JP3268005B2 - Olefin copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

INDUSTRIAL APPLICABILITY The present invention contains an unsaturated bond and can be modified by a crosslinking reaction or a graft reaction, and can be suitably used as a molding material for medical parts, automobile parts, industrial parts and the like. Olefin copolymers ,
The present invention relates to a production method, various molding materials including the same, and a packaging film .

[0002]

2. Description of the Related Art
As films and sheets made of polyolefin resin,
High-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer and the like extrusion or inflation molded films, sheets, packaging materials,
Widely used for tapes, trays, cups, etc. However, these polyolefin-based resin films and sheets that have been used conventionally have insufficient elastic recovery, and thus have a problem that necking occurs when a tensile stress or the like is applied and permanent deformation occurs. In addition, there is a disadvantage that a large amount of energy is required for packaging due to a high elastic modulus.

On the other hand, the present inventors have proposed an elastic recovery property,
An α-olefin / cyclic olefin copolymer excellent in transparency and the like has been previously proposed (Japanese Patent Application No. 3-210142). This copolymer has a glass transition temperature (Tg) of less than 30 ° C. and has excellent low-temperature properties. However,
At present, in the medical field, automotive exterior parts field, and the like, resins that are excellent not only in low-temperature characteristics but also in high-temperature characteristics are demanded.

At present, a method of modifying a resin by a crosslinking reaction, a graft reaction, or the like has been put to practical use. For example, JP-A-62-34924 discloses a method of crosslinking a random copolymer of cyclic olefin and ethylene, and also discloses a cyclic diene as a copolymerizable polyene. However, the copolymer shown here has a high glass transition temperature (Tg) and a high rigidity.

On the other hand, Japanese Patent Application Laid-Open No. 1-197511 discloses an α-olefin component having 3 to 20 carbon atoms and a cyclic polyene component,
Further, an olefin random copolymer having a cyclic olefin component as required is disclosed. However, the copolymer exemplified here has an intrinsic viscosity of 0.2 dl /
g or less and cannot be used as a material for molded articles such as films and sheets.

In the copolymerization of such an α-olefin with a cyclic polyene or a cyclic olefin, a method using a catalyst comprising a vanadium compound and an organoaluminum compound (JP-A-61-271308) or A method using a catalyst comprising a specific transition metal compound and methylaluminoxane (JP-A-61-221206)
It has been known. However, these methods involve polymerization activity,
In particular, it was unsatisfactory in that the aluminum activity was low and the copolymerizability was insufficient.

The present invention has been made in view of the above circumstances, and has excellent elastic recovery properties, low-temperature properties, and has properties such as high-temperature properties, adhesiveness, and compatibility with other resins by being modified by a crosslinking reaction or a graft reaction. capable of improving error
Tylene / cyclic diene terpolymer and ethylene / cyclic diene / cyclic olefin terpolymer, their efficient
Manufacturing method and various molding materials and packaging materials containing them
The purpose is to provide a film .

[0008]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies, the specific olefin-based binary or terpolymer containing a cyclic diene component has excellent elastic recovery properties and low-temperature properties. It is found that denaturation is possible, and the softening temperature is increased by these reactions, heat resistance is improved, and that the olefin-based copolymer can be efficiently produced by using a specific catalyst described later. Thus, the present invention has been accomplished.

That is, the present invention provides:ethyleneAnd annular di
A repeating unit derived from ene orethylene, Cyclic diene
And repeating units derived from cyclic olefins.
A polymer comprising ethylene and a cyclic diene or ethylene
, Cyclic diene and cyclic olefin
(1)ethyleneContent of repeating units derived from
９９99.9 mol%, repeating unit derived from cyclic diene
Content of5.6 to 0.1 mol%For cyclic olefins
(2) a glass transition temperature (Tg) of 30 ° C. or less,(3) Tensile modulus is 2000Kg / cm ^Two Less than,  To provide an olefin-based copolymer characterized by being
You.

The present invention also provides a copolymer of an α-olefin and a cyclic diene using a catalyst containing the following compounds (A) and (B) or (A), (B) and (C) as main components. Alternatively, the present invention provides a method for producing the olefin copolymer, which comprises copolymerizing an α-olefin, a cyclic diene, and a cyclic olefin. (A) a transition metal compound containing a tetravalent transition metal of Group IVB; (B) a compound which reacts with the transition metal compound (A) to form an ionic complex; and (C) an organoaluminum compound. FIG. 1 shows a method for producing the olefin copolymer of the present invention. Further, the present invention relates to the olefin-based copolymer described above.
Various molding materials including a body and a film for packaging are provided.

Hereinafter, the present invention will be described in more detail.
The olefin-based copolymer of the present invention has a repeating unit derived from ethylene and a repeating unit derived from a cyclic diene, and further has a repeating unit derived from a cyclic olefin as needed.

[0012]

[0013]

The cyclic diene is not particularly restricted but includes, for example, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-
Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,3-
Cyclooctadiene, 1,4-cyclooctadiene,
1,5-cyclooctadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 3-vinylcyclohexene, 4-vinylcyclohexene, 5-vinylnorbornene, 5- Allyl norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, dimethyldicyclopentadiene,

Embedded image And the like. Among these, 5-ethylidene-2-norbornene, 5-vinylnorbornene and dicyclopentadiene are particularly preferred. The cyclic diene may have at least two double bonds, and includes, for example, a cyclic triene.

Although the cyclic olefin is not necessarily limited, for example, the following general formula [Y]

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) Which give a repeating unit represented by

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom
To 20 hydrocarbon groups or substituents containing a halogen atom, an oxygen atom or a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Alkyl groups having 1 to 20 carbon atoms such as -butyl group, isobutyl group, t-butyl group, hexyl group, etc .; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl. , A methylidene group, an ethylidene group, a propylidene group, etc.
Carbon number 2 such as alkylidene group, vinyl group, allyl group of 0
And -20 alkenyl groups. However,
R ^b , R ^c , R ^f and R ^g exclude an alkylidene group. Note that R
^{When any of d} , R ^e , and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

Specific examples of the substituent containing a halogen atom include halogen substituents such as fluorine, chlorine, bromine and iodine, and halogen substituents having 1 to 20 carbon atoms such as chloromethyl, bromomethyl and chloroethyl. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specifically as a substituent containing a nitrogen atom,
Examples thereof include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the cyclic olefin giving a repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned. Among these, norbornene or a derivative thereof is particularly preferred.

The cyclic olefin-based copolymer of the present invention is basically obtained by copolymerizing ethylene and a cyclic diene as described above and, if necessary, a cyclic olefin. Other copolymerizable unsaturated monomer components may be used, if desired, in addition to these three components as long as the components are not impaired. As such unsaturated monomers which may be optionally copolymerized, specifically, propylene
Α-olefins other than ethylene, such as
Those not previously used among the aforementioned cyclic dienes,
Among the above-mentioned cyclic olefins, those not previously used, chain dienes such as butadiene, isoprene, and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene are exemplified.

The olefin copolymer of the present invention, ethylene
Content of emission unit 80 to 99.9 mol%, the content of the cyclic diene units from 5.6 to 0.1 mol%, but the content of the cyclic olefin unit is from 0 to 19.9 mol%. Echile
If the content of the carboxylic acid unit is less than 80 mol%, the low-temperature characteristics deteriorate. Further, the content of the cyclic diene unit is 0.1 mol%.
If it is less than 10, the elastic recovery property is reduced, and it is not suitable for a crosslinking reaction or a graft reaction. A more preferred content of ethylene units is 82 to 99.5 mol%, particularly 85 to 98 mol%, and a more preferred content of cyclic diene units is 0.5 to 5.6 mol%, particularly 2 to 5.6 mol%. , The more preferred content of the cyclic olefin unit is 0 to 17.5 mol%, particularly 0 to 13 mol%.
Mol%.

The olefin copolymer of the present invention includes:
Repeating units or d derived from ethylene and cyclic dienes
Styrene, it is preferable repeating unit derived from a cyclic diene and cyclic olefin is a copolymer which is arranged in substantially linear, melt molding is possible, including a gel component which does not dissolve in the 135 ° C. decalin It may be something.

The olefin copolymer of the present invention preferably has a melt index of 1.03 to 500 g / 10 minutes . When the melt index is less than 1.03 g / 10 minutes , the moldability may be deteriorated, and 500 g /
If the time exceeds 10 minutes, the strength may be insufficient. A more preferred melt index is 1.03 to 300 g /
10 minutes , especially 1.03 to 200 g / 10 minutes .

The soluble olefin copolymer of the present invention preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.005 to 30 dl / g. If the intrinsic viscosity [η] is less than 0.005 dl / g, the strength may be remarkably reduced, and if it exceeds 30 dl / g, the moldability may be significantly deteriorated. More preferred intrinsic viscosity [η] is 0.01 to 20 dl / g, particularly 0.0 to 20 dl / g.
5 to 10 dl / g. The olefin copolymer of the present invention may be insoluble in a solvent depending on the type and amount of the cyclic diene.

Although the molecular weight of the olefin copolymer of the present invention is not particularly limited, the weight average molecular weight Mw of the soluble olefin copolymer measured by gel permeation chromatography (GPC) is 1%. 2,000 to 2,000,000, especially 5,000 to
1,000,000, number average molecular weight Mn is 500 to 1,
And the molecular weight distribution (Mw / Mn) is 1.3-4, especially 1.
It is preferably 4 to 3. Molecular weight distribution (Mw / M
When n) is more than 4, the content of the low molecular weight substance increases, which may cause stickiness when formed into a film, a sheet or the like.

Further, the olefin copolymer of the present invention comprises:
The crystallinity measured by the X-ray diffraction method is preferably 0 to 40%. When the crystallinity exceeds 40%, elastic recovery and transparency may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

Further, the olefin copolymer of the present invention has an uncrosslinked state having a tensile modulus of 2000 kg / cm ^2.
Is less than . When the tensile elastic modulus is 2000 kg / cm ² or more, for example, when used for a packaging film, a large amount of energy is required at the time of packaging, and beautiful packaging suitable for the shape of the article to be packaged may be difficult. . A more preferred tensile modulus is 50 to 1,500 Kg / cm ² .

The olefin copolymer of the present invention needs to have a glass transition temperature (Tg) of less than 30 ° C. By using such a copolymer, a film, a sheet, or the like that can be suitably used at a low temperature can be obtained. A more preferred glass transition temperature (Tg) is -30 to 20C, particularly -30 to 10C. In this case, the olefin copolymer of the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer, and the intended use, the temperature used, etc. The glass transition temperature (Tg) can be arbitrarily changed according to the conditions.

Further, the olefin copolymer of the present invention comprises:
The melting peak by DSC is preferably lower than 100 ° C. Copolymers having a DSC melting peak of 100 ° C. or higher have insufficient compositional uniformity of ethylene , cyclic diene, and cyclic olefin, and may deteriorate properties such as transparency. The melting peak by DSC was 9
More preferably, it is less than 5 ° C. In the DSC measurement, the melting point (melting) peak of the olefin-based copolymer of the present invention is not sharp, and especially in the case of low crystallinity, almost no peak is observed at the level of ordinary polyethylene measurement conditions. Not. Due to these characteristics of thermal properties, not only the physical properties of the molded product can be obtained, but also a high-quality molded product can be stably molded, for example, the molding temperature range is widened.

The olefin copolymer of the present invention includes:
It may be a copolymer consisting of only those having physical properties in the above-mentioned range, or may be a copolymer partially containing a copolymer having physical properties out of the above-mentioned range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the olefin copolymer of the present invention is not limited, but a catalyst containing the following compounds (A) and (B) as main components or the following compounds (A), (B) and (C) is mainly used. Efficient production can be achieved by copolymerizing an α-olefin with a cyclic diene or copolymerizing an α-olefin with a cyclic diene and a cyclic olefin using a catalyst as a component. (A) a transition metal compound containing a tetravalent transition metal of Group IVB (B) a compound which reacts with the transition metal compound (A) to form an ionic complex (C) an organoaluminum compound

[0031]

As such a transition metal compound (A),
Although various compounds can be mentioned, the following general formulas (I) and (I)
A cyclopentadienyl compound represented by I) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as 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. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the crosslink by a covalent bond of A in the above formula (III) include, for example, a methylene bridge, a dimethylmethylene bridge, an ethylene bridge, 1,1′-
Examples include a cyclohexylene cross-link, a dimethylsilylene cross-link, a dimethylgermylene cross-link, and a dimethylstannylene cross-link.

Examples of such compounds include the following and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compounds of formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) (Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkyl group, an alkoxy group, and a halogen atom, such as a compound in which zirconium is replaced with hafnium or titanium. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxytrichloro zirconium, dibutoxy dichloro zirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

[0039]

[0040]

[0041]

[0042]

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group, V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p- bromo- N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, ethyl
Esters such as rubenzoate . Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, S
b, etc., preferably B or P, as completely as examples of M ⁵ L
i, Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5- bis (trifluoromethyl) phenyl group; F, Cl, Br,
I; 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 ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R
Specific examples of the substituted cyclopentadienyl group ⁹ 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 5. (V), (V
Among the compounds of the formula (I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V): triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltributyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
-Cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Tetraphenylphosphonium (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis
[3,5-bis (trifluoromethyl) phenyl] dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (ferromanganese tetraphenylporphyrin), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris
[3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0053]

Embedded image (R ¹² is the same as in formula (VII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0054]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50, and preferably 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained.
Further, the aluminoxane may be a modified aluminoxane which is obtained by modifying an aluminoxane with a compound having active hydrogen such as water and which is insoluble in a general solvent.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out 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 added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The catalyst used in the production of the olefin copolymer of the present invention may be any of the above components (A) and (B) or (A),
(B) and (C) are the main components. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1:
It is preferably from 0.01 to 1: 100, particularly preferably from 1: 0.5 to 1:10, especially preferably from 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The component (C) is used in an amount of usually 0 to 2,000 mol, preferably 5 to 2,000 mol per mol of the component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable.

There are no particular restrictions on the manner of use of the catalyst component. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. It may be used in contact. Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance.
The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / the component (A) (molar ratio) or the raw material monomer / the component (B) (molar ratio) is 1 to 10 ⁹ , especially 1
It is preferable to be a 00-10 ^7.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane;
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent.

Regarding the polymerization conditions, the polymerization temperature is -100 to 2
The temperature is preferably set to 50 ° C., particularly −50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 10 hours.
0 kg / cm ² G, preferably normal pressure to 50 kg / cm ² G
It is. As a method for adjusting the molecular weight of the copolymer, it is possible to select the amount of each catalyst component used and the polymerization temperature, and furthermore, to carry out the polymerization reaction in the presence of hydrogen.

The olefin copolymer of the present invention can be formed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixed extruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder Extrusion molding, injection molding, blow molding, rotational molding and the like can be performed using a screwless extruder or the like. Also, T-die molding method,
A film or sheet can be prepared by an inflation molding method or the like. In the molding process, if necessary, well-known additives such as a heat stabilizer, a light stabilizer,
Antistatic agents, slip agents, antiblocking agents, deodorants, lubricants, synthetic oils, natural oils, inorganic and organic fillers, dyes, pigments and the like may be added.

The olefin-based copolymer of the present invention is excellent in low-temperature properties and elastic recovery properties, and is improved in high-temperature properties and adhesiveness by a crosslinking reaction and a grafting reaction. For medical devices, automotive components, industrial components, packaging films, etc.

[0064]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, physical properties were measured as follows.

The content of cyclic diene and cyclic olefin was determined by ¹³ C-NMR. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Crystallinity Using a test piece prepared by hot pressing, X at room temperature
It was determined by a line diffraction method. Vibron II- manufactured by Toyo Bolding Co., Ltd. as a glass transition temperature (Tg) measuring device
Using EA type, width 4mm, length 40mm, thickness 0.1m
m was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz, and the peak was obtained from the loss elastic modulus (E ″) at this time.

Melting point (Tm) 1 by DSC of PerkinElmer 7 series
The temperature was measured at a rate of 0 ° C./min in the range of −50 ° C. to 150 ° C. Molecular weight distribution (Mw / Mn) Waters ALC / GPC-150C [column:
Tosoh TSK HM + GMH-6 × 2], solvent:
The measurement was performed in accordance with JIS-K7113 using 1,2,4-trichlorobenzene, temperature: 135 ° C., and a tensile modulus autograph measured in terms of polyethylene. It carried out according to JIS-K7113 using the tensile breaking strength autograph. It carried out according to JIS-K7113 using the tensile elongation at break .

Using an elastic recovery autograph, a tensile speed of 62 mm / min and a width of 6 m
m, a measuring piece having a distance of 50 mm (L ₀ ) between the clamps was stretched by 150%, pulled and kept as it was for 5 minutes, then rapidly contracted without being rebounded, and after 1 minute, the sheet length (L ₁ ) was measured and determined by the following equation. Elastic recovery rate (%) = [1 − {(L ₁ −L ₀ ) / L ₀ }] ×
100 In this case, a good elastic recovery rate is 10% or more, especially 30%.
As mentioned above, it is 60% or more especially. Total light transmittance, Haze Digital Haze Computer (DIGITAL HAZE COMPU
TER) (manufactured by Suga Test Instruments Co., Ltd.)
The measurement was performed according to 7105. Melt index (MI) The measurement was performed at 190 ° C. and 2.16 kg in accordance with JIS-K7210.

Example 1 (1) Synthesis of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyl lithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was mixed with 45 mmol of boron trichloride in hexane. And tris (pentafluorophenyl) boron was obtained as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of lithium pentafluorophenyl , and lithium tetrakis (pentafluorophenyl) boron was isolated as a white solid. Then, lithium te
10. Reaction of 16 mmol of trakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride in water to give dimethylanilinium tetrakis (pentafluorophenyl) borate as a white solid.
4 mmol were obtained. The fact that the product is the desired product is based on ¹ H-
Confirmed by NMR and ¹³ C-NMR.

(2) Copolymerization of ethylene and 5-ethylidene-2-norbornene At room temperature under nitrogen atmosphere, 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA) and biscyclopentadienyl zirconium were placed in a 1-liter autoclave at room temperature. 2 micromoles of dichloride and 4 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in the above (1) are added in this order, and subsequently 0.2 mol of 5-ethylidene-2-norbornene is added. After the temperature was raised, the reaction was carried out for 30 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ² . After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, which was collected by filtration and dried.

(3) Film Forming Using the copolymer obtained in the above (2), at a temperature of 190 ° C.
Hot press molding was performed at a pressure of 100 kg / cm ² to prepare a film having a thickness of 0.1 mm, and various tests were performed.

Reference Example 2, Examples 3 to 5, Comparative Example 1 Types of catalyst component (A), cyclic diene and cyclic olefin,
The procedure was performed in the same manner as in Example 1 except that the amounts were changed as shown in Table 1. In Comparative Example 1, the polymerization time was 90 minutes.

Tables 1 and 2 show the catalyst components, polymerization components, polymerization results, physical properties of the obtained copolymer and physical properties of the obtained sheets in the above Examples, Reference Examples and Comparative Examples.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

As described above, the olefin copolymer of the present invention has excellent elastic recovery properties and low-temperature properties, and can improve high-temperature properties by being modified by a crosslinking reaction and a graft reaction. It is.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for producing the olefin copolymer of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-221206 (JP, A) JP-A-2-64111 (JP, A) JP-A-1-197511 (JP, A) JP-A-4- 189806 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 210/00-210/18 C08F 232/00-232/08

Claims (8)

(57) [Claims] 1. A copolymer comprising a repeating unit derived from ethylene and a cyclic diene or a repeating unit derived from ethylene, a cyclic diene and a cyclic olefin, wherein the copolymer comprises ethylene and a cyclic diene or ethylene, a cyclic diene and a cyclic olefin. (1) when the content of the repeating unit derived from ethylene is 80%,
９９99.9 mol% , the content of the repeating unit derived from the cyclic diene is 5.6 to 0.1 mol% , the content of the repeating unit derived from the cyclic olefin is 0 to 19.9 mol%, (2) An olefin copolymer having a glass transition temperature (Tg) of 30 ° C. or lower, and (3) a tensile modulus of less than 2000 kg / cm ² . 2. The melt index is 1.03 to 500.
The olefin-based copolymer according to claim 1, which is g / 10 minutes . 3. The olefin copolymer according to claim 1, wherein a melting peak by DSC is lower than 100 ° C. 4. A copolymer of ethylene and a cyclic diene or a copolymer of ethylene and a cyclic diene using a catalyst containing the following compounds (A) and (B) or (A), (B) and (C) as main components. The method for producing an olefin-based copolymer according to any one of claims 1 to 3, wherein copolymerization with a cyclic olefin is performed. (A) a transition metal compound containing a tetravalent transition metal of group IVB; (B) a compound which reacts with the transition metal compound (A) to form an ionic complex by reacting; (C) an organoaluminum compound 5. The oleum according to claim 1, wherein
A molding material for medical members containing a fin-based copolymer. 6. A molding material for an automobile member , comprising the olefin copolymer according to claim 1. Description: 7. The oleum according to claim 1, wherein
A molding material for industrial members containing a fin-based copolymer . 8. The oleic according to claim 1, wherein
A packaging film containing a fin-based copolymer.