JP3463884B2 - Olefin copolymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to automobiles, building materials,
The present invention relates to a method for producing an olefin-based copolymer that is preferably used as a packaging material or a molding material in various fields such as civil engineering, medical care, and agriculture.

[0002]

2. Description of the Related Art As a polyolefin polymer film or sheet, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer and the like are extrusion-molded or inflation-molded. There are films and sheets, and they are widely used as packaging materials such as tapes and molding materials such as trays and cups. However, since the films and sheets of these polyolefin-based polymers that have been used conventionally have insufficient elastic recovery properties, there is a problem that necking occurs when tensile stress or the like acts and permanent deformation occurs. Further, since the elastic modulus is high, there is a problem that a large amount of energy is required for packaging. Further, the polyolefin-based copolymer is essentially inferior in adhesiveness and has a limitation in use.

On the other hand, the present inventors have found that elastic recovery,
We have previously proposed an α-olefin / cyclic olefin copolymer having excellent transparency (Japanese Patent Application No. 3-210142). This copolymer has a glass transition temperature (Tg) of less than 30 ° C. and has excellent low-temperature characteristics.

[0004]

However, this copolymer may contain a slight amount of terminal double bonds, and causes a crosslinking reaction during hot melt molding, resulting in gel fish eyes in the film. There was something that happened. Also, because it can cause deterioration by ultraviolet rays,
It was not always satisfactory. Further, the inventors of the present invention, in Japanese Patent Application No. 4-92175, include an unsaturated bond, and by modifying the unsaturated bond by a crosslinking reaction, a graft reaction, or the like, it is possible to improve the high temperature characteristics and the compatibility. Although a binary copolymer of an olefin and a cyclic diene, and a ternary copolymer of an α-olefin, a cyclic olefin and a cyclic diene have been proposed, they contain an unsaturated bond and therefore have a heat stability aspect. Therefore, it was not always satisfactory. In addition, JP-A-63
No. 243103 discloses a method for producing a hydrogenated product of a copolymer of ethylene and dicyclopentadiene. However, since the copolymer shown here has a high glass transition temperature, it has low temperature characteristics. , And toughness was not always sufficient. The present invention has been made in view of the above-mentioned problems, and it is possible to produce an olefin-based copolymer excellent in both elastic recovery, adhesiveness, thermal stability, melt processability, and weather resistance. It is an object of the present invention to provide a production method capable of achieving diversification of copolymer monomers.

[0005]

According to the present invention, α-o
Reffins and / or cyclic olefins and / or cyclic dienes
Having a repeating unit derived from
0 ° C or less, tensile modulus of less than 2,000 kg / cm ²
Present and characterized by being hydrogenated
An in-based copolymer is provided.

[0006]

The composition of the cyclic olefin copolymer is such that the repeating unit (a) derived from α-olefin is 80 to 99.9 mol% and the repeating unit (b) is 20 to 20 derived from cyclic olefin. Mol% and a repeating unit (c) derived from a cyclic diene in a proportion of 0 to 20 mol%, and a repeating unit (b) derived from a cyclic olefin, and a repeating unit derived from a cyclic diene ( The sum of c) is 0.1 to 2 of the whole copolymer.
Olefin-based copolymer , characterized in that the proportion is 0 mol%
A polymer is provided.

Further, α-olefin and cyclic olefin
Of the following compounds (A) and
A catalyst containing (B) as a main component, or (A), (B) and
Copolymerization using a catalyst containing (C) as a main component, the cyclic
A reffin-based copolymer is produced and the cyclic olefin-based copolymer is produced.
There is provided a method for producing an olefin-based copolymer, which comprises hydrotreating a polymer. (A) Transition metal compound containing a transition metal selected from Group IVB of the Periodic Table (B) Transition metal compound (A) or compound (C) organic compound capable of forming an ionic complex from its derivative Aluminum compound

The olefin-based copolymer obtained in the present invention will be specifically described below. 1. Composition Component α-Olefin The α-olefin used in the present invention is not particularly limited, but for example, the following general formula [X]

[Chemical 5] (In the formula [X], R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

In the repeating unit represented by the above general formula [X], R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n-butyl group, n-hexyl group, n-octyl group. Group, n-octadecyl group and the like. In addition, the general formula [X]
Specific examples of the α-olefin giving the repeating unit represented by are, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-eikosen, etc. can be mentioned.

Cyclic olefins-1 Cyclic olefin The cyclic olefin used in the present invention is represented by the following general formula [Y].

[Chemical 6] (In the formula [Y], R ^{b to} R ^m each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n is an integer of 0 or more. R ^j or R ^k and R ¹ or R ^m may form a ring with each other, and R ^{b to} R ^m may be the same or different from each other. I can give you things to give.

In the repeating unit represented by the above general formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 hydrocarbon groups, or a substituent 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, methyl group, ethyl group, n-propyl group, isopropyl group,
C1-C20 alkyl group such as n-butyl group, isobutyl group, t-butyl group, hexyl group, etc., C6-C20 aryl group such as phenyl group, tolyl group, benzyl group, alkylaryl group or aryl 1 to 20 carbon atoms such as alkyl group, methylidene group, ethylidene group, propylidene group
2 to 2 carbon atoms such as alkylidene group, vinyl group and allyl group
There may be mentioned 20 alkenyl groups and the like. However, R
^b , R ^c , R ^f , and R ^{g do not} include an alkylidene group. In addition,
When any of R ^d , R ^e and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is attached has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen groups such as fluorine, chlorine, bromine and iodine, and halogen substitution having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. An alkyl group etc. can be mentioned. 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 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And an alkoxycarbonyl group. Specifically as a substituent containing a nitrogen atom,
For example, a C1-C20 alkylamino group, such as a dimethylamino group and a diethylamino group, a cyano group, etc. can be mentioned.

Specific examples of the cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1 -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-dimethano-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.

[0015] As the cyclic diene used -2 cyclic diene present invention, 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-methylene-2-norbornene, dicyclopentadiene, dimethyldicyclopentadiene, and

[Chemical 7] Etc. can be mentioned. Among these, norbornene, norbornene derivatives, 5-ethylidene-2-norbornene, 5-vinylnorbornene and dicyclopentadiene are particularly preferable. The cyclic diene may have at least two double bonds, and includes, for example, cyclic triene and the like.

In addition, within a range not impairing the object of the present invention,
In addition to these three components, other copolymerizable unsaturated monomer components may be used if desired. As such an unsaturated monomer which may be optionally copolymerized, specifically,
Among the above-mentioned α-olefins, those which have not been used before, those which have not previously been used among the above-mentioned cyclic dienes, those which have not previously been used among the above-mentioned cyclic olefins, butadiene, isoprene, 1,5 Examples thereof include chain dienes such as hexadiene, monocyclic olefins such as cyclopentene and cycloheptene, and the like.

2. Composition Ratio Regarding the composition ratio of the olefin-based copolymer of the present invention,
As described above, the repeating unit (a) derived from the α-olefin needs to be 80 to 99.9 mol%. If it is less than 80 mol%, the low temperature physical properties deteriorate. Of the cyclic olefins, the composition ratio of the repeating unit (b) derived from the cyclic olefin and the repeating unit (c) derived from the cyclic diene is both 0 to 20 mol%.
And the total (cyclic olefins: (b) + (c))
Should be 0.1 to 20 mol% of the whole copolymer. If it is less than 0.1 mol%, the elastic recovery property deteriorates.
Preferably, the repeating unit (a) derived from α-olefin is 82 to 99.5 mol%, the repeating unit derived from cyclic olefin (b) is 0.5 to 18 mol%, and the repeating unit derived from cyclic diene. Unit (c) 0-1
7.5 mol%, more preferably 85 to 98 mol% of the repeating unit (a) derived from α-olefin,
Repeating unit (b) 2 derived from cyclic olefin
15 mol% and 0 to 13 mol% of the repeating unit (c) derived from a cyclic diene.

As the α-olefin, ethylene,
And the following general formula [z]

[Chemical 8] (R ^p is a hydrocarbon group having 1 to 20 carbon atoms, preferably propylene, 1-butene, 4-methyl-1-butene, 1-
It is octene. When two kinds of the α-olefin represented by (4) are used, the composition ratio thereof is ethylene 5 to 99.
8 mol% and α-olefin of general formula [z] 75-
It is necessary to use 0.1 mol% and cyclic olefins of 20 to 0.1 mol%. Preferably ethylene 32-9
9 mol% and α-olefin [z] 50 to 0.5 mol%, and cyclic olefins 18 to 0.5 mol%. More preferably, ethylene is 55 to 98 mol%, α-olefin [z] is 30 to 1 mol%, and cyclic olefins are 15 to 1 mol%. In this case, ethylene and α-olefin [z] are 8% of the total amount of the copolymer.
It should be 0-99.9 mol%.

3. Method for producing cyclic olefin-based copolymer The method for producing the cyclic olefin-based copolymer used in the present invention is not particularly limited, but a catalyst containing the following compounds (A) and (B) as a main component or the following compound (A ), (B), and (C) as a main component, the α-olefin and the cyclic olefin are copolymerized to perform efficient production. (A) Transition metal compound (B) Transition metal compound (A), or compound capable of forming an ionic complex from its derivative (C) Organoaluminum compound

[0020]

The transition metal compound (A) is represented by IVB in the periodic table.
A transition metal selected from the group: titanium (T
i), zirconium (Zr) or hafnium (Hf)
contains. In particular, a cyclopentadienyl compound represented by the following general formula (I), (II) 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,
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 is shown. R ¹ , R ² , R ³ and R ⁴ are each σ
A binding ligand, a chelating ligand, a Lewis base, or other ligand is shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon number of 1 to 1. 20 alkyl groups, C 1-20 alkoxy groups, C 6-
Examples include 20 aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, substituents containing a silicon atom, and the like. Examples thereof include an acetylacetonate group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b, c and d
Are integers of 0 to 4, respectively, 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 the 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. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. Further, specific examples of R ^{1 to} R ⁴ in the above formulas (I) to (IV) include:
For example, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; as an alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; phenyl group, tolyl group as aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms Group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: dimethyl ether, diethyl ether, tetrahydrofuran etc. as a Lewis base Ethers, Tetra Thioethers such as drothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline , Triethylphosphine,
Phosphines such as triphenylphosphine; ethylene, butadiene, 1-pentene as chain unsaturated hydrocarbon,
Isoprene, pentadiene, 1-hexene and their derivatives; cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives. . Examples of the cross-linking by the covalent bond of A in the formula (III) include methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-cyclohexylene cross-link, dimethyl silylene cross-link, dimethyl germylene cross-link, dimethyl stannylene cross-link. Etc. can be mentioned.

Examples of such compounds include the following compounds and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound 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) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydrido zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethyl zirconium, dimethylsilylene bis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclope Tajieniru)
(9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
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 the 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 thereof include zirconium compounds having one or more kinds of alkyl groups, alkoxy groups and halogen atoms, such as compounds in which zirconium is replaced with hafnium or titanium, hafnium compounds, and titanium compounds. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetraphenoxyzirconium, tetra (2-ethylhexyloxy) zirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,6-di-t-butyl). Phenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy)
Dichlorozirconium, zirconium tetrakis (acetylacetonate),

The transition metal compound containing a VB to VIII group transition metal is not particularly limited, and specific examples of the chromium compound include tetramethylchromium and tetra (t).
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Examples thereof include chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like.

Specific examples of manganese compounds include tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like. .

Specific examples of nickel compounds include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), and chlorohydridobis (tricyclohexyl). Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allyl nickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel chloride, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) CH = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ }, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) C (SO ₃ Na) = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ } and the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butylisocyanide) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
Examples include (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, and the like.

Further, examples of the transition metal compound include those represented by the following general formula [w].

[Chemical 9] Wherein, ^{R q} is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ^{Y a} is ^{-O -, - S -, -} NR s -, - PR s
-Or a neutral two-atom donor ligand selected from OR ^s , SR ^s , NR ^s ₂ , and PR ^s ₂ , and M ¹
Is an element selected from Group IVB of the periodic table, and Z ^a is S
iR ^s ₂ , CR ^s ₂ , SiR ^s ₂ -SiR ^s ₂ , CR ^s
₂ -CR ^s ₂ , CR ^s = CR ^s , or GeR ^s ₂ , B
R ^s and BR ^s ₂ . R ^s is a hydrogen atom and has 1 to 1 carbon atoms.
A moiety selected from the group consisting of 20 hydrocarbon groups, halogen atoms, substituents containing oxygen or nitrogen or silicon atoms, and combinations thereof having up to 20 non-hydrogen atoms, or Y ^a , Z ^a or Y Two or more R ^s groups from both ^a and Z ^a form a fused ring. ]

Next, the compound (B) is not necessarily limited, but any compound that can form an ionic complex from the transition metal compound (A) or a derivative thereof can be used. For example, transition metal compound (A)
Alternatively, an ionic compound (B-1) capable of forming an ionic complex from a derivative thereof, specifically, a compound composed of a cation and an anion in which a plurality of groups are bound to an element, particularly a cation and a plurality of groups are formed into an element. A coordination complex compound composed of a bound anion can be preferably used. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the following formula (V) or (VI) can be preferably used. ([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 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 and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Elements selected from Group VA, preferably elements selected from Group IIIA, Group IVA and Group VA, M ⁵ and M ⁶ are Group IIIB, Group IVB, Group VB, Group VIB, Group V of the periodic table, respectively.
An element selected from Group III, Group IA, Group IB, Group IIA, Group IIB, and Group VIIA, Z ^{1 to} Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryloxy group, C1-C20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group, C1-C20 halogen-substituted hydrocarbon group, C1-C20 acyloxy It represents a group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to
20 represents an aryl group, an alkylaryl group or an arylalkyl group, R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is a C 1-20 carbon atom. An alkyl group, an aryl group, an alkylaryl group or an arylalkyl group is shown. R ¹¹ is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M ³ , M
^With an atomic valence of ⁴ , an integer of 1 to 7, n is an integer of 2 to 8, k is an integer of 1 to 7 with an ionic valence of [L ¹ -R ⁷ ], [L ² ],
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethylthioether and tetrahydrothiophene, and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si,
Specific examples of P, As, Sb, etc., preferably B or P, M ⁵ include Li, Na, Ag, Cu, Br, I, I _3, etc.,
Specific examples of M ⁶ include Mn, Fe, Co, Ni and Zn.

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, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; and a carbon number of 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group having an alkyl group having 1 to 20 carbon atoms,
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; aryl group having 6 to 20 carbon atoms,
As an alkylaryl group or an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 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, as halogen atoms
I: Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those listed above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R 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. Among the compounds of formulas (V) and (VI), M
It is preferable that ³ , M ⁴ is boron.

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

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
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, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (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), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis ( Pentafluorophenyl) borate tetraphenylphosphonium, tetrakis (pentafluorophenyl) borate triphenylphosphonium, tetrakis (3,5-ditrifluoromethylphenyl) borate dimethylanilinium, hexafluoroarsenate triethylammonium,

Compound of Formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) borate formylferrocenium, 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) boric acid (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those represented by formulas (V) and (VI), such as tris (pentafluorophenyl) boron, tris (3,5-bis (trifluoromethyl) phenyl) boron, triphenylboron, etc., can also be used. is there. Moreover, aluminoxane (B-1) can also be used as a compound (B). Specific examples of the aluminoxanes include:

[0042]

[Chemical 10] (R ¹² represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms, a halogen atom. S represents a degree of polymerization and is usually 3 to 50, preferably 7 to 40). Aluminoxane.

[0043]

[Chemical 11] (R ¹² is the same as that of formula (VII), s is the degree of polymerization, and the number of repeating units is preferably 3 to 50, preferably 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (VIII), methylaluminoxane, ethylaluminoxane and isobutylaluminoxane having a degree of polymerization of 7 or more are preferable. Further, the aluminoxane may be a modified aluminoxane insoluble in a general solvent, which is obtained by modifying aluminoxane with a compound having active hydrogen such as water.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited.
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 then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formula (IX). R ¹² _r AlQ _3-r (IX) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 alkyl groups, alkenyl groups, aryl groups, arylalkyl groups, etc., Q is a hydrogen atom, Represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3. Specific examples of the compound of the formula (IX) include trimethylaluminum, triethylaluminum, and triisopropyl. Aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

The catalyst used in the production of the cyclic olefin copolymer used in the present invention is (A) and (B) [(B-
1) or (B-2)] component or (A), (B)
The main component is [(B-1)] and the component (C). In this case, the use conditions of the component (A) and the component (B-1) are not limited, but the ratio (molar ratio) of the component (A): component (B-1) is 1: 0.01 to 1: 100. , Especially 1: 0.
It is preferably 5 to 1:10, and more preferably 1: 1 to 1: 5. The conditions for using the components (A) and (B-2) are as follows: component (A): component (B-2) (molar ratio as metal atom): 1:10 to 1: 10,000, particularly 1 : 20 ~
It is preferably 1: 5,000. The operating temperature is preferably in the range of −100 to 250 ° C., and the pressure and time can be set arbitrarily.

The amount of the component (C) used is usually 0 to 2,000 mol, preferably 5 to 1 mol of the component (A).
The amount is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the polymer, which is not preferable.

The mode of use of the catalyst component is not limited, and for example, the components (A) and (B) may be contacted in advance, or the contact product may be separated and washed before use. You may use it by making a contact. Further, the component (C) may be used by being brought into contact with a contact product of the component (A), the component (B) or the component (A) and the component (B) in advance.
The contact may be made in advance or in the polymerization system. Furthermore, the catalyst component can be added to the monomer or the polymerization solvent in advance, 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 ratio of the catalyst to the reaction raw material is 1 to 10 ^{9 of} raw material monomer / component (A) (molar ratio) or raw material monomer / component (B) (molar ratio), and particularly 1
It is preferably from 00 to 10 ⁷ .

Polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization or 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, 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 α-olefin may be used as a solvent.

Regarding the polymerization conditions, the polymerization temperature is -100 to 2
The temperature is preferably 50 ° C, particularly preferably -50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10
0 kg / cm ² G, preferably atmospheric pressure to 50 kg / cm ² G
Is. The method for adjusting the molecular weight of the copolymer can be selected by the amount of each catalyst component used, the polymerization temperature, and the polymerization reaction in the presence of hydrogen.

4. Method for Hydrogenating Cyclic Olefin Copolymer The glass transition temperature (Tg) before hydrogenation of the cyclic olefin copolymer produced by the above method needs to be 50 ° C or lower. By using such a copolymer, it is possible to obtain a film, a sheet or the like which can be suitably used at a low temperature. Preferred glass transition temperature (T
g) is -30 to 30 ° C. In this case, the glass transition temperature (Tg) of the cyclic olefin-based copolymer can be arbitrarily controlled by changing the type and composition of the monomer, and the glass transition temperature (Tg) can be controlled depending on the intended use, the temperature to be used, etc. The glass transition temperature (Tg) can be changed arbitrarily.

The method of hydrogenating (hydrogenating) this cyclic olefin copolymer is usually carried out in an organic solvent solution of the polymer. As the solvent, a hydrocarbon solvent such as cyclohexane, methylcyclohexane, benzene, toluene or xylene is used. Although the concentration of the cyclic olefin-based copolymer solution can be appropriately determined, hydrogenation is usually carried out at a concentration of 0.1 to 30% by weight, preferably 1 to 20% by weight. The hydrogenation catalyst used in the method of the present invention can be any catalyst that is commonly used in the hydrogenation of olefin compounds, and is not particularly limited, and examples thereof include the following. . As the heterogeneous catalyst, nickel, palladium, platinum or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth,
Palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like can be mentioned. Examples of the nickel-based catalyst include Raney nickel catalyst, and examples of the platinum-based catalyst include platinum oxide catalyst and platinum black. As the homogeneous catalyst, those based on a metal of Group VIII of the periodic table, for example, Ni and Co compounds such as cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, etc. Examples thereof include those composed of organometallic compounds of metals selected from the groups IA, IIA and IIIB of the periodic table, and Rh compounds. In addition, MS Saloan (M.S.S.
Aloan et al. disclosed Ziegler-based hydrogenation catalyst (J. Am. Chem. Soc., 85, 4014 (1).
983)) can also be effectively used. Examples of these catalysts include the following. T
_{i (O-iC 3 H 7} ) 4 - (iC 4 H 9) 3 Al, Ti
_{(O-iC 3 H 7)} 4 - (C 2 H 5) 3 Al, (C 2 H
₅ ) ₂ TiCl ₂ — (C ₂ H ₅ ) ₃ Al, Cr (aca
_{c) 3 - (C 2 H} 5) 3 Al, Na (acac) 3 -
(IC ₄ H ₉ ) ₃ Al, Mn (acac) _3- (C ₂ H
₅ ) ₃ Al, Fe (acac) _3- (C ₂ H ₅ ) ₃ A
_{l, Ca (acac) 2 -} (C 2 H 5) 3 Al, (C 7
_{H 5 COO) 3 Co- (C} 2 H 5) 3 Al, hydrogenated (hydrogenation) reaction, in homogeneous or heterogeneous depending on the type of catalyst, of 1 to 150 atm hydrogen pressurization, 0 to 180 ° C. It is preferably carried out at a reaction temperature of 20 to 120 ° C. The hydrogenation rate can be arbitrarily adjusted within the range of 0 to 100% by changing the reaction conditions such as hydrogen pressure, reaction temperature, reaction time, catalyst concentration, and the like. The above-mentioned hydrogenated cyclic olefin copolymer In order to exhibit excellent thermal stability, 30% or more of the unsaturated bonds in the copolymer are preferably hydrogenated, more preferably 50% or more, still more preferably 8%.
The hydrogenation rate is 0% or more. As a post-treatment, after the hydrogenation reaction, the catalyst is removed by centrifugation, filtration, or in the case of a Ziegler type catalyst, the catalyst is deactivated by an acid, and then the reaction product is precipitated in a large amount of a polar solvent such as acetone or alcohol. Then, the solvent is removed and the product is dried to obtain a hydride of the olefin-based copolymer.

5. Physical Properties of Olefin Copolymer After Hydrogenation As the olefin copolymer obtained in the present invention, α-
It is preferable that the repeating units derived from olefins and cyclic olefins are substantially linearly arranged copolymers, but if melt-molding is possible, a gel component that does not dissolve in decalin at 135 ° C is included. May be

The olefinic copolymer obtained in the present invention has a melt index of 0.001 to 10,000 g.
/ 10 minutes is preferable. If the melt index is less than 0.001 g / 10 minutes, the moldability may deteriorate, and if it exceeds 10,000 g / 10 minutes, the strength may be insufficient. More preferable melt index is 0.01 to 1,000 g / 10 min, especially 0.05
~ 500 g / 10 minutes.

The soluble olefin copolymer obtained in the present invention preferably has an intrinsic viscosity [η] of 0.005 to 20 dl / g measured in decalin at 135 ° C. If the intrinsic viscosity [η] is less than 0.005 dl / g, the strength may be remarkably lowered, and if it exceeds 20 dl / g, the moldability may be remarkably deteriorated. A more preferable intrinsic viscosity [η] is 0.05 to 10 dl / g. The olefin-based copolymer obtained in the present invention may become insoluble in a solvent depending on the type and amount of cyclic olefins.

The molecular weight of the olefin copolymer obtained in the present invention is not particularly limited, but the weight average molecular weight Mw of the soluble olefin copolymer measured by gel permeation chromatography (GPC). Is 1,000 to 2,000,000, especially 5,000
0 to 1,000,000, number average molecular weight Mn is 500 to
1,000,000, especially 2,000 to 800,000
It is preferable that the molecular weight distribution (Mw / Mn) is 1.3 to 4, and particularly 1.4 to 3. Molecular weight distribution (Mw /
When Mn) is more than 4, the content of low molecular weight substances increases, which may cause stickiness when formed into a film, sheet or the like.

The olefin copolymer obtained in the present invention preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. When the crystallinity exceeds 40%, elastic recovery and transparency may be deteriorated. A more preferable crystallinity is 0 to 30%, especially 0 to 25%.

The olefinic copolymer obtained in the present invention has a tensile modulus of 2,000 kg / cm in an uncrosslinked state.
It is preferably less than ² . Tensile modulus of 2,000
When it is not less than kg / cm ² , for example, when it is used for a packaging film, a large amount of energy is required at the time of packaging and it may be difficult to form a beautiful packaging conforming to the shape of the article to be packaged. More preferable tensile elastic modulus is 50 to 1,5
It is 00 kg / cm ² .

The olefinic copolymer obtained in the present invention preferably has a tensile breaking strength of 50 to 2,000 kg / cm ² . When it is less than 50 kg / cm ² , for example, the strength is insufficient when used for a packaging film,
If it is 2,000 kg / cm ² or more, the cutting property deteriorates.

The olefinic copolymer obtained in the present invention preferably has a tensile elongation at break of 30% or more,
It is more preferably 50% or more, and most preferably 100% or more. If it is less than 30%, for example, when used for a packaging film, the elongation of the film is insufficient during packaging,
Not preferable.

The olefin copolymer obtained in the present invention preferably has an elastic recovery rate of 10% or more, more preferably 30% or more, and most preferably 60% or more.

The olefin copolymer obtained in the present invention has a glass transition temperature (Tg) of 50 ° C. or lower (-30 to 5).
0 ° C.) is preferable. If such a copolymer is used, a film that can be suitably used at low temperature,
Sheets and the like can be obtained. A more preferable glass transition temperature (Tg) is -30 to 30 ° C. In this case, the olefin-based copolymer obtained in the present invention has a glass transition temperature (Tg) by changing the kind and composition of the monomer.
Can be controlled arbitrarily, and the glass transition temperature (Tg) can be arbitrarily changed according to the intended use, the temperature used, and the like.

The olefinic copolymer obtained in the present invention preferably has a melting peak by DSC of less than 100 ° C. A copolymer having a melting peak by DSC of 100 [deg.] C. or higher may have insufficient uniformity of the composition of the [alpha] -olefin and cyclic olefins, and may deteriorate properties such as transparency. The melting peak by DSC is more preferably in the range of 10 to 85 ° C. D
In the SC measurement, the melting point (melting) peak of the olefin-based copolymer obtained in the present invention cannot be seen sharply, and especially in the case of low crystallinity, the level of the usual polyethylene measurement conditions So there are almost no peaks. Due to these characteristics of the thermal properties, the physical properties of the molded product can be obtained, and a high quality molded product, such as a wide molding temperature range, can be stably molded.

The olefin-based copolymer obtained in the present invention may be a copolymer having only the physical properties within the above range, and may partially include the copolymer having physical properties outside the above range. It may be one that has been installed. In the latter case, all physical property values may be included in the above range.

[0066]

EXAMPLES The present invention will be described in more detail below with reference to examples. The physical properties were measured as follows. Cyclic diene, and cyclic olefin content and hydrogenation rate were determined by 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 the line diffraction method. Glass transition temperature (Tg) Using Vibron II-EA type manufactured by Toyo Boulding Co.,
Width 4 mm, thickness 0.1 mm, heating rate of 3 ° C. / min to measure pieces of length 40 mm, measured at a frequency 3.5 Hz, determined from the peak of loss modulus at this (E "). Mp ( Tm) 10 by Perkinermer 7 series DSC
It measured in the range of -50 degreeC-150 degreeC with the temperature rising rate of C / min. Molecular weight distribution (Mw / Mn) Waters ALC / GPC-150C [column:
Tosoh TSK HM + GMH-6 × 2], solvent:
1,2,4-trichlorobenzene, temperature: 135 ° C., measured in terms of polyethylene. Tensile elastic modulus It carried out according to JIS-K7113 using an autograph. Tensile breaking strength It was performed according to JIS-K7113 using an autograph. Tensile breaking elongation It was performed according to JIS-K7113 using an autograph. Elastic recovery rate Using autograph, pulling speed 62mm / min, width 6m
m, 50 mm (L ₀ ) between the clamps is stretched and stretched by 150% and kept for 5 minutes, then suddenly contracted without being repelled, and after 1 minute, the sheet length between the clamps (L ₁ ) was measured and calculated by the following formula. Elastic recovery rate (%) = [1- {L ₁ −L ₀ } / L ₀ ] × 1
00 Total light transmittance, haze Digital haze computer (DIGITAL HAZE COMPUTE
R) (manufactured by Suga Test Instruments Co., Ltd.) using JIS-K71
The measurement was performed according to 05. Melt index (MI) The measurement was performed according to JIS-K7210 under the conditions of 190 ° C. and 2.16 kg.

[0067]Reference example 1 (1) Tetrakis (pentafluorophenyl) borate dime
Synthesis of chillanilinium 152 mmol of bromopentafluorobenzene and butyl
Pentafluoro prepared from 152 mmol lithium
Phenyllithium in hexane 45 mmol trichloride
Tris (pentafluorophenyl) boron reacted with boron
The element was obtained as a white solid. The obtained tris (pentaful
Orophenyl) boron 41 mmol and pentafluorofe
Reaction with 41 mmol of nyllithium gives lithium tet
Lakys (pentafluorophenyl) boron as white solid
Isolated. Next, lithium tetrakis (pentafluor
16 mmol of (rophenyl) boron and dimethylaniline salt
By reacting the acid salt with 16 mmol in water,
Trakis (pentafluorophenyl) borate dimethylani
11.4 mmol of linium was obtained as a white solid. Generate
An object is a target¹H-NMR,¹³C-NMR
Confirmed in.

(2) Ethylene and 5-ethylidene-2-no
Copolymerization with Rubornene 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), 2 micromoles of bis (cyclopentadienyl) zirconium dichloride in a 1 liter autoclave at room temperature under a nitrogen atmosphere, prepared by the above (1) 4 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was added in this order, 0.48 mol of 5-ethylidene-2-norbornene was subsequently added, and the temperature was raised to 80 ° C., after which the ethylene partial pressure was adjusted to 7. The reaction was carried out for 90 minutes while continuously introducing ethylene so that the pressure was 5 kg / cm ² . After completion of the reaction, the polymer solution was poured into 1 liter of methanol to precipitate a polymer, and the polymer was collected by filtration and dried. Table 1 shows the polymerization components and the polymerization results, and Table 2 shows the physical properties of the polymer.
Shown in.

Example 1 400 g of a cyclohexane solution containing 10% of the polymer obtained in Reference Example 1 was placed in an autoclave having a volume of 1 liter.
Then, 5 g of palladium carbon was charged, the inside of the reactor was replaced with hydrogen, and the temperature was raised to 120 ° C. When the temperature inside the reactor became constant, the hydrogen pressure was increased to 70 atm, and the reaction was performed for 8 hours while supplementing the hydrogen consumed by the reaction. Next, the catalyst in the reaction product was removed by centrifugation and filtration, and the product was poured into a large amount of methanol to precipitate a polymer, which was then filtered and dried to obtain 38.5 g of a hydrogenated product. . ^When analyzed by ¹ H-NMR,
The olefinic unsaturated bond group at 5.4 ppm was completely hydrogenated. Table 3 shows the hydrogenation rate, the yield of the hydrogenated product after the reaction, and the physical properties of the hydrogenated product.

Reference Examples 2 to 5 Catalyst component (A), cyclic diene, type of cyclic olefin,
A polymer was obtained in the same manner as in Reference Example 1 except that the amount was changed as shown in Table 1. The polymerization components and the polymerization results are shown in Table 1, and the physical properties of the polymer are shown in Table 2.

Examples 2 to 5 Hydrogenated products were obtained in the same manner as in Example 1 except that the polymers obtained in Reference Examples 2 to 5 were used. Table 3 shows the hydrogenation rate, the yield of the hydrogenated product after the reaction, and the physical properties of the hydrogenated product. Next, using the hydrogenated polymers obtained in Examples 1 to 5 and the non-hydrogenated polymer obtained in Reference Example 1, the same resin was subjected to melt index measurement 1 to 3 times to obtain MI. The changes were examined (Experiment Nos. 1-6). While the MI of the hydrogenated product obtained in the present invention hardly changed, the MI of the hydrogenated product obtained in Reference Example 2 was M.
I was reduced and coloration of the polymer was seen. The results are shown in Table 4.

Reference Example 6 (1) (tertiary butylamide) (dimethyl) (tetramer
Cyl- [eta] ⁵ -cyclopentadienyl) silane titanium
Preparation of Loride Preparation 1 (a) (Chloro) (dimethyl) (tetramethylcyclopentadi-2,4-enyl) silane-21.5 g in 150 ml THF cooled to -40 ° C.
To a solution of (167 mmol) dimethyldichlorosilane was gradually added 8.00 g (56.8 mmol) of sodium 1,2,3,4-tetramethylcyclopentadienide in 80 ml of THF. The reaction mixture was warmed to room temperature and stirred overnight. The solvent was removed, the residue was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil. Yield 10.50g (8
It was 3.0%). ¹ H-NMR (C ₆ D ₆ ) δ 2.89 (s, 1H),
1.91 (s, 6H), 1.71 (s, 6H), 0.1
4 (s, 6H); ¹³ C-NMR (C ₆ D ₆ ) δ 137.8, 131.5,
56.6 14.6, 11.4, 0.81. (B) (tertiary butylamido) (dimethyl) (tetramethylcyclopentadi-2,4-enyl) silane A solution of 11.07 g (151 mmol) t-butylamine in 20 ml THF was added to 13. ml in 300 ml THF.
00 g (60.5 mmol) of (chloro) (dimethyl)
Added to the solution of (tetramethylcyclopentadienyl) silane over 5 minutes. A precipitate formed immediately. 3 slurries
After stirring for a day, the solvent was removed, the residual liquid was extracted with pentane and filtered. The pentane was removed under reduced pressure to give the product as a light yellow oil. The yield was 14.8 g (97.2%). MS: 251 ¹ H-NMR (C ₆ D ₆ ) δ 2.76 (s, 1H),
2.01 (s, 6H), 1.84 (s, 6H), 1.0
9 (s, 9H), 0.10 (s, 6H); ¹³ C-NMR (C ₆ D ₆ ) δ 135.4, 133.2.
57.0, 49.3, 33.8, 15.0, 11.2,
1.3. (C) Dilithium (tertiary butylamide) (dimethyl)
To a solution of 3.000 g (11.98 mmol) of (tertiary butylamido) (dimethyl) (tetramethylcyclopentadienyl) in 100 ml of (tetramethylcyclo-pentadienyl) silane silane in a mixed C ₆ alkane solvent. 2.61 (23.95 mmol) Butyllithium 9.21 ml was added slowly. A white precipitate formed and the reaction mixture was stirred overnight and then filtered. The solid was washed several times with ether and then dried under reduced pressure to give the product as a white powder. The yield was 3.134 g (99.
8%). (D) (tertiary butylamido) (dimethyl) (tetramethyl-eta ⁵ - cyclopentadienyl) TiCl ₄ to 30 of silane titanium dichloride 0.721 g (3.80 mmol)
Added to ml of frozen (-196 ° C) THF. The mixture-
The temperature was raised to 78 ° C. (dry ice bath). 30 to the resulting yellow solution
A solution of 1.000 g (3.80 mmol) of dilithium (tertiary butylamido) (dimethyl) (tetramethylcyclopentadienyl) silane in ml THF was added.
The solution was warmed to room temperature with stirring overnight. The solvent was removed from the resulting very dark solution. The residual liquid was extracted with pentane and filtered. The very soluble dark reddish brown material was separated from the pale yellow-green crystalline solid by cooling in a freezer.
The solid was filtered and recrystallized from pentane to give an olive green product. The yield was 0.143 g (10.2%).

(2) Coexistence of ethylene and 2-norbornene
In a polymerization nitrogen atmosphere, at room temperature, in an autoclave of 1 liter, 420 ml of toluene, 1.2 mmol of triisobutylaluminum (TIBA), 4 μmol of the titanium compound obtained in the above (1), tetrakis (pentafluorophenyl) boric acid. Add 8 micromoles of anilinium in this order, followed by 7 parts of 2-norbornene.
75 ml of a toluene solution containing 0% by weight (2-
400 mmol) as norbornene) was added. 120
After the temperature was raised to 0 ° C., the reaction was carried out for 30 minutes while continuously introducing ethylene so that the ethylene partial pressure became 6 kg / cm ² . After the reaction was completed, the polymer solution was poured into 1 liter of methanol to precipitate the polymer. This polymer was collected by filtration and dried to obtain a cyclic olefin-based copolymer. The yield of the cyclic olefin-based copolymer was 10.2 g. The polymerization activity was 28 kg / g · Zr.

The physical properties of the obtained cyclic olefin-based copolymer were as follows. The sum of the peaks due to ethylene and the peaks due to methylene at the 5th and 6th positions of norbornene appearing at around 30 ppm in ¹³ C-NMR and 32.5 ppm
Based on the methylene group at the 7-position of norbornene appearing in the vicinity, the norbornene content calculated from the ratio with the peak is 14 mol%
Met. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 4.83 dl / g, and the crystallinity determined by the X-ray diffraction method was 1.5%. Table 5 shows the polymerization components, polymerization results, and physical properties of the polymer.

Reference Example 7 Copolymerization of ethylene, propylene and 2-norbornene Dry toluene 400 m in a 1 liter autoclave.
1, triisobutylaluminum (TIBA) 0.6 mmol, bis (cyclopentadienyl) zirconium dichloride 6 μmol, tetrakis (pentafluorophenyl) borate dimethylanilinium 12 μmol prepared in Reference Example 1, 2-norbornene 230 Millimoles were charged, propylene 2 kg / cm ² was introduced at 25 ° C., the temperature was raised to 60 ° C., and then ethylene was added at a partial pressure of 7 kg / cm ^2.
It was continuously fed so that the volume became cm ^2, and the polymerization was carried out for 1.5 hours. As a result, 49 g of a terpolymer was obtained. Polymerization activity is 89 kg / g · Zr, α-olefin content is 4.5 mol%, norbornene content is 8.6 mol%,
[Η] was 2.60 dl / g, and the crystallinity was 0.5%. Table 5 shows the polymerization components, polymerization results, and physical properties of the polymer.

Reference Example 8 Copolymerization of ethylene and 2-norbornene In a nitrogen atmosphere, 140 ml of dry hexane, 0.6 mmol of triisobutylaluminum and 70 parts of 2-norbornene were placed in a 2 liter autoclave at room temperature.
Hexane solution containing 560 wt% (2-
Norbornene (3 mol) was added in this order, and the temperature was raised to 150 ° C. Then, 120 ml of dry hexane, 0.6 mmol of triisobutylaluminum,
6 micromoles of tetrabutoxyzirconium and 12 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate were added in this order. First, ethylene was introduced into this autoclave so that the ethylene partial pressure became 13 kg / cm ² , then the catalyst solution was immediately introduced through the catalyst introduction pipe, and then the ethylene partial pressure was 53 kg / c.
The reaction was carried out for 5 minutes while continuously introducing ethylene so that m ² was obtained. After completion of the reaction, the polymerization was stopped with isopropyl alcohol and the mixture was flashed on a flash drum to obtain a powdery copolymer. The yield of this copolymer is 4
The polymerization activity was 5.8 g, the polymerization activity was 82 kg / g · Zr, the norbornene content was 8.7 mol%, [η] was 1.14, and the crystallinity was 3.5 mol%. Table 5 shows the polymerization components, polymerization results, and physical properties of the polymer.

[0077] Using the polymer obtained in Example 6-8 Example 6-8, the reaction time 4
A hydrogenated product was obtained in the same manner as in Example 1 except that the polymer concentration was changed so that the cyclohexane solution of the polymer became 400 g in time. Table 6 shows the hydrogenation rate, the yield of hydrogenated product after the reaction, and the physical properties. Next, using the hydrogenated products obtained in Examples 6 to 8 and the non-hydrogenated product obtained in Reference Example 7, the same resin was subjected to melt index measurement 1 to 3 times to change MI. Examined. (Experiment number 7
-10) The MI of the hydrogenated product obtained in the present invention was hardly changed, and the polymer was not colored. The results are shown in Table 6.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

According to the present invention, elastic recovery, adhesiveness,
It is possible to produce an olefin-based copolymer having excellent thermal stability, hot melt processability, and weather resistance, and to diversify the copolymerized monomer.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (3)

(57) [Claims] 1. An α-olefin and the following general formula [Y]:
A cyclic olefin giving a repeating unit represented by
Or derived from a cyclic diene selected from the following group
It has a repeating unit, a glass transition temperature of 50 ° C or less, and a tensile modulus of 2,000.
less than kg / cm ² and hydrogenated
An olefin-based copolymer characterized by: The general formula [Y]: [Formula 1] (In the formula [Y], R ^{b to} R ^m are a hydrogen atom and a carbon, respectively.
Number 1 to 20 hydrocarbon group, halogen atom, oxygen atom
Or represents a substituent containing a nitrogen atom, and n is an integer of 0 or more.
Indicates a number. R ^j or R ^k and R ¹ or R ^m are rings each other.
You may form. R ^{b to} R ^m are the same as each other.
It may be one or different. ) Group: 1,3-cyclopentadiene, 1,3-cyclohexadiene
Ene, 1,4-cyclohexadiene, 5-ethyl-1,
3-cyclohexadiene, 1,3-cycloheptadie
1,4-cycloheptadiene, 1,3-cyclooctane
Tadiene, 1,4-cyclooctadiene, 1,5-cyclo
Rooctadiene, 5-methylene-2-norbornene, di
Cyclopentadiene, dimethyldicyclopentadiene,
And, ## STR2 ## 2. The composition of the olefin-based copolymer is α
-Repeating unit (a) 80 derived from olefin-
99.9 mol%, a repeating unit (b) 0 to 20 mol% derived from a cyclic olefin, and a repeating unit (c) 0 to 20 mol% derived from a cyclic diene, and a cyclic olefin repeating units derived from (b), and the total amount of the repeating units (c) derived from cyclic dienes, characterized in that a proportion of 0.1 to 20 mol% of the total copolymer according to claim 1 Listed olefins
-Based copolymer . 3. An α-olefin and the following general formula [Y]
Cyclic olefins and / or also providing the repeating units shown
Is a cyclic diene selected from the following group,
A catalyst containing (A) and (B) as a main component, or (A),
Copolymerized using a catalyst containing (B) and (C) as main components
To produce a cyclic olefin-based copolymer,
A contract characterized by hydrotreating a fin-based copolymer
The method for producing an olefin-based copolymer according to claim 1 or 2 . (A) Transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) Transition metal compound (A), or compound (C) capable of forming an ionic complex from a derivative thereof organoaluminum compound formula [Y]: ## STR3 ## (In the formula [Y], R ^{b to} R ^m are a hydrogen atom and a carbon, respectively.
Number 1 to 20 hydrocarbon group, halogen atom, oxygen atom
Or represents a substituent containing a nitrogen atom, and n is an integer of 0 or more.
Indicates a number. R ^j or R ^k and R ¹ or R ^m are rings each other.
You may form. R ^{b to} R ^m are the same as each other.
It may be one or different. ) Group: 1,3-cyclopentadiene, 1,3-cyclohexadiene
Ene, 1,4-cyclohexadiene, 5-ethyl-1,
3-cyclohexadiene, 1,3-cycloheptadie
1,4-cycloheptadiene, 1,3-cyclooctane
Tadiene, 1,4-cyclooctadiene, 1,5-cyclo
Rooctadiene, 5-methylene-2-norbornene, di
Cyclopentadiene, dimethyldicyclopentadiene,
And, [of 4]