alkoxy group having 20 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen substitution having 1 to 20 carbon atoms hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group or a halogen atom, Z ¹ to Z ^e is may form a ring of two or more thereof with each other. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹⁰ and R ¹¹ are each a cyclopentadienyl group,
A substituted cyclopentadienyl group, indenyl group or fluorenyl group, and R ¹² represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. f is an valence of M ³ or M ⁴ and is an integer of 1 to 7, e is an integer of 2 to 8, and u is [L ¹ −
R ⁹ ] and [L ² ] are ionic valences and are integers from 1 to 7, and v is 1
The above integer, w = (v × u) / (ef). ] It is a compound represented by these.

[0033] Here, specific examples of the Lewis base represented by L ^1, ammonia, methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, tri -n- butylamine, N , N-dimethylaniline, methyldiphenylamine, pyridine;
Amines such as 2'-bipyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline and phenanthroline; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; Examples thereof include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran oxane; thioethers such as diethyl thioether and tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Further, specific examples of M ³ and M ⁴ include:
B, Al, Si, P, As, Sb , etc. Specific examples of M ⁵ are, Li, Na, Ag, Cu , Br, I, I 3 , etc., M
Specific examples of ⁶ include Mn, Fe, Co, Ni, Zn and the like. Specific examples of Z ¹ to Z ^e is, for example,
Dimethylamino group, diethylamino group as a dialkylamino group; methoxy group, ethoxy group, n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; phenoxy group, 2,6-dimethylphenoxy as an aryloxy group having 6 to 20 carbon atoms Group, naphthyloxy group; alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-octyl group, 2-ethylhexyl group; 20 aryl, alkylaryl or arylalkyl groups such as phenyl, p-tolyl, benzyl, pentafluorophenyl, 3,5-di (trifluoromethyl)
Phenyl group, 4-tert-butylphenyl group, 2,
6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group, 1,2-dimethylphenyl group;
P-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoro A methyl) phenyl group; F, Cl, Br,
l; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁹ and R ¹² include the same as those described above. R ¹⁰ and R ¹¹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 4.

Among the compounds of the above general formulas (VIII) and (IX), those wherein M ³ and M ⁴ are boron are preferred. General formula (V
Among the compounds of III) and (IX), specifically, the following compounds can be particularly preferably used. For example, compounds of the general formula (VIII) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) tetraphenylborate Ammonium, benzyltriphenylborate tri (n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyl tetraphenylborate Methylsulfonium, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl)
Tetraethylammonium borate, tetra (pentafluorophenyl) borate [methyltri (n-butyl) ammonium] borate, tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetra (pentafluorophenyl) borate, Methyltriphenylammonium (pentafluorophenyl) borate, dimethyldiphenylammonium tetra (pentafluorophenyl) borate, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate Anilinium, trimethylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate (m-d Roanilinium), dimethyl tetra (pentafluorophenylmethyl) borate (p-bromoanilinium), pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetrafelphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-
Dimethylanilinium ditrifluoromethylphenyl) borate, triethylammonium tow hexafluoroarsenate, and the like.

On the other hand, compounds of the general formula (IX) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate, Decamethylferrocenium (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, tetra ( Silver pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate , Silver hexafluoroarsenate, and silver hexafluoroantimonate tow. As compounds other than the general formulas (VIII) and (IX), for example, tri (pentafluorophenyl) boric acid, tri [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid and the like are also used. be able to.

The catalyst used in the production method of the present invention comprises the above-mentioned transition metal compound and other components as main components,
They are used in combination. Among them,
In particular, the olefin copolymer of the present invention can be efficiently produced when used in combination as follows. That is, a catalyst mainly composed of a transition metal compound (a) and an aluminoxane (b). A catalyst mainly composed of a transition metal compound (a) and a halogen-substituted organometallic compound (c). It is a catalyst comprising a catalyst containing a compound (d) as a main component which can form an ionic complex by reacting with a metal compound. Although the addition ratio of each component in the catalyst is not particularly limited, in a catalyst containing a transition metal compound (a) and an aluminoxane (b) as main components, the molar ratio of the component (a):
1:20 to 1: 10,000, especially 1: 100 to 1: 2.0
00 is preferable. In the catalyst containing the transition metal compound (a) and the halogen-substituted organometallic compound (c) as main components, the molar ratio of the component (a) to the component (c) is 1: 0.5 to 1: 1000, Especially 1:10 to 1: 5
00 is preferable. Further, in a catalyst containing a transition metal compound (a) and a compound (d) capable of reacting with the transition metal compound to form an ionic complex as a main component, the molar ratio of the component (a) to the component (d) is changed. , 1: 0.01-
The ratio is preferably set to 1: 100, particularly 1: 1 to 1:10. When the olefin-based copolymer of the present invention is produced using these catalysts, the ratio of each component of the catalyst to the styrene-based monomer is not particularly limited, but based on the transition metal compound, the transition metal compound: The molar ratio of the styrene monomer is from 1:10 to 1:10 ⁹ , especially 1: 1.
0 ^2-1: is preferably 10 ^7. The order of addition of each component of these catalysts is not particularly limited. In the present invention, an organometallic compound can be mixed and used as desired with the above-mentioned catalyst which can efficiently produce an olefin-based copolymer.

As the organometallic compound which can be mixed and used as desired with the catalyst, a compound represented by the general formula (X) M ⁷ (R ¹⁴ ) _p ... (X) is used. In the general formula (X), R ¹⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or carbon atom. Number 7
-20 represents an aralkyl group. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples thereof include an n-butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. And M
⁷ represents lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon or tin. P represents the valence of M ² . There are various compounds represented by the general formula (X). Specifically, for example, alkyllithium compounds such as methyllithium, ethyllithium, propyllithium, and butyllithium; alkylmagnesium compounds such as diethylmagnesium, ethylbutylmagnesium, and dinormalbutylmagnesium; dimethylzinc, diethylzinc, dipropylzinc, Dialkyl zinc compounds such as dibutyl zinc, trimethyl gallium,
Examples thereof include alkyl gallium compounds such as triethyl gallium and tripropyl gallium; alkyl boron compounds such as triethyl boron, tripropyl boron and tributyl boron; and alkyl tin compounds such as tetraethyl tin and tetraphenyl tin. When M ⁷ is aluminum, there are various compounds. Specifically, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum,
Examples thereof include trialkylaluminum compounds such as tri-n-hexylaluminum and trioctylaluminum.

The olefin copolymer of the present invention is produced by copolymerizing the styrene monomer and an olefin in the presence of any of the above catalysts. About the copolymerization of the styrene monomer and the olefin,
The polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent and the like may be appropriately selected. That is, as the copolymerization method,
Examples thereof include slurry polymerization, solution polymerization, bulk polymerization, and gas phase polymerization, and may be any of continuous polymerization and discontinuous polymerization. Here, in the solution polymerization, benzene,
Aromatic hydrocarbons such as toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, pentane, hexane,
Aliphatic hydrocarbons such as heptane and octane can be used. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight or composition of the obtained copolymer may be controlled by a commonly used method. Molecular weight control, for example,
It can be controlled by hydrogen, temperature, monomer concentration, etc. The composition can be controlled, for example, by terpolymerization with ethylene and propylene, for example, by changing the monomer charge ratio and the type of catalyst. Further, the control of the random and block structures produces a highly random copolymer when copolymerization is carried out in the presence of a monomer. In addition, when the homopolymerization is performed in advance, and then the comonomer component is added to proceed with the copolymerization, a copolymer having a high blocking property can be obtained. As the stereoregularity, those having an isotactic structure, a syndiotactic structure, and an atactic structure can be obtained.

[0040]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited by the following examples. Example 1 (1) Preparation of methylaluminoxane In a glass container having an inner volume of 500 ml and being purged with argon,
Toluene 200 ml, copper sulfate pentahydrate (CuSO ₄ · 5H
17.8 g (71 mmol) of ₂ O) and 24 ml (250 mmol) of trimethylaluminum were added and reacted at 40 ° C. for 8 hours. Thereafter, toluene was further distilled off from the solution obtained by removing the solid components under reduced pressure to obtain 6.7 g of a catalyst product (methylaluminoxane). Its molecular weight measured by freezing point depression method was 610. Further, ¹ H-N based on JP-A-62-325391 is disclosed.
When the proton nuclear magnetic resonance spectrum is observed in a toluene solution at room temperature at a high magnetic field component by MR measurement, the methyl proton signal based on the “Al—CH ₃ ” bond is 1.0 to −0.5 pp based on tetramethylsilane.
m. Since the proton signal (0 ppm) of tetramethylsilane is in the observation region based on the methyl proton based on the “Al—CH ₃ ” bond, this “Al
The methyl proton signal based on the —CH ₃ ”bond was measured based on 2.35 ppm of the methyl proton signal of toluene based on tetramethylsilane, and the high magnetic field component (i.e., -0.1 to -0.5 ppm) and other The magnetic field component (ie,
(1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

(2) Production of copolymer Toluene 1 was placed in a reaction vessel having an internal volume of 500 ml and equipped with a stirrer.
Then, 20 ml of p- (3-butenyl) styrene and 20 mmol of methylaminoxane prepared in the above (1) were added thereto.
Millimol was added, immersed in a thermostat at 50 ° C., and stirring was started. To this, 0.01 mmol of dicyclopentadienyltitanium dichloride was added, and ethylene was added at 1.0 kg / cmG.
For 2 hours. After completion of the reaction, unreacted gas was removed, and the polymer was washed with methanol, and 3.93 g of a white polymer was obtained.
I got FIG. 1 shows the IR absorption spectrum of the obtained polymer. 1, which is based on p- (3-butenyl) styrene residue
Only the stretching vibration of the carbon-carbon double bond of the olefin unit at 640 cm ^-1 was observed. Further, when ¹ H-NMR was measured, unreacted olefins were found to be 4.8 to 5.1 and 5.7 to 6.
It was found at 0 ppm. This clearly indicates an olefin derived from the p- (3-butenyl) group. The melting point of the copolymer was measured and found to be 122 ° C. This indicates that the methylene chain is disturbed, that is, the copolymer is randomly copolymerized. Furthermore, the reduced viscosity (1, 2, 4
-In trichlorobenzene, 135 ° C, concentration 0.05 g / d
Measured by l: The same applies hereinafter. ) Is 0.19 dl / g, and the content of p- (3-butenyl) styrene in the copolymer is ¹ H-NMR.
Was 17.0 mol%.

Example 2 A copolymer was prepared in the same manner as in Example 1- (2) except that dicyclopentadienylzirconium dichloride was used instead of dicyclopentadienyltitanium dichloride. As a result, the copolymer yield was 5.94.
g, p- (3-butenyl) styrene content: 15.2 mol%, melting point: 128 ° C., reduced viscosity: 0.67 dl / g.
As in Example 1, the IR absorption spectrum contained 1,640
There was an absorption due to one type of carbon-carbon bond in cm- ¹ . Example 3 In Example 1- (2), dicyclopentadienylzirconium dichloride was used in place of dicyclopentadienyltitanium dichloride, and propylene was saturated at 0.5 kg / cm ² G before ethylene was introduced. 0.5 more ethylene
Ternary copolymerization was carried out in the same manner as in Example 1 except that the introduction was carried out at kg / cm ² G. As a result, the copolymer yield was 5.9.
4g, also symmetric deformation vibration of methyl groups attributed to propylene 1380 cm ^-1 in the IR absorption spectrum, rocking vibration of methine attributed to ethylene was observed near 720~730cm ^-1. Furthermore, as in Example 1- (2), 164
At 0 cm ^-1 there was an absorption due to the carbon-carbon double bond.
The copolymer composition was 73.2 mol% ethylene, 1 propylene.
4.0 mol%, p- (3-butenyl) styrene 12.8 mol%, reduced viscosity 0.078 dl / g, melting point 99 ° C. Example 4 In Example 3, 3 ml of a 6.7 mol / l toluene solution of 2-norbornene was used in place of propylene, the ethylene pressure was 2.0 kg / cm ² G, and p- (3-butenyl) styrene was 8 mmol. Except for this, terpolymerization was carried out in the same manner as in Example 3. As a result, the copolymer yield was 3.22.
g, copolymer composition: 95.8 mol% of ethylene, 2.2 mol% of 2-norbornene, p- (3-butenyl) styrene 2
Mol%, reduced viscosity 0.77 dl / g, melting point 110 ° C. Further, similarly to Example 1- (2), absorption based on a carbon-carbon double bond was present at 1640 cm ^-1 .

Example 5 (1) Tri-n-tetra (pentafluorophenyl) borate
Preparation of butyl ammonium pentafluorophenyl lithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) is reacted with 45 mmol of boron trichloride in hexane to convert tri (pentafluorophenyl) boron to white. Obtained as a solid. By reacting 41 mmol of this tri (pentafluorophenyl) boron with 41 mmol of lithium pentafluorophenyl, lithium tetra (pentafluorophenyl) borate was obtained as a white solid. Next, 16 mmol of lithium tetra (pentafluorophenyl) borate and 16 mmol of tri-n-butylammonium hydrochloride were reacted in water to obtain 12.8 mmol of tri-n-butylammonium tetra (pentafluorophenyl) borate as a white solid. Could be obtained.

(2) Production of copolymer In the same manner as in Example 1- (2), 100 ml of toluene and p-
8 mmol of (3-butenyl) styrene, 0.5 mmol of triisobutylaluminum and 0.02 mmol of the boron compound prepared in the above (1) were added. To this, 0.01 mmol of dicyclopentadienyl zirconium chloride was added, and ethylene was copolymerized at 1.0 kg / cm ² G for 2 hours. After the completion of the reaction, the unreacted gas was removed, and the polymer was washed with methanol to obtain 3.9 g of a white polymer. The IR absorption spectrum shows that 1-attributable to p- (3-butenyl) styrene residue.
Only the stretching vibration of the carbon-carbon double bond of the olefin unit at 640 cm ^-1 was observed. Further, when the melting point was measured, it was 91.9 ° C., indicating that the ethylene chain was disturbed, that is, random copolymerization was performed. The reduced viscosity was 0.38 dl / g. The copolymer composition is ¹ H-
As a result of NMR analysis, the content of p- (3-butenyl) styrene was 36.0 mol%.

Example 6 A copolymerization was carried out in the same manner as in Example 5 except that dicyclopentadienyl hafnium dichloride was used instead of dicyclopentadienyl zirconium chloride. As a result, the copolymer yield was 3.95 g, p
The content of-(3-butenyl) styrene was 19.6 mol%, the melting point was 105 ° C, and the reduced viscosity was 0.31 dl / g. As in Example 1- (2), the IR absorption spectrum contained 1,640
There was an absorption due to one type of carbon-carbon double bond at cm- ¹ . Example 7 Ternary copolymerization was carried out in the same manner as in Example 5- (2), except that propylene was saturated at 0.5 kg / g before introducing ethylene. As a result, the copolymer yield was 6.
20 g and the same absorption as in Example 3 was found in the IR absorption spectrum. The copolymer composition is ethylene 84.8
Mol%, propylene 9.2 mol%, p- (3-butenyl)
Styrene 6.0 mol%, melting point 112 ° C, reduced viscosity 0.21 d
1 / g.

Example 8 In Example 1- (2), the amount of toluene used was 50 m
1,1.4 mmol of 1, p- (3-butenyl) styrene, an ethylene pressure of 0.75 kg / cm ² G, a polymerization temperature of 40 ° C., and dicyclopentadienyl zirconium dichloride instead of dicyclopentadienyl titanium dichloride. Copolymerization was carried out in the same manner as in Example 1, except that the copolymer was used. As a result, the copolymer yield was 0.8 g, p- (3-butenyl) styrene was 91 mol%, and the reduced viscosity was 0.038 dl / g.
The copolymer was amorphous without a melting point. Example 9 In Example 1- (2), the solvent p-
0.2 mmol of (3-butenyl) styrene was added, and propylene was saturated with 4 kg / cm ² G, followed by ethylene 5 kg / cm ²
While continuously supplying G, 1 mmol of methylaluminoxane, 0.1 mg of dicyclopentadienyltitanium dichloride were added.
01 mmol was added and copolymerization was carried out for 1 hour. As a result, the copolymer yield was 25 g, and the composition ratio of ethylene and propylene in the copolymer was 81:19 (molar ratio). Separately synthesized equal ethylene copolymerization ratio - in the IR absorption spectrum of the propylene copolymer and the p-(3- butenyl) blend of styrene homopolymer, an absorption based on a methylene group of 2723cm ^-1, 1512cm ^-1 P- (3-
A calibration curve was prepared from the absorbance ratio of the absorption based on the butenyl) styrene aromatic ring, and the content of p- (3-butenyl) styrene determined using this curve was 0.02% by weight. In the IR absorption spectrum of the copolymer, one kind of carbon-carbon double bond absorption was present at 1640 cm ^-1 . The melting point of the copolymer was 121 ° C. and the reduced viscosity was 1.5 dl / g. Example 10 The copolymerization was carried out in the same manner as in Example 1 except that p- (3-methyl-3-butenyl) styrene was used instead of p- (3-butenyl) styrene in Example 1- (2). did. As a result, the copolymer yield was 3.6 g, and p- (3-methyl-3-
Butenyl) styrene content 17 mol%, melting point 121 ° C.
The reduced viscosity was 0.30 dl / g. Example 11 In Example 1- (2), the amount of toluene used was changed to 200 m.
and 2.0 mmol of diethylaluminum monochloride in place of methylaluminoxane, 0.05 mmol of chromium stearate in place of dicyclopentadienyl dichloride, and 8 mmol of p- (3-butenyl) styrene. Was set to 2.0 kg / cm ² G, and copolymerization was carried out in the same manner as in Example 1. As a result, the copolymer yield was 0.31.
g, p- (3-butenyl) styrene content 34 mol%,
The melting point was 124 ° C. and the reduced viscosity was 0.21 dl / g.

[0047]

The olefin copolymer of the present invention is a copolymer having a polyolefin chain into which a reactive unsaturated group is introduced and having an α-olefinically unsaturated bond in the side chain. Utilizing the chemical reactivity of the groups, olefin copolymers further modified in various ways can be obtained. That is, it can be easily modified by a chemical reaction such as production of a crosslinked product, graft copolymerization with an olefin, a diene, or a polar monomer or an addition reaction, and can introduce a large amount of unsaturated groups. Therefore, the olefin-based copolymer of the present invention can be modified such as adhesion to other resins or imparting resin compatibilizing ability. This enables application development to composite materials.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of a copolymer obtained in Example 1.

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms;
R ² represents a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ and R ⁴ each represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms. m is 0 to 4
Is an integer. An olefin copolymer comprising a repeating unit represented by the formula (1) and a repeating unit derived from an olefin and having no polyolefin long-chain branch. 2. The composition according to claim 1, wherein the content of the repeating unit represented by the general formula (I) is 10 ^{-6 to} 95 mol%.
Concentration 0.0 measured at 135 DEG C. in 4-trichlorobenzene.
The reduced viscosity at 5 g / dl is 0.01 to 30 dl / g.
The olefin-based copolymer according to claim 1, wherein 3. The olefin copolymer according to claim 1, wherein the repeating unit represented by the general formula (I) is 5 to 70 mol%.