JPH05230147A - Cyclic olefinic copolymer and its production - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject copolymer excellent in low temperature characteristics such as low temperature impact resistance and suitable as a molding material for automotive external parts, etc., by copolymerizing ethylene, an alpha-olefin and a cyclic olefin in the presence of a specific catalyst. CONSTITUTION:Ethylene, an alpha-olefin of formula I (R<a> is 1-20C hydrocarbon) and cyclic olefin of formula II (R<b>-R<m> are H, 1-20C hydrocarbon, etc.,) (preferably norbornene) are copolymerized in the presence of a catalyst comprising a transition metal compound [preferably (cyclopentadienyl)trimethylzirconium], a compound forming an ion complex by the reaction with the above compound (preferably silver tetraphenyl borate and an organic Al compound (preferably triisobutylaluminum) to produce the objective copolymer comprising 5-99.8mol.wt. of the unit derived from ethylene, 0.1-75mol.% of the unit of formula III and 0.1-20mol.% of the unit of formula IV, and having an intrinsic viscosity [eta]of 0.01-20dl/g and a glass transition temperature Tg of <=20 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to ethylene and 3 to 3 carbon atoms.
No. 22, a terpolymer of an α-olefin and a cyclic olefin, and a method for producing the same, will be described in more detail. Excellent in low-temperature characteristics such as low-temperature impact resistance, molding material for automobile exterior parts, and impact resistance improvement for polyolefin. The present invention relates to a cyclic olefin copolymer preferably used as an agent and the like and a method for producing the same.

[0002]

2. Description of the Related Art In recent years,
In the field of automobile exterior parts, applications that are used under severe low temperature conditions are increasing. Therefore, glass transition temperature (Tg)
Therefore, there is a demand for a resin molding material having a low temperature and excellent low temperature characteristics such as low temperature impact resistance. On the other hand, the present inventors
Of α-olefin / cyclic olefin copolymer having excellent low-temperature properties at a temperature of less than 30 ° C (Japanese Patent Application No. 3-210142).
No.), a resin having further improved low temperature characteristics is desired.

On the other hand, conventionally, in the copolymerization of two or more components such as α-olefins and cyclic olefins, a method using a catalyst composed of a vanadium compound and an organoaluminum compound (JP-A-3-205410: ternary or Quaternary copolymer), a method using a catalyst composed of a specific transition metal compound and methylaluminoxane (JP-A-61-221206). However, these methods have low polymerization activity, particularly low aluminum activity and poor production efficiency,
In addition, the copolymerizability was unsatisfactory in that it was insufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ethylene / α-olefin / cyclic olefin terpolymer having excellent low-temperature properties and an efficient method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific cyclic olefin-based terpolymer described later has a high α-olefin component content and a low cyclic olefin component content. However, because of its low crystallinity and low glass transition temperature, it has excellent low-temperature properties such as low-temperature impact resistance, and by using a specific catalyst described later, this terpolymer The present invention has been completed by finding that the above can be efficiently produced.

That is, the present invention is a copolymer having a repeating unit derived from ethylene, a repeating unit represented by the following general formula [X], and a repeating unit represented by the following general formula [Y]. ,

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

[Chemical 6] (In the formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. (1) The content of repeating units derived from ethylene is 5 to
99.8 mol%, the content of the repeating unit represented by the formula [X] is 0.1 to 75 mol%, the content of the repeating unit represented by the formula [Y] is 0.1 to 20 mol%, (2 ) Provided is a cyclic olefin-based copolymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g and (3) a glass transition temperature (Tg) of 20 ° C or lower.

Further, the present invention uses the following compounds (A) and (B) or a catalyst containing (A), (B) and (C) as a main component, (A) transition metal compound (B) transition Compound that reacts with metal compound to form ionic complex (C) Organoaluminum compound Copolymerization of ethylene, α-olefin represented by the following general formula [x] and cyclic olefin represented by the following general formula [y] The present invention provides a method for producing a cyclic olefin-based copolymer, which comprises:

[Chemical 7] (In the formula [x], Ra represents ^a hydrocarbon group having 1 to 20 carbon atoms.)

[Chemical 8] (In the formula [y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) Here, the manufacturing method of the cyclic olefin type copolymer of this invention is shown in FIG.

[0008] Incidentally, JP-A-62-252406 discloses a random copolymer of ethylene and a cyclic olefin. Among them, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is further disclosed. Although suggesting the possibility, there is no description about the specific properties, production method, etc. of such a multi-component copolymer. Further, JP-A-61-115912 discloses a multi-component copolymer having an ethylene component, another α-olefin component and a cyclic olefin component. But,
The multi-component copolymer disclosed here has a high glass transition temperature of 80 to 190 ° C., and is intended for high temperature characteristics. Therefore, the cyclic olefin-based copolymer of the present invention is different from any of the multicomponent copolymers described in these publications.

The present invention will be described in more detail below.
The cyclic olefin-based copolymer of the present invention has a repeating unit derived from ethylene, a repeating unit represented by the general formula [X], and a repeating unit represented by the general formula [Y].

Here, in the repeating unit represented by the general formula [X], Ra represents ^a hydrocarbon group having 1 to 20 carbon atoms. 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, n-octadecyl group and the like can be mentioned. Specific examples of the α-olefin giving the repeating unit represented by the general formula [X] include α-olefins represented by the general formula [x], for example, propylene, 1-butene, 3-methyl-1-butene, 4 -Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-eicosene and the like can be mentioned.

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m are each 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. Is shown. 1 to 2 carbon atoms
Specific examples of the hydrocarbon group of 0 include a methyl group,
An alkyl group having 1 to 20 carbon atoms such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, hexyl group and the like, and 6 carbon atoms such as phenyl group, tolyl group and benzyl group. ~ 20 aryl groups, alkylaryl groups or arylalkyl groups, methylidene groups,
Alkylidene group having 1 to 20 carbon atoms such as ethylidene group and propylidene group, 2 to 20 carbon atoms such as vinyl group and allyl group
The alkenyl group and the like can be mentioned. However, R ^b ,
R ^c , R ^f , and R ^g exclude alkylidene groups. Note that R ^d , R
^{When any of e} , R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is attached has no other substituent.

Here, as the substituent containing a halogen atom, specifically, for example, a halogen group such as fluorine, chlorine, bromine, iodine, etc., and a halogen having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group, chloroethyl group, etc. A substituted alkyl group etc. can be mentioned. Specific examples of the substituent containing an oxygen atom include 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 number 1 to 20 such as a methoxycarbonyl group and an ethoxycarbonyl group. Alkoxycarbonyl group and the like can be mentioned. Specific examples of the substituent containing a nitrogen atom 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 the repeating unit represented by the general formula [Y] include cyclic olefins represented by the general formula [y], such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5- Propyl norbornene, 5,6-dimethyl norbornene, 1-methyl norbornene, 7-methyl norbornene, 5,5,6-trimethyl norbornene, 5-phenyl norbornene, 5-benzyl norbornene, 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,
Examples thereof include 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, and 5-cyanonorbornene. Among these, norbornene or its derivative is particularly preferable.

The cyclic olefin copolymer of the present invention is basically a copolymer of the above-mentioned ethylene, α-olefin and cyclic olefin, but does not impair the object of the present invention. In addition to these three essential components, other copolymerizable unsaturated monomer components may be used if necessary. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above α-olefin components, those not previously used, among the above cyclic olefin components, Not used, cyclic dienes such as dicyclopentadiene and norbornadiene, butadiene, isoprene, 1,5-
Examples thereof include chain dienes such as hexadiene and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin copolymer of the present invention has a content of repeating units derived from ethylene of 5 to 99.8.
Mol%, the content of the repeating unit of the formula [X] is 0.1 to 7
5 mol%, the content of the repeating unit of the formula [Y] is 0.1 to
It is 20 mol%. If the content of repeating units derived from ethylene is less than 5 mol%, the glass transition temperature becomes high and the low temperature properties become insufficient. Further, if it exceeds 99.8 mol%, the crystallinity of the copolymer becomes high and the elasticity and transparency become insufficient. When the content of the repeating unit of the formula [X] is less than 0.1 mol%, the crystallinity of the copolymer becomes high and the elasticity and transparency become insufficient. Further, if it exceeds 75 mol%, the glass transition temperature becomes high and the low temperature characteristics become insufficient. When the content of the repeating unit of the formula [Y] is less than 0.1 mol%, the crystallinity of the copolymer becomes high and the elasticity and transparency become insufficient. On the other hand, if it exceeds 20 mol%, the glass transition temperature becomes high and the low temperature properties become insufficient. The more preferable content of the repeating unit derived from ethylene is 3
2 to 99 mol%, especially 55 to 98 mol%, more preferable content of the repeating unit of the formula [X] is 0.5 to 50 mol%, particularly 1 to 30 mol%, more than that of the repeating unit of the formula [Y]. The preferred content is 0.5 to 18 mol%, particularly 1 to 15
Mol%.

The cyclic olefin-based copolymer of the present invention is a substantially linear copolymer in which repeating units derived from ethylene, repeating units of the formula [X] and repeating units of the formula [Y] are randomly arranged. It is preferable that it does not have a gel-like crosslinked structure. It can be confirmed that the copolymer does not have a gel-like crosslinked structure by completely dissolving the copolymer in decalin at 135 ° C.

The cyclic olefin copolymer of the present invention comprises 1
Intrinsic viscosity [η] measured in decalin at 35 ° C is 0.0
1 to 20 dl / g. The intrinsic viscosity [η] is 0.
If it is less than 01 dl / g, the strength is remarkably reduced,
When it exceeds 1 / g, the moldability is remarkably deteriorated. A more preferable intrinsic viscosity [η] is 0.05 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer of the present invention is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2,000,000. ,
Especially 5,000 to 1,000,000, number average molecular weight M
n is 500 to 1,000,000, particularly 2,000 to 8
The molecular weight distribution (Mw / Mn) is 1.000.
It is preferably 3 to 4, particularly 1.4 to 3. When the molecular weight distribution (Mw / Mn) is greater than 4, the content of low molecular weight substances increases, which may cause stickiness of the molded product.

The cyclic olefin-based copolymer of the present invention has a glass transition temperature (Tg) of 20 ° C. or lower. If such a copolymer is used, a molded article having excellent low temperature properties such as low temperature impact resistance can be obtained. A more preferable glass transition temperature (Tg) is -30 to 15 ° C, particularly -30 to 1
It is 0 ° C. This glass transition temperature (Tg) can be arbitrarily changed by changing the kind and composition of the monomer of the copolymer according to the intended use and the required physical properties.

The cyclic olefin-based copolymer of the present invention preferably has a melting peak by DSC of less than 90 ° C. A copolymer having a melting peak at 90 ° C. or higher by DSC may have insufficient uniformity of composition of the cyclic olefin and α-olefin and may have insufficient elastic recovery of the molded product. The melting peak by DSC is more preferably in the range of 10 to 90 ° C. D
In the SC measurement, the melting point (melting) peak of the cyclic olefin-based copolymer of the present invention is not seen sharply, and especially in the case of low crystallinity, it is almost a peak at the normal polyethylene measurement condition level. But not. 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.

Further, the cyclic olefin-based copolymer of the present invention preferably has a crystallinity of less than 40% as measured by an X-ray diffraction method. If the crystallinity is 40% or more, elastic recovery and transparency may be deteriorated. More preferred crystallinity is less than 30%, especially less than 25%.

The cyclic olefin copolymer of the present invention preferably has a tensile elastic modulus of less than 3,000 Kg / cm ² . If the tensile modulus is 3,000 Kg / cm ² or more, the toughness of the molded product may be insufficient. More preferable tensile elastic modulus is 50 to 2,000 Kg / cm ^2.
Is.

The olefin copolymer of the present invention includes
It may be a copolymer having only the physical properties in the above range, or may partially contain a copolymer having the physical properties outside the above range. In the latter case, all physical property values may be included in the above range.

The method for producing the cyclic olefin copolymer of the present invention is not limited, but, for example, a catalyst containing the following compounds (A) and (B) or (A), (B) and (C) as a main component: Can be preferably used to carry out the copolymerization of ethylene with an α-olefin of the general formula [x] and a cyclic olefin of the general formula [y], whereby the cyclic olefin-based copolymer of the present invention can be obtained. It can be manufactured efficiently.
In this case, in order to obtain the cyclic olefin-based copolymer of the present invention by the above method, the copolymerization amount is determined so that the content of the repeating unit derived from each component is the above ratio. (A) Transition metal compound (B) Compound which reacts with transition metal compound to form an ionic complex (C) Organoaluminum compound

In this case, as the transition metal compound (A), there are IVB group, VB group, VIB group, VIIB group and VI of the periodic table.
Transition metal compounds containing transition metals belonging to Group II can be used. Specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable as the above transition metal, and among them, zirconium, hafnium, titanium, nickel and palladium are preferable.

Examples of such a transition metal compound (A) include various compounds, but in particular, a compound containing a transition metal of IVB group or VIII group, especially a transition metal selected from IVB group of the periodic table, that is, A compound containing titanium (Ti), zirconium (Zr) or hafnium (Hf) can be preferably used, and particularly, a compound represented by the following general formula (I),
A cyclopentadienyl compound represented by (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 another 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, 1-20 carbon alkoxy groups, 6 carbon atoms
Examples include 20 aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, and substituents containing a silicon atom, and examples of chelating ligands include 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 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. In addition, (I) ~ (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 n-propyl 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 alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as an arylalkyl 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: 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; ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives as chain unsaturated hydrocarbons;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. 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′-
Examples thereof include cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds 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) monochloromonohydride 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 (cyclopen Tadienyl)
(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 a zirconium compound, a hafnium compound, and a titanium compound 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. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (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, tricarbonyl tris (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-butyl isocyanide) 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.

Any compound can be used as the compound (B) as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound composed of a bound anion, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element can be preferably used. The compound consisting of such a cation and an anion in which a plurality of groups are bound to an element is represented by the following formula (V) or (VI)
The compound represented by 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 VIB of the periodic table, respectively.
Elements selected from Group III, Group IA, Group IB, Group IIA, Group IIB and Group VIIA, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 respectively.
To C20 aryloxy group, C1 to C20 alkyl group, C6 to C20 aryl group, alkylaryl group, arylalkyl group, C1 to C20 halogen-substituted hydrocarbon group, C1 to C20 2 represents an acyloxy 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 6 to 6 carbon atoms
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 group. 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
^{4 has} an valence of 1 to 7, n is an integer of 2 to 8, k is an ionic number of [L ¹ -R ⁷ ] and [L ² ] and is an integer of 1 to 7,
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-promo-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 diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As and Sb.
Etc., preferably B or P, and specific examples of M ⁵ are Li,
Specific examples of Na, Ag, Cu, Br, I, I _3, etc. and M ⁶ include 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, 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 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-di (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 include:
Examples are the same as those listed above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 5. (V), (V
Among the compounds of 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 can be used particularly preferably. Compound of formula (V) triethylammonium 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) tetraphenylphosphonium borate, tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis (3,5-ditrifluoromethylphenyl) dimethylanilinium borate, triethylammonium hexafluoroarsenate,

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 tri (pentafluorophenyl) boron, tri (3,3)
5-di (trifluoromethyl) phenyl) boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include those represented by the following general formula (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms, Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3. Examples of the compound of the formula (VII) 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.

[0047]

[Chemical 9] (R < ¹² > shows the same thing as a formula (VII). S shows a polymerization degree and is 3-50 normally, Preferably it is 7-40.) The chain | strand-shaped aluminoxane shown by these.

[0048]

[Chemical 10] (R ¹² represents the same as in formula (VII), s represents the degree of polymerization, and the preferred number of repeating units is 3 to 50, preferably 7 to 40.) Cyclic alkyl having a repeating unit Aluminoxane. Among the compounds represented by the formulas (VII) to (IX), an alkyl group-containing aluminum compound or aluminoxane having at least one alkyl group having 3 or more carbon atoms, and particularly having at least one branched alkyl group is preferable. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained.

As a method for producing the aluminoxane, there may be mentioned 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, 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 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.

The catalyst used in the production of the cyclic olefin copolymer is mainly composed of the above-mentioned component (A) and component (B) or the above-mentioned component (A), component (B) and component (C). is there. 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: 0.01 to 1: 100, and particularly 1: 0.
It is preferably 5 to 1:10, and more preferably 1: 1 to 1: 5. 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. There is no limitation on the use mode of the catalyst. For example, the components (A) and (B) may be contacted in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (C) may be used by being brought into contact with the 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. Further, the catalyst component can be added to the monomer or the polymerization solvent in advance, or can be added to the polymerization system. If necessary, the catalyst component can be used by supporting it on an inorganic or organic carrier.

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. Regarding polymerization conditions,
Polymerization temperature is -100 to 250 ° C, especially -50 to 200 ° C.
It is preferable that Further, the ratio of the catalyst used to the reaction raw material is as follows: raw material monomer / component (A) (molar ratio)
Alternatively, the ratio of raw material monomer / component (B) (molar ratio) is 1
It is preferably from 10 to ⁹ , particularly preferably from 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 100 kg / cm ² G, preferably atmospheric pressure to 50 kg / cm ^2.
cm ² G. As a method for adjusting the molecular weight of the polymer,
The amount of each catalyst component used, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can 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, pentane, hexane,
Aliphatic hydrocarbons such as 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.

The copolymer of the present invention can be processed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, practicator, mixing extruder, twin-screw conical screw extruder, planetary screw extruder, gear type extruder Extrusion molding, injection molding, compression molding, blow molding, rotational molding or thermoforming from a sheet using a screwless extruder or the like. In molding, well-known additives such as heat stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, deodorants, lubricants, synthetic oils, natural oils, inorganic and organic fillers, if necessary. Agents, dyes, pigments and the like may be added.

Since the cyclic olefin copolymer of the present invention is excellent in low temperature characteristics such as low temperature impact resistance, it is used as a molding material for automobile exterior parts such as side moldings, mudguards and bumpers, and an impact resistance improving agent for polyolefin. It can be used in various fields such as film fields such as commercial stretch films, shrink films and sealant films, building materials fields, damping materials, toys and the like.

[0056]

EXAMPLES Next, the present invention will be specifically shown by 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.

Content of α-olefin and norbornene Determined by ¹³ C-NMR. ALC / GPC-150C manufactured by Mw / Mn Waters [Column:
Tosoh TSK GMH-6 × 2], solvent: 1, 2,
4-trichlorobenzene, temperature: 135 ° C, intrinsic viscosity measured in terms of polyethylene [η] It was measured in decalin of 135 ° C. Using a test piece prepared by hot pressing the crystallinity , X at room temperature
It was determined by the line diffraction method. Vibron II manufactured by Toyo Boulding Co., Ltd. as a glass transition temperature (Tg) measuring device
EA type, width 4mm, length 40mm, thickness 0.1m
The measurement piece of m was measured at a temperature rising rate of 3 ° C./min at a frequency of 3.5 Hz, and the loss elastic modulus (E ″) at this time was obtained.

Melting point (Tm) : 1 by Perkin Elmer 7 series DSC
It measured in the range of -50 degreeC-150 degreeC with the temperature rising rate of 0 degreeC / min. It was performed according to JIS-K7113 using a tensile modulus autograph. The tensile rupture strength autograph was performed according to JIS-K7113. Tensile elongation at break Autograph was performed according to JIS-K7113.

Elastic recovery rate Using an autograph, a pulling speed of 62 mm / min and a width of 6 m
m, 50 mm (L ₀ ) between clamps was stretched and stretched by 150%, held for 5 minutes, and then contracted suddenly without rebounding, and after 1 minute, the sheet length between clamps (L ₁ ) was measured and determined by the following formula. Elastic recovery rate (%) = [1-{(L ₁ −L ₀ ) / L ₀ }] ×
100 In this case, good elastic recovery is 10% or more, especially 30%
Above all, above 60%. Total light transmittance, Haze Digital haze computer (DIGITAL HAZE COMPU
TER) (manufactured by Suga Test Instruments Co., Ltd.) using JIS-K
The measurement was performed according to 7105.

Example 1 (1) Synthesis of dimethylanilinium tetra (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was added to 45 mmol of boron trichloride in hexane. To give tri (pentafluorophenyl) boron as a white solid. The obtained tri (pentafluorophenyl) boron 41 mmol was reacted with pentafluorophenyllithium 41 mmol to isolate lithium tetra (pentafluorophenyl) boron as a white solid. Next, 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of dimethylanilinium tetra (pentafluorophenyl) borate as a white solid. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product.

(2) Copolymerization of ethylene, propylene and 2-norbornene Dry toluene 400 m in a 1 liter autoclave.
1, triisobutylaluminum (TIBA) 0.6 mmol, biscyclopentadienyl zirconium dichloride 6 μmol, tetra (pentafluorophenyl) borate dimethylanilinium 12 μmol prepared in (1), 2-norbornene 230 mmol. Charge and introduce ² Kg / cm ² of propylene at 25 ° C., 60
After the temperature was raised to 0 ° C., ethylene was continuously fed so that the partial pressure was 7 kg / cm ^2, and the copolymerization was carried out for 1.5 hours to obtain 49 g of a terpolymer.

(3) Molding of sheet Using the copolymer obtained in (2) above, a temperature of 190 ° C.
Hot press molding was performed at a pressure of 100 Kg / cm ² , a sheet having a thickness of 0.1 mm was prepared, and various tests were conducted.

Examples 2 to 5 The procedure of Example 1 was repeated, except that the type of α-olefin, the type of catalyst (A) and the copolymerization conditions were changed as shown in Table 1.

Reference Example (Copolymerization of Ethylene and 2-Norbornene) 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), 6 microliters of biscyclopentadienyl zirconium dichloride in a 1 liter autoclave at room temperature under a nitrogen atmosphere. Mole, Example 1
4 μmol of dimethylanilinium tetra (pentafluorophenyl) borate prepared in (1) was added in this order, followed by 60 ml of a toluene solution containing 70% by weight of 2-norbornene (400 mmol of 2-norbornene).
Was added and the temperature was raised to 90 ° C, the ethylene partial pressure was 7 kg.
While continuously introducing ethylene to 9 / cm ²
The reaction was carried out for 0 minutes. After completion of the reaction, add 1 polymer solution
The polymer was deposited by pouring it into liter of methanol, and the polymer was collected by filtration and dried.

Polymerization conditions in the above Examples and Reference Examples,
The polymerization results are shown in Table 1, and the physical properties of the obtained copolymer are shown in Table 2.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

As described above, the cyclic olefin-based copolymer of the present invention has a low content of the cyclic olefin component, a low glass transition temperature, low crystallinity, and a low elastic modulus, and therefore has low temperature resistance. It has excellent low temperature properties such as impact resistance.

[Brief description of drawings]

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

Claims (3)

[Claims] 1. A copolymer having a repeating unit derived from ethylene, a repeating unit represented by the following general formula [X], and a repeating unit represented by the following general formula [Y], wherein: ] (In the formula [X], Ra represents ^a hydrocarbon group having 1 to 20 carbon atoms.) (In the formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. (1) The content of repeating units derived from ethylene is 5 to
99.8 mol%, the content of the repeating unit represented by the formula [X] is 0.1 to 75 mol%, the content of the repeating unit represented by the formula [Y] is 0.1 to 20 mol%, (2 ) A cyclic olefin-based copolymer having an intrinsic viscosity [η] of 0.01 to 20 dl / g and (3) a glass transition temperature (Tg) of 20 ° C or lower. 2. The cyclic olefin-based copolymer according to claim 1, which has a melting point (Tm) of 90 ° C. or lower. 3. A transition metal compound (A) using a catalyst containing the following compounds (A) and (B) as a main component or a catalyst containing the following compounds (A), (B) and (C) as a main component: (B) Compound that reacts with transition metal compound to form ionic complex (C) Organoaluminum compound Ethylene, α-olefin represented by the following general formula [x], and cyclic olefin represented by the following general formula [y] A method for producing a cyclic olefin-based copolymer, which comprises performing copolymerization with [Chemical 3] (In the formula [x], R ^a represents a hydrocarbon group having 1 to 20 carbon atoms.) (In the formula [y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. )