JPH10330429A - Ethylene/polar group-containing cyclic olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a random addition copolymer of a cyclic olefin having a polar group such as an ester group or an acid anhydride group with ethylene. SOLUTION: This copolymer has (a) a structural unit derived from ethylene and (b) a structural unit derived from a polar group-containing cyclic olefin expressed by the formula [A and B are each a hydrogen atom or a 1-10C hydrocarbon group; either of X and Y is an ester group expressed by (CH2 )n COOR R is a 1-20C hydrocarbon group and (n) is an integer of 0-10} and the other is a hydrogen atom, a 1-10C hydrocarbon group or an ester group expressed by (CH2 )n COOR R and (n) are respectively same as the above}, or X and Y bond with each other to form a bifunctional group expressed by (CH2 )n -CO-O- CO-(CH2 )n (n) is same as the above}; (m) is 0 or 1]. The copolymer has 1,000-100,000 number-average molecular weight calculated as polystyrene and a content of the structural unit derived from the polar group-containing cyclic olefin in the copolymer of 1-99 mol.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ethylene / polar group-containing cyclic olefin copolymer.

[0002]

2. Description of the Related Art Polyolefins represented by polyethylene and polypropylene, and α-olefin copolymers are:
It is excellent in heat resistance, aging resistance, chemical resistance, etc., and has been put to practical use as a general-purpose resin in a wide range of industrial fields including automobile parts. Among them, polyolefins having a polar group such as an ester group are expected to have advantages such as development for optical applications due to their transparency and good adhesion to metals and other materials.

[0003] Conventionally, a copolymer of ethylene and an olefin having a polar group has been disclosed in International Publication WO96-23.
In 010, a catalyst comprising a diimine ligand complex having Pd or Ni as a central metal and an organoaluminum compound such as aluminoxane was proposed, and an addition group using this catalyst system (referred to as a Brookhart type catalyst) was used to represent an ester group. It has become possible to obtain a random copolymer of a linear olefin having a polar group and ethylene. Also, Risse et al. Pd
Production of homoaddition polymers of polycyclic olefins having polar groups such as ester groups and carboxylic acid groups by combining a complex with a cationizing agent has been reported (Makromo
l. Chem., 193, 2915, 1992).

[0004]

However, the production of a random addition polymer of a linear polar olefin represented by methyl acrylate and ethylene by the use of a Brookhart type catalyst has been reported, but a cyclic group-containing cyclic olefin has been reported. A copolymer of ethylene and ethylene cannot be produced. Further, the catalyst system of Risse et al. Enables homoaddition polymerization of a cyclic group-containing olefin, but does not provide a copolymer with a general-purpose olefin such as ethylene. In view of the above, an object of the present invention is to provide a random addition copolymer of ethylene with a cyclic olefin having a polar group such as an ester group or an acid anhydride group.

[0005]

That is, the present invention comprises: a) a structural unit derived from ethylene; and b) a general formula (1):

[0006]

Embedded image Wherein A and B are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; one of X and Y is a group represented by the formula: — (CH 2) n COOR (where R is the number of carbon atoms) A hydrocarbon group having 1 to 20; n represents an integer of 0 to 10), and the other is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a formula:-(CH2 ) nCOOR (where R and n
Represents an ester group represented by the above), or X and Y are mutually bonded to form the formula:-[(CH ₂ ) _{n-
CO-O-CO- (CH 2} ) n ] - (where the two n identical or different, being as defined above) to form a divalent group represented by. n represents 0 or 1 as described above. A copolymer having a structural unit derived from a polar group-containing cyclic olefin represented by the formula, the number average molecular weight in terms of polystyrene is 1,000 to 100,000, and the polar group-containing in the copolymer The present invention provides an ethylene / polar group-containing cyclic olefin copolymer in which the structural unit derived from a cyclic olefin is 1 to 99 mol%.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Copolymer The copolymer of the present invention contains a structural unit derived from ethylene and a structural unit derived from a polar group-containing polycyclic olefin as essential structural units. It may contain a structure derived from another monomer copolymerizable with these monomers as long as the structure is not impaired.

[0008] Polar group-containing cyclic olefin: The structural unit derived from the polar group-containing polycyclic olefin represented by the general formula (1) is used in the copolymer of the present invention in the general formula (2):

[0009]

Embedded image [Wherein A, B, X, Y and m are as described above].

In the above general formula (1), A and B may be the same or different and each has a hydrogen atom or 1 carbon atom.
~ 10 hydrocarbon groups. A typical example is a hydrogen atom, a linear alkyl such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc., which may be the same or different.

One of X and Y is an ester group represented by the formula-(CH2) nCOOR, and the other is a hydrogen atom or a carbon atom.
It is a hydrocarbon group of 1 to 10 or an ester group represented by the formula-(CH2) nCOOR. In the ester group-(CH) nCOOR, R is a hydrocarbon group having 1 to 20 carbon atoms, for example, a chain alkyl such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and n is 0 to 10. Indicates an integer.
X and Y are mutually bonded to form a compound of the formula:-[(CH ₂ ) _n -CO
—O—CO— (CH ₂ ) _n ] — (where two n's are the same or different and are as described above) may form a divalent group.

In the general formula (1), m is 0 or 1. In the general formula (1), one or both of X and Y are preferably represented by the formula — (CH ₂ ) _n COOR (R is a methyl group, an ethyl group, an isobutyl group, a t-butyl group, a hexyl group, a phenyl group Or a cyclohexyl group, wherein n is 0 or 2
And when one of X and Y is not the ester group, it is a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, t-butyl or the like having 1 carbon atom. ~ 20 chain alkyl, and m is 0
~ 1 compound. Further, typical examples from the viewpoint of synthesis include a case where both X and Y are the above-mentioned ester group, and a case where one of X and Y is the above-mentioned ester group and the other is a hydrogen atom.

Specific examples of such a cyclic group-containing cyclic olefin include 8-methyl-8-carboxymethyltetracyclo.
[4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-carboxyanhydride methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 5-carboxymethyl - bicyclo [2.2 .1] -2-Heptene, 5,6
-Dicarboxy-bicyclo [2.2.1] -2-heptenoic anhydride;

Other monomers: Specific examples of other polymerizable monomers other than ethylene and the polar group-containing cyclic olefin which may be contained in the copolymer include propylene, 1
-Butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, α-olefin having 3 or more carbon atoms such as 1-decene, cyclopentene, cyclohexene, Cycloolefins such as 3-methylcyclohexene; styrenes such as styrene and α-methylstyrene; norbornenes such as norbornene, methylnorbornene, ethylnorbornene and isobutylnorbornene; and 2,3,3a, 7a-tetrahydro-4,7-methanoe. -1H-indene, 3a, 5,6,7a-tetrahydro-4,7-
Endomethylene compounds such as methano-1H-indene or 1,4-hexadiene, dicyclopentadiene, 5-
Non-conjugated dienes such as ethylidene-2-norbornene, 7-methyl-1,6-octadiene and 1,9-decadiene can be mentioned. Structural units derived from these other monomers may be contained in the copolymer in a range of 50 mol% or less.

The copolymer of the present invention has a polystyrene-equivalent number average molecular weight (Mn) obtained by gel permeation chromatography (hereinafter referred to as GPC) measurement of 1,00.
It is in the range of 0-100,000. The molecular weight distribution represented by Mw / Mn (Mw is the weight average molecular weight) is usually in the range of 2.8 to 4.0, and only one peak is observed in GPC. further,
The glass transition temperature (hereinafter referred to as Tg) is 80-120 ° C. Method for Producing Copolymer To produce the copolymer of the present invention, ethylene and a polar group-containing cyclic olefin may be polymerized using a catalyst comprising the following compounds (A) and (B). (A) Transition metal compound (B) Organoaluminum compound The catalyst may optionally further contain (C) an ionic compound.

Catalyst: [Component (A)] The transition metal compound (hereinafter referred to as “transition metal compound (A)”) as the component (A) of the catalyst has a transition metal and at least one cyclic amide ligand. A transition metal compound comprising:

The central metal of the transition metal compound (A) is a metal element belonging to Groups 3 to 11 of the periodic table, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper,
Hafnium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and lanthanoid-based metals, for example,
Neodymium, samarium, europium, lutetium, a transition metal selected from ytterbium and gadolinium, preferably titanium, zirconium, hafnium, vanadium, tantalum, nickel, palladium, cobalt, ruthenium, rhodium, and lanthanide series of samarium, yttrium, neodymium And more preferably titanium and zirconium.

The ligand contained in the transition metal compound (A) is a compound composed mainly of carbon atoms and bonded to the central metal via at least one nitrogen atom, and having a main chain skeleton forming a ring. is there. One or more cyclic ligands may be present for the central metal. The cyclic main chain skeleton is an element other than carbon and nitrogen, for example, silicon,
It may contain oxygen, sulfur, boron, phosphorus and the like. When the ligand forms the transition metal compound (A) with the central metal, the bond between the central metal and the nitrogen atom may be a covalent bond or a coordinate bond.

The transition metal compound (A) may contain one or more ligands other than the cyclic amide ligand,
Examples thereof include a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an alkoxy group, a carboxyl group, an ester group, a halogen, a halogenated hydrocarbon, and an alkylsilyl group.

Among the transition metal compounds (A), preferred are those having 2 to 4 nitrogen atoms in the ligand ring, for example, those represented by the general formulas (1) -A, (1) -B, 2) -A, (2) -B,
Transition metal compounds represented by (2) -C, (3) -A, (3) -B, (3) -C, and (3) -D are exemplified.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

Embedded image (Wherein n ¹ , n ² , n ³ and n ⁴ are integers of 1 or more, preferably 1 to 10. n ¹ , n ² , n ³ and n ⁴
May be the same or different. R ^{1 to} R ¹¹ may be the same or different and represent a hydrogen atom such as methyl, ethyl, propyl, n-butyl, t-butyl, hexyl, cyclohexyl, octyl, phenyl, 4-carboxyphenyl,
Hydrocarbon groups having 1 to 20 carbon atoms such as benzyl, 4-carboxybenzyl and 4-methoxycarbonylphenyl, for example, alkoxy groups having 1 to 22 carbon atoms such as methoxy, ethoxy, isopropoxy and t-butoxy, phenoxy An aryloxy or aralkyloxy group having 6 to 22 carbon atoms such as benzoxy, a carboxyl group, for example,
A general formula such as acetyl or the like -COORx (Rx is an alkyl group having 1 to 20 carbon atoms, an aryloxy group or an aralkyloxy group, for example, methyl, ethyl, propyl, n-butyl,
ester groups represented by t-butyl, hexyl, cyclohexyl, octyl, phenyl, and benzyl), halogen atoms such as fluorine, chlorine, and bromine, for example, (mono, di or tri) fluoromethyl, (mono, di or Halogenated hydrocarbon groups such as tri) chloromesyl, tetra (fluoro, chloro or bromo) phenyl, penta (fluoro, chloro or bromo) phenyl, tetra (fluoro, chloro, bromo) cyclopentene, or for example, trimethylsilyl, dimethylethylsilyl, And trialkylsilyl groups such as triethylsilyl, dimethoxysilyl, and diethoxysilyl. M is Periodic Table No. 3-1
Group 1 transition metals, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, hafnium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, tantalum, tungsten, rhenium, osmium, iridium, Transition metals such as platinum, and lanthanoid metals such as neodymium, samarium, europium, lutetium, ytterbium, and gadolinium. X is a halogen atom such as fluorine, chlorine, bromine or the like, a σ-binding ligand or a chelating ligand. m is an integer of 0 to 3 and is an integer that is the number of N coordinated to M + m = M oxidation number. Particularly preferred among the transition metal compounds (A) exemplified above are the general formulas (2) -A, (2) -B, (3) -B and (3) -C. It is a compound represented.

Representative examples of the preferred transition metal compound (A) are shown below. Examples of transition metal compounds of the general formula (2) -A: 1,3,5-triazacyclohexanyl titanium chloride, 1,4,7-triazacyclononanyl titanium chloride, 1,5,9-triaza Cyclododecanyl titanium chloride, 1,6,11-
Triazacyclopentadecanyl titanium chloride, 1,
7,13-triazacyclooctadecanyl titanium chloride, (2-methyl) 1,4,7-triazacyclononanyl titanium chloride, (2-methyl) 1,5,9-triazacyclododecanyl titanium chloride , (2-phenyl) 1,4,7-triazacyclononanyl titanium chloride, (2-phenyl) 1,5,9-triazacyclododecanyl titanium chloride, (2-acetyl) 1,4,7- Triazacyclononanyl titanium chloride, (2-acetyl) 1,5,9-triazacyclododecanyl titanium chloride, (2-trifluoromethyl) 1,4,7-triazacyclononanyl titanium chloride, (2 -Trifluoromethyl) 1,5,9-triazacyclododecanyl titanium chloride, (2-methoxy) 1,4,7-triazacyclononanyl titanium chloride, ( 2-methoxy) 1,5,9-
Triazacyclododecanyl titanium chloride, (2-phenoxy) 1,4,7-triazacyclononanyl titanium chloride, (2-phenoxy) 1,5,9-triazacyclododecanyl titanium chloride, (2,5 , 8-Trimethyl) 1,4,7-triazacyclononanyl titanium chloride, (2,6,10-trimethyl) 1,5,9-triazacyclododecanyl titanium chloride, (2,5,8-trimethyl) Phenyl) 1,4,7-triazacyclononanyl titanium chloride, (2,6,10-triphenyl) 1,5,9-triazacyclododecanyl titanium chloride, (2,5,8-
(Triacetyl) 1,4,7-triazacyclononanyl titanium chloride, (2,6,10-triacetyl) 1,5,9
-Triazacyclododecanyl titanium chloride, (2,
(5,8-trifluoromethyl) 1,4,7-triazacyclononanyl titanium chloride, (2,6,10-trifluoromethyl) 1,5,9-triazacyclododecanyl titanium chloride, (2, 5,8-trimethoxy)
1,4,7-triazacyclononanyl titanium chloride,
(2,6,10-trimethoxy) 1,5,9-triazacyclododecanyl titanium chloride, (2,5,8-triphenoxy) 1,4,7-triazacyclononanyl titanium chloride, (2, (6,10-triphenoxy) 1,5,9-triazacyclododecanyl titanium chloride and the like.

Examples of transition metal compounds of the general formula (2) -B: N-
Methyl-1,3,5-triazacyclohexanyl titanium dichloride, N-methyl-1,4,7-triazacyclononanyl titanium dichloride, N-methyl-1,5,9-triazacyclododecanyl titanium Dichloride, N-methyl-1,6,11-triazacyclopentadecanyl titanium dichloride, N-methyl-1,7,13-triazacyclooctadecanyl titanium dichloride, N-methyl-
(2-methyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2-methyl) 1,5,9
-Triazacyclododecanyl titanium dichloride, N-
Methyl- (2-phenyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2-phenyl) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2 -Acetyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl-
(2-acetyl) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2-trifluoromethyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2 -Trifluoromethyl) 1,
5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2-methoxy) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2
-Methoxy) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2-phenoxy) 1,
4,7-triazacyclononanyl titanium dichloride,
N-methyl- (2-phenoxy) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl-
(2,5,8-trimethyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2,6,10
-Trimethyl) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2,5,8-triphenyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- ( 2,6,10-triphenyl)
1,5,9-Triazacyclododecanyl titanium dichloride, N-methyl- (2,5,8-triacetyl) 1,4,7
-Triazacyclononanyl titanium dichloride, N-methyl- (2,6,10-triacetyl) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl-
(2,5,8-trifluorotrifluoromethyl) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl-
(2,6,10-tritrifluoromethyl) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2,5,8-trimethoxy) 1,4,7-triazacyclononanyl titanium Dichloride, N-methyl- (2,6,
10-trimethoxy) 1,5,9-triazacyclododecanyl titanium dichloride, N-methyl- (2,5,8-triphenoxy) 1,4,7-triazacyclononanyl titanium dichloride, N-methyl- (2,6,10-Triphenoxy) 1,5,9-triazacyclododecanyl titanium dichloride and the like.

In the above example, R ¹ in the general formula (2) -B
Is a methyl group, but R ¹ is a phenyl group, a benzyl group, an acetyl group, a trifluoroacetyl group, a trifluoromethyl group, a methoxy group, a phenoxy group, a cyano group, a halogen atom (fluorine, chlorine or Bromine) or the like.

Examples of the transition metal compound (A) of the general formula (3) -B: N-methyl-1,3,5,7-tetraazacyclooctanyl titanium chloride, N-methyl-1,4,7, 10
-Tetraazacyclododecanyl titanium chloride, N-
Methyl-1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl-1,6,11,16
-Tetraazacycloeicosanyl titanium chloride, N
-Methyl- (2-methyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl- (2
-Methyl) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl- (2-phenyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl- ( 2-phenyl) 1,5,
9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl- (2-acetyl) 1,4,7,10
-Tetraazacyclododecanyl titanium chloride, N-
Methyl- (2-acetyl) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl-
(2-fluoro) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl- (2-fluoro) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl -(2-trifluoromethyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl- (2-trifluoromethyl) 1,5,9,13-tetraazacyclohexadecanyl titanium Chloride, N-methyl- (2-methoxy) 1,
4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl- (2-methoxy) 1,5,9,13-
Tetraazacyclohexadecanyl titanium chloride, N
-Methyl- (2,5,8,11-tetramethyl) 1,4,7,
10-tetraazacyclododecanyl titanium chloride,
N-methyl- (2,6,10,14-tetramethyl) 1,
5,9,13-Tetraazacyclohexadecanyl titanium chloride, N-methyl- (2,5,8,11-tetraphenyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl -(2,6,10,14-tetraphenyl) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl- (2,5,
8,11-tetraacetyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl-
(2,6,10,14-tetraacetyl) 1,5,9,13-
Tetraazacyclohexadecanyl titanium chloride, N
-Methyl- (2,5,8,11-tetrafluoro) 1,4,
7,10-tetraazacyclododecanyl titanium chloride, N-methyl- (2,6,10,14-tetrafluoro) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride, N-methyl- ( 2,5,8,11-tetratrifluoromethyl) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl-
(2,6,10,14-tetratrifluoromethyl) 1,
5,9,13-Tetraazacyclohexadecanyl titanium chloride, N-methyl- (2,5,8,11-tetramethoxy) 1,4,7,10-tetraazacyclododecanyl titanium chloride, N-methyl -(2,6,10,14-tetramethoxy) 1,5,9,13-tetraazacyclohexadecanyl titanium chloride and the like.

In the above example, R ¹ in the general formula (3) -B
Is a methyl group, but R ¹ represents a phenyl group, a benzyl group, an acetyl group, a trifluoroacetyl group, a trifluoromethyl group, a methoxy group, a phenoxy group, a cyano group, a halogen group instead of a methyl group. Atoms (fluorine,
Chlorine or bromine) or the like, but is not limited thereto.

Examples of transition metal compounds of the general formula (3) -C: N-
Methyl-N'-methyl-1,3,5,7-tetraazacyclooctanyl titanium dichloride, N-methyl-N'-
Methyl-1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N′-methyl-1,
5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl-1,6,11,
16-tetraazacycloeicosanyl titanium dichloride, N-methyl-N'-methyl- (2-methyl) 1,4,
7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N′-methyl- (2-methyl) 1,
5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2-phenyl) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N '-Methyl- (2-phenyl) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl-
(2-acetyl) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2-acetyl) 1,5,9,13-tetraazacyclohexadecanyl titanium Dichloride, N-methyl-
N'-methyl- (2-fluoro) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2-fluoro) 1,5,9,13-
Tetraazacyclohexadecanyl titanium dichloride,
N-methyl-N'-methyl- (2-trifluoromethyl) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2-trifluoromethyl) 1, 5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N '
-Methyl- (2-methoxy) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-
N'-methyl- (2-methoxy) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-
Methyl-N′-methyl- (2,5,8,11-tetramethyl) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N′-methyl- (2,6,
10,14-tetramethyl) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2,5,8,11-tetraphenyl)
1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2,6,1
0,14-tetraphenyl) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2,5,8,11-tetraacetyl)
1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2,6,1
0,14-tetraacetyl) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2,5,8,11-tetrafluoro)
1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl- (2,6,1
0,14-tetrafluoro) 1,5,9,13-tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2,5,8,11-tetratrifluoromethyl) 1,4 , 7,10-Tetraazacyclododecanyl titanium dichloride, N-methyl-N'-methyl-
(2,6,10,14-tetratrifluoromethyl) 1,
5,9,13-Tetraazacyclohexadecanyl titanium dichloride, N-methyl-N'-methyl- (2,5,8,
11-tetramethoxy) 1,4,7,10-tetraazacyclododecanyl titanium dichloride, N-methyl-N '
-Methyl- (2,6,10,14-tetramethoxy) 1,
5,9,13-tetraazacyclohexadecanyl titanium dichloride and the like.

In the above example, R ¹ in the general formula (3) -C
And R ⁴ is a methyl group, but R ¹ and R ⁴ are phenyl, benzyl, acetyl, trifluoroacetyl, trifluoromethyl, methoxy, phenoxy, cyano, halogen Atoms (fluorine,
Chlorine or bromine). As the catalyst, one of the transition metal compounds (A) described above may be used alone, or two or more may be used in combination.

[Component (B)] Examples of the organoaluminum compound (hereinafter referred to as organoaluminum compound (B)) as the component (B) of the catalyst include, for example, a general formula (4): RaAlZ3-a (4) Wherein R is a hydrocarbon group having 1 to 20 carbon atoms;
Is a hydrogen atom, an alkoxy group or a halogen atom,
a is a number satisfying 0 ≦ a <3. And an organic aluminum compound represented by the general formula (5):-[Al (Rxx) -O] b- (5) [where Rxx represents an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms. An aralkyl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms,
Is an integer of 1 or more.] A chain or cyclic aluminoxane compound having a structure represented by the following formula: These may be used alone or in combination of two or more.

In the general formula (4), the hydrocarbon group having 1 to 20 carbon atoms represented by Rxx is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl Octyl, phenyl, benzyl, 1,5-diisopropylphenyl and tetramethylphenyl, preferably methyl, ethyl and isobutyl, and the alkoxy group represented by Z is, for example, methoxy, ethoxy, n-butoxy, isobutoxy , Phenoxy, benzoxy, and halogen atoms are fluorine, chlorine,
Bromine and the like, and preferred Z is a hydrogen atom, methoxy, itbutoxy, or chlorine atom. The preferred range of a is 2-3
It is.

Specific examples of such an organoaluminum compound of the general formula (4) include trimethylaluminum, triethylaluminum, tributylaluminum, triisopropylaluminum, diisopropylaluminum chloride, isopropylaluminum dichloride, triisobutylaluminum chloride, diisobutylaluminum chloride, Alkyl aluminum halides such as isobutylaluminum dichloride, trit-butylaluminum, dit-butylaluminum chloride, t-butylaluminum dichloride, triamylaluminum, diamylaluminum chloride, amylaluminum dichloride, triethyldialuminum trichloride, dimethylaluminum hydride , Diisobutylal Um hydride, alkyl aluminum hydride such as dioctyl aluminum hydride, methyl aluminum dimethoxide, diisobutylaluminum methoxide, alkylaluminum alkoxide such as isobutyl aluminum ethoxide.

In the general formula (5), the alkyl group having 1 to 20 carbon atoms represented by Rxx is, for example, methyl, ethyl, isobutyl, isopropyl, n-butyl, hexyl, octyl, pentyl, The aryl group of the numbers 6 to 40 is, for example, phenyl or benzyl. Rxx
Are preferably a methyl group, an ethyl group and an isobutyl group, and particularly preferably a methyl group.

Specific examples of such a compound of the general formula (5) include tetramethyldialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane,
Ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane and the like can be mentioned.

Among the organoaluminum compounds (B) described above, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferable among the organoaluminum compounds of the general formula (4) because of their excellent catalytic activity. , General formula
Among the organoaluminum compounds (5), methylaluminoxane is preferred.

[Component (C)] The ionic compound which is the component (C) of the catalyst can have at least one anion and at least one cation in the compound, and is separated into a cation and an anion in a solution. Is a compound that exists as A typical example is a compound represented by the following general formula (6). ([L] ^{k +} ) p (M '(A) n] ^- ) q (6) [wherein [L] ^{k +} is a Bronsted acid or a Lewis acid, and M' is group 13 to 15 of the periodic table. N is an integer of 2 to 8, and n n of A are independently a hydrogen atom, F, C
l, Br, halogen atoms such as I, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, octyl, alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl, dimethylamino, diethylamino, Dialkylamino groups having 1 to 30 carbon atoms such as diphenylamino, and carbon atoms such as methoxy, ethoxy, propoxy and butoxy
An alkoxy group of 1 to 20, a phenyl group, a tolyl group, a xylyl group, an aryl or aralkyl group having 6 to 40 carbon atoms such as a benzyl group, a phenoxy, tolyloxy, xylyloxy, benzoxy, 2,6-dimethylphenoxy group,
An aryloxy group or an aralkyloxy group having 6 to 40 carbon atoms such as naphthyloxy, p-fluorophenyl,
Halogen-substituted hydrocarbon groups having 1 to 40 carbon atoms, such as 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl, 3,5-ditrifluoromethylphenyl, and acetoxy groups ,
An ethyloxy group, an acyloxy group having 1 to 20 carbon atoms such as a phenylacetoxy group or 5-methylstibino,
Organic metalloid groups such as trimethylsilyl, trimethylgermyl, diphenylarsino, dicyclohexylstibino, and diphenylboryl;
Is an integer of 1 to 3, p is an integer of 1 or more, and q = (k
× p). In the general formula (6), examples of the Bronsted acid or Lewis acid represented by L include ammonia, methylamine, aniline, dimethylamine, N-methylaniline, diphenylamine, N, N-dimethylamine,
Examples include amines such as pyridine and p-bromo-N, N-dimethylaniline, and phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, and preferably dimethylether, diethylether, and the like.
Ethers such as THF and dioxane; amines (especially dimethylamine, diphenylamine and N, N-dimethylamine); thioethers such as diethylthioether and tetrahydrothiophene; and ethylbenzoate. Examples of the elements of Groups 13 to 15 of the periodic table represented by M ′ include B, Al, Ga, In, C, Si, Ge, Sn, Pb,
Examples include N, P, As, Sb, and Bi, with B and P being particularly preferred.

Specific examples of component (C) include trimethylammonium tetraphenylborate, methyl (dibutyl) ammonium tetraphenylborate, dimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, and methylpyridinium tetraphenylborate (2-cyanopyridinium). ), Trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl]
Examples thereof include dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, and ferrocenium tetrakis (pentafluorophenyl) borate. Among such compounds, dimethylanilinium tetrakis (pentafluorophenyl) borate is more preferable among the compounds represented by the general formula (6) in view of particularly excellent catalytic activity, but is not limited thereto. The ionic compounds described above can be used alone or in combination of two or more.

The component (A) and the component (B) of the catalyst, and optionally the component (C), may be used by supporting at least one of them on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier, for example, silica,
Alumina, zirconia, titania and the like, other inorganic carriers, for example, zeolite, activated clay, montmorillonite, silica-alumina, ferrite, and organic carriers,
For example, any of carbon black and the like can be used. There is no particular limitation on the loading method, and a known method may be appropriately used.

As the combination of the constituent components of the catalyst,
(A) Transition metal compound (A) + organoaluminum compound (B)
And (b) transition metal compound (A) + organoaluminum compound (B) + ionic compound (C).
As the combination (a), a combination of the transition metal compound (A) and the aluminoxane compound represented by the general formula (5) is preferable. As the combination of (b), the transition metal compound (A), the organoaluminum compound (among others, trialkylaluminum) represented by the general formula (4) and the ionic compound (C) are dimethyl tetrakis (pentafluorophenyl) borate. A combination of anilinium is preferred.

The proportions of the components (A), (B) and (C) are not particularly limited, but are preferably in a molar ratio of (A) :( B) = 1: 0.01 to 1:20.
000, (B) :( C) = 1: 0.01 to 1: 1000. The catalyst components (A), (B), and (C) may be individually supplied to the reaction system, or two or three types may be brought into contact with the components in advance and then supplied to the reaction system. .

Conditions: The polymerization of the above-mentioned monomer using the above-mentioned catalyst can be carried out in a solution or a slurry. When the polymerization is performed in a solution, any organic solvent generally used as a solvent may be used, and specific examples thereof include benzene, toluene, xylene, pentane, hexane, cyclohexane, and methylene chloride. It may be used as a solvent.

The polymerization temperature is not particularly limited, but may be from -100 ° C to 3 ° C.
It can be carried out up to 00 ° C, but is preferably between -20 ° C and 200 ° C. The polymerization pressure is not particularly limited, but is 0.5 to 1 in terms of being industrial and economical.
About 500 atmospheres is desirable. More preferably, it is in the range of 1 to 500 atm. The polymerization method can be a continuous type or a batch type. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight.

Any known catalyst other than the above-mentioned catalysts can be used in combination as long as the effects of the present invention are not impaired. Utility One example of the field of application of the copolymer of the present invention is as follows. In the case of low molecular weight products (number average molecular weight of about 1,000 to 5,000), fields in which synthetic waxes can be usually used, that is, paper processing materials, sizing materials,
Examples include rubber aging inhibitors, electrical insulators, water repellents, lubricants for molding synthetic resins, adhesives and the like. In the case of a high molecular weight substance (number average molecular weight of about 5,000 to 100,000), various kinds of optical fields utilizing its transparency, applications such as optical lenses, optical fibers, optical disks, sheets, films, etc., and various binders due to having a polar group. Applications, electric and electronic fields, liquid crystal display materials, high frequency circuit board materials, housings for various instruments, medical fields such as syringes, and various molded products such as general-purpose sheets, films, cases, etc. If the structural unit derived from the polar group-containing cyclic olefin is 30 mol% or more, the transparency is used in the optical field, and
If it is less than mol%, it can be used as a material for improving the adhesion of olefin resin to metals or other materials.

[0051]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, physical properties were measured as follows. (A) Ester-containing cyclic olefin content (% by weight) was determined by ¹ H-NMR. (B) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The polymer of the sample was dissolved in tetrahydrofuran (THF) using a WATERS 150C type gel permeation chromatography apparatus and measured at 30 ° C. . (C) Glass transition temperature (Tg) 50 ° C using a differential scanning calorimeter (DSC) SSC5200H manufactured by SII
The measurement was performed in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min in the range of −300 ° C.

(Example 1) Purified toluene 1.
9 l, 8-methyl-8-key-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 0.1 l, 6 mmol of an aluminum atom in terms dissolved in purified toluene 4 ml methylaluminoxane At 30 ° C
And then pressurize with ethylene to reduce the ethylene partial pressure.
It was 1 kg / cm ² . Then, 1.2 μmol of 1,5,9-triazacyclododecanyl titanium chloride dissolved in 1.2 ml of purified toluene was added to initiate polymerization. During the reaction, maintain the temperature at 30 ° C and the ethylene partial pressure is 1 kg / c
while continuously feeding ethylene so as to maintain the m ² 1
A time reaction was performed. After the reaction was completed, the polymer solution was poured into 2 liters of methanol to precipitate a polymer, and the polymer was separated by filtration and dried under reduced pressure to obtain 1.25 g of a polymer.

This polymer had a cyclic olefin content of 89 mol%, a number average molecular weight (Mn) of 9,800, and a molecular weight distribution (Mw / Mn) of 2.87, ethylene / 8-methyl-8-carboxymethyltetracyclo [4.4 .0.1 ^2,5 .1 ^7,10] -3 it was dodecene copolymer. The Tg of this copolymer was 121 ° C. The ¹ H-NMR chart of the obtained copolymer is shown in FIG.

(Example 2) Purified toluene 1. was placed in a 3-liter stainless steel autoclave sufficiently purged with nitrogen.
9 l, 8-methyl-8-key-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene 0.1 liters, triisobutylaluminum 0.6 mmol, dissolved in purified toluene 4 ml was added, further Dimethylanilinium tetrakis (pentafluorophenyl) borate 1.
After adding 5 μmol and heating to 30 ° C., the mixture was pressurized with ethylene to obtain a partial pressure of ethylene of 1 kg / cm ² .

Then, 1.2 μmol of 1,5,9-triazacyclododecanyl titanium chloride dissolved in 1.2 ml of purified toluene was added to initiate polymerization. During the reaction, the temperature was maintained at 30 ° C., ethylene was continuously supplied so that the ethylene partial pressure was maintained at 1 kg / cm ^2, and the reaction was carried out for 1 hour. After completion of the reaction, the polymer solution was poured into 2 liters of methanol to precipitate a polymer. The polymer was separated by filtration and dried under reduced pressure to obtain 2.36 g of a polymer. This polymer had a cyclic olefin content of 82 mol%, a number average molecular weight (Mn) of 12200, and a molecular weight distribution (Mw / M
n) is an ethylene / 8-methyl-8-key-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene copolymer of 2.80. The Tg of this copolymer was 102 ° C.

(Example 3) In Example 1, ^5- methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5.1 ^7,10 ] -3-dodecene was used as the polar group-containing cyclic olefin instead of 8-methyl-8-carboxymethyltetracyclo.
0.78 g of a polymer was obtained in the same manner as in Example except that -carboxymethyl-bicyclo [2.2.1] -2-heptene was used. This polymer had a cyclic olefin content of 95
Mol%, number average molecular weight (Mn) 9700, molecular weight distribution (Mw / M
n) is ethylene / 5-carboxymethyl-bicyclo of 3.01
[2.2.1] -2-heptene copolymer. The Tg of this copolymer was 104 ° C.

(Example 4) In Example 2, ^5- methyl-8-carboxymethyltetracyclo [4.4.0.1 2,5.1 ^7,10 ] -3-dodecene was used as the polar group-containing cyclic olefin instead of 8-methyl-8-carboxymethyltetracyclo.
In the same manner as in Example 2 except that -carboxymethyl-bicyclo [2.2.1] -2-heptene was used, 1.55 g of a polymer was obtained. The polymer has a cyclic olefin content of
90 mol%, number average molecular weight (Mn) is 10800, molecular weight distribution (Mw
/ Mn) was 2.99, which was an ethylene / 5-carboxymethyl-bicyclo [2.2.1] -2-heptene copolymer. The Tg of this copolymer was 107 ° C.

(Example 5) In Example 1, 1,5,9-triazacyclododecanyl titanium chloride was replaced with 1,1
0.59 g of a polymer was obtained in the same manner as in Example 1 except that 4,7-triazacyclononanyl titanium chloride was used. This polymer had a cyclic olefin content of 88 mol%, a number average molecular weight (Mn) of 10200, and a molecular weight distribution (Mw / M
n) is an ethylene / 8-methyl-8-key-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene copolymer of 3.05. The Tg of this copolymer was 107 ° C.

(Example 6) In Example 2, instead of 1,5,9-triazacyclododecanyl titanium chloride, 1,4,
1.82 g of a polymer was obtained in the same manner as in Example 2 except that 7-triazacyclononanyl titanium chloride was used.
This polymer had a cyclic olefin content of 93 mol.
%, Number average molecular weight (Mn) is 9200, molecular weight distribution (Mw / Mn)
3.11 was an ethylene / 8-methyl-8-key-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene copolymer. The Tg of this copolymer was 112 ° C.

[0060]

According to the present invention, there is provided a novel ethylene / polar group-containing cyclic olefin copolymer having utility in the above various fields.

[Brief description of the drawings]

FIG. 1 shows the ethylene / 8-methyl-8- obtained in Example 1.
Carboxyanhydride methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
¹ is a ¹ H-NMR chart of a dodecene copolymer.

Claims (1)

[Claims] (1) a) a structural unit derived from ethylene, and (b) a general formula (1): Wherein A and B are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; one of X and Y is a group represented by the formula: — (CH 2) n COOR (where R is the number of carbon atoms) A hydrocarbon group having 1 to 20; n represents an integer of 0 to 10), and the other is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a formula:-(CH2 ) nCOOR (where R and n
Represents an ester group represented by the above), or X and Y are mutually bonded to form the formula:-[(CH ₂ ) _n -CO
-O-CO- (CH _{2) n]} - (where the two n identical or different, being as defined above) to form a divalent group represented by. m represents 0 or 1. Copolymer having a structural unit derived from a polar group-containing cyclic olefin represented by the polystyrene equivalent number average molecular weight of 1,000 to 1
Ethylene, wherein the structural unit derived from the polar group-containing cyclic olefin in the copolymer is 1 to 99 mol%.
Polar group-containing cyclic olefin copolymer.