KR20170012223A - Method for producing cyclic olefin copolymer - Google Patents

Abstract

The present invention provides a method for producing a copolymer having a smaller amount of a catalyst, which is excellent in mechanical properties and can obtain a cyclic olefin copolymer having a molecular weight suitable for ordinary molding processing.
Olefin monomer (B) derived from at least norbornene-derived cyclic olefin monomer (A) and C4-C12 alpha -olefin monomer (B) in the presence of a titanocene catalyst to obtain a copolymer, Wherein the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst and the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a cyclic olefin copolymer,

The present invention relates to a process for producing a cyclic olefin copolymer.

The cyclic olefin polymer and the cyclic olefin copolymer (also referred to as "COP" and "COC", respectively) have low hygroscopicity and high transparency and can be used for various applications including optical disk substrates, optical films and optical fibers . As a representative COC, there is a copolymer of cyclic olefin and ethylene. Since the glass transition temperature of the copolymer can be changed to the copolymerization composition of cyclic olefin and ethylene, it can be produced as a copolymer having a glass transition temperature (Tg) higher than that of COP And can achieve a Tg of more than 200 DEG C, which is difficult in COP, but it has a problem of low mechanical strength, poor handleability and processability because it has hard and soft properties.

In addition, there are various kinds of high Tg polymers, but since they have a polar group, there is a limitation in hygroscopicity and dielectric properties. For this reason, there is a demand for a high-Tg polymer which does not have a polar group and is composed of an olefin skeleton and has excellent optical characteristics, dielectric properties, and mechanical strength.

As a method for improving the mechanical strength of high Tg COC, there is a method of copolymerizing a cyclic olefin with an? -Olefin other than ethylene (hereinafter, referred to as "specific? -Olefin"). Various studies have been made on the copolymerization of the cyclic olefin and the specific? -Olefin.

The copolymerization of the cyclic olefin and the specific? -Olefin is greatly different from the copolymerization of the cyclic olefin and ethylene. In the copolymerization of the cyclic olefin and the specific? -Olefin, a chain transfer reaction originating in a specific? -Olefin is generated under the condition that a high molecular weight product is obtained by copolymerization of the cyclic olefin and ethylene. Hence, it has been difficult to obtain a high molecular weight product. Therefore, a copolymer of a cyclic olefin and a specific? -Olefin is not suitable as a molding material (see, for example, Non-Patent Document 1).

In Patent Document 1, a high molecular weight material comprising a cyclic olefin and a specific? -Olefin was obtained from a specific Ti-based catalyst, and a film having excellent physical properties with a Tg of 245 to 262 ° C, low moisture absorption and a coefficient of linear expansion of less than 80 ppm was obtained . However, in the polymerization method disclosed in Patent Document 1, since a large amount of the catalyst and promoter are used, it is difficult to save resources, the cost for obtaining the copolymer is high, and the catalyst and co- The transparency of the film is deteriorated. In Patent Document 1, it is described that a copolymer of 92-164 g is obtained per 1 g of the catalyst.

Patent Document 2 discloses a film having excellent puncturing property, but Tg is less than 170 占 폚. In Patent Document 2, since a large amount of a catalyst and a promoter are used, it is difficult to save resources, the cost for obtaining the copolymer is high, and the transparency and thermal stability of the film are impaired. In Patent Document 2, it is described that a copolymer of 127-275 g per 1 g of the catalyst is obtained.

Japanese Patent Application Laid-Open No. 2009-298999 Japanese Patent No. 5017222

Jung, H. Y., Polyhedron, 2005, Vol. 24, p.1269-1273

SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing a copolymer capable of obtaining a cyclic olefin copolymer having a smaller catalytic amount and a molecular weight suitable for ordinary molding, .

The present inventors have found that by using a smaller amount of titanocene catalyst, it is possible to obtain more cyclic olefin copolymers having excellent mechanical properties and molecular weight suitable for general molding processing, and have completed the present invention. More specifically, the present invention provides the following.

(1) a polymerization step of polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha -olefin monomer (B) derived from an alpha -olefin of C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer Wherein the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst and the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less.

(2) The production method according to (1), wherein the polymerization step is carried out in the presence of a cocatalyst comprising alkylaluminoxane and a chain transfer agent together with the titanocene catalyst.

(3) The production process according to (2), wherein the chain transfer agent is alkylaluminum.

(4) The process according to (3), wherein the alkylaluminum is trimethylaluminum.

(5) The production process according to any one of (1) to (4), wherein the glass transition temperature (Tg) of the copolymer is 170 占 폚 or higher.

According to the present invention, it is possible to provide a method for producing a copolymer which is capable of obtaining a cyclic olefin copolymer having a smaller amount of catalyst, excellent mechanical properties, and a molecular weight suitable for ordinary molding processing. In particular, by controlling the amount of the chain transfer agent, the effect of the present invention can be further improved. In the present invention, since the amount of the catalyst to be used is small, the amount of the cocatalyst can be reduced accordingly. Therefore, it is possible to increase the amount of the cyclic olefin copolymer per one batch while maintaining the range of the molecular weight at a low cost with a smaller amount of catalyst and promoter, thereby realizing resource saving. In addition, since the catalyst and the cocatalyst remaining in the resulting copolymer are small, a molded product such as a film obtained from such a copolymer tends to have improved transparency and mechanical properties.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The process for producing a copolymer according to the present invention comprises polymerizing at least a norbornene-derived cyclic olefin monomer (A) and an? -Olefin monomer (B) derived from a C4 to C12? -Olefin in the presence of a titanocene catalyst Wherein the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst and the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less. According to the process for producing a copolymer according to the present invention, it is possible to obtain a higher molecular weight cyclic olefin copolymer in one batch while maintaining a molecular weight range, even at a smaller catalyst amount. Particularly, from the viewpoint of the amount of the catalyst to be used, the amount of the obtained copolymer and the number average molecular weight, in the process for producing the copolymer according to the present invention, the polymerization step is carried out in the presence of the titanocene catalyst, It is preferably carried out in the presence of a chain transfer agent.

[Copolymer]

The copolymer obtained by the process for producing a copolymer according to the present invention is a copolymer obtained by copolymerizing a structural unit derived from a cyclic olefin monomer (A) derived from norbornene and an? -Olefin monomer (B) derived from a C4 to C12? Derived structural units.

The amount of the copolymer obtained by the polymerization process included in the above production method is 1000 g or more per 1 g of the titanocene catalyst used in the above polymerization step, preferably 2,000 g or more.

The number average molecular weight of the copolymer in the present invention is preferably 20,000 or more and 200,000 or less, more preferably 30,000 or more and 150,000 or less. When the number-average molecular weight is 20,000 or more, the resulting copolymer does not have an excessively low glass transition temperature (Tg). When the number-average molecular weight is 200,000 or less, the viscosity of the obtained solution of the copolymer is not excessively high. In the present specification, the number average molecular weight refers to the number average molecular weight in terms of polystyrene measured by gel permeation chromatography.

The glass transition temperature (Tg) of the copolymer in the present invention is 170 占 폚 or higher, preferably 200 占 폚 or higher, more preferably 230 占 폚 or higher, particularly preferably 260 占 폚 or higher. When the glass transition temperature is 170 占 폚 or higher, the transparent film obtained from the copolymer has a sufficient heat resistance and can therefore be suitably used as, for example, an ITO vapor deposition substrate. In particular, when the glass transition temperature is 260 占 폚 or higher, the transparent film obtained from the copolymer has more sufficient heat resistance, so that even if it contacts molten lead-free solder, distortion, cracking, So that it can be suitably used as a member for lead-free solder. The upper limit of the glass transition temperature of the copolymer is not particularly limited. However, the higher the glass transition temperature, the smaller the structural units derived from the -olefin in the copolymer, and thus the improvement effect of the mechanical strength by the- The glass transition temperature is preferably 350 DEG C or lower, and more preferably 330 DEG C or lower. In this specification, the glass transition temperature is a value measured by a DSC method (a method described in JIS K7121) at a temperature raising rate of 20 deg. C / min.

[Titanocene catalyst]

The titanocene catalyst is not particularly limited, and known catalysts can be used. The titanocene catalysts can be used singly or in combination of two or more.

Examples of the titanocene catalyst include those represented by the following formula (1).

R ¹ to R ³ each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopentyl and cyclohexyl; An aryl group such as a phenyl group, a biphenyl group, a phenyl group or a biphenyl group having the alkyl group as a substituent, a naphthyl group, and a naphthyl group having the alkyl group as a substituent.

R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, ; A substituted or unsubstituted aryl group having a substituent such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, An alkyl group of these; A phenyl group, a biphenyl group, a naphthyl group, and the above-mentioned aryl group having a halogen atom or an alkyl group as a substituent.

R ⁶ to R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silyl group having 1 to 12 carbon monovalent hydrocarbon groups as substituents. Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, Cyclohexyl group, and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and an aryl group having the alkyl group as a substituent. Specific examples of the silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t- And a silyl group having, as a substituent, an alkyl group having 1 to 12 carbon atoms such as a heptyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group.

Specific examples of the titanocene catalyst represented by the general formula (1) include dimethyl (9-fluorenyl) silanetitanium dimethyl, (isobutylamido) dimethyl-9-fluorenylsilanetitanium dimethyl, (Isopropylamido) dimethyl-9-fluorenylsilanetitanium dichloride, (isobutylamido) dimethyl-9- (3,6-dimethylfluorenyl) dimethyl- Dimethyl-9- (3,6-dimethylfluorenyl) silanetitanium dichloride, (isobutyl) silanetitanium dichloride, (t-butylamido) dimethyl-9-fluorenylsilanetitanium dichloride, Amide) Dimethyl-9- (3,6-dimethylfluorenyl) silanetitanium dichloride, (t-butylamido) dimethyl-9- (3,6-dimethylfluorenyl) silanetitanium dimethyl, (isopropylamide) Dimethyl-9- [3,6-di (i-propyl) fluorenyl] silanetitanium dichloride, (isobutylamido) dimethyl- (Isopropylamido) dimethyl-9- [3,3-di (i-propyl) fluorenyl] silanetitanium dichloride, dimethyl (Tert-butyl) fluorenyl] silanetitanium dichloride, (isobutylamido) dimethyl-9- [3,6-di (t- Amide) Dimethyl-9- [3,6-di (t-butyl) fluorenyl] silanetitanium dimethyl, (isopropyl amide) dimethyl- (T-butyl amide) dimethyl-9- [2,7-di (tert-butyl) fluorenyl] silanetitanium dichloride, (isopropylamido) dimethyl-9- (2,3,6,7-tetramethylfluorenyl) silanetitanium dichloride, (isobutylamido) dimethyl-9- (2,3,6,7-tetramethylfluorenyl) silanetitanium dichloride, (t-butylamido) dimethyl-9- (2,3,6,7- Fluoren-yl) silane titanium dimethyl, and the like. Dimethyl-9-fluorenylsilanetitanium dimethyl ((t-BuNSiMe ₂ Flu) TiMe ₂ ). (t-BuNSiMe ₂ Flu) TiMe ₂ is a titanium complex represented by the following formula (2) and can be easily synthesized based on the description of "Macromolecules, Vol. 31, p. 3184, 1998" have.

(Wherein Me represents a methyl group and t-Bu represents a tert-butyl group.)

[Co-catalyst comprising alkylaluminoxane]

The cocatalyst used in the present invention is composed of alkylaluminoxane. The cocatalyst may be used alone or in combination of two or more.

The alkylaluminoxane is not particularly limited and includes, for example, compounds represented by the following formula (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) is a product obtained by the reaction of trialkylaluminum with water.

(Wherein R represents an alkyl group having 1 to 4 carbon atoms and n represents an integer of 0 to 40, preferably 2 to 30.)

Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl groups of methylaluminoxane are replaced with another alkyl group. The modified methylaluminoxane is preferably, for example, a methylaluminoxane having a substituted alkyl group having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group, And a modified methyl aluminoxane in which a part of the methyl group is substituted with an isobutyl group is more preferable. Specific examples of the alkyl aluminoxane include methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, methyl ethyl aluminoxane, methyl butyl aluminoxane, and methyl isobutyl aluminoxane. Of these, methylaluminoxane and methylisobutylaluminoxane are preferred.

The alkylaluminoxane can be prepared by a known method. As the alkylaluminoxane, commercially available products may also be used. Examples of commercially available products of alkylaluminoxanes include MMAO-3A, TMAO-200 series and TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.) and methylaluminoxane solution have.

[Chain transfer agent]

The chain transfer agent used in the present invention is a compound having chain transfer ability (migration ability). The chain transfer agent may be used singly or in combination of two or more kinds.

The chain transfer agent is not particularly limited, and known compounds having chain transfer ability can be used, and examples thereof include alkyl aluminum. As the alkylaluminum, for example, a compound represented by the following formula (5) can be mentioned.

(R ¹⁰ ) _z AlX _{3 - z} (5)

(Wherein R ¹⁰ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3.)

Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an n-octyl group.

Specific examples of the alkylaluminum include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum and tri-n-octylaluminum; Dialkylaluminum hydrides such as dimethylaluminum chloride and diisobutylaluminum chloride; Dialkylaluminum hydrides such as diisobutylaluminum hydride; And dialkyl aluminum alkoxide such as dimethyl aluminum methoxide.

Chain shuttling systems known as polymerization in metallocene catalysts can be used as other chain transfer agents. Examples of the chain shuttling agent include alkyl aluminum and alkyl zinc described above. Examples of the alkyl zinc include compounds represented by the following general formula (6).

(R ¹¹ ) _z ZnX _{2 - y} (6)

(Wherein R ¹¹ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and y is an integer of 0 to 2.)

Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an n-octyl group.

Specific examples of alkyl zinc include dialkyl zinc such as dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-sec-butyl zinc aluminum and di-n-octyl zinc; Alkyl zinc hydrides such as methyl zinc chloride and isobutyl zinc chloride; Alkyl zinc hydrides such as isobutyl zinc hydride; Alkyl zinc alkoxides such as methyl zinc methoxide; And zinc halides such as zinc chloride.

The alkyl aluminum or alkyl zinc may be directly introduced into the polymerization system or may be added in the state of being contained in the alkylaluminoxane. It may also be an alkyl aluminum source which is used in the production of alkylaluminoxanes and which remains after the production. Alkyl aluminum and alkyl zinc may also be used in combination.

[Cyclic Olefinic Monomer (A)]

Examples of the cyclic olefin monomer (A) derived from norbornene include norbornene and substituted norbornene, and norbornene is preferable. The cyclic olefin monomers (A) may be used singly or in combination of two or more.

The substituted norbornene is not particularly limited, and examples of the substituent of the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (I).

(Wherein R ¹ to R ¹² may be the same or different and each is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,

R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may be monosubstituted to form a bivalent hydrocarbon group,

R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.

N represents 0 or a positive integer,

When n is 2 or more, R ⁵ to R ⁸ may be the same or different among the respective repeating units.

However, when n = 0, at least one of R ¹ to R ⁴ and R ⁹ to R ¹² is not a hydrogen atom.)

The substituted norbornene represented by the general formula (I) will be described. R ¹ to R ¹² in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ¹ to R ⁸ include, for example, a hydrogen atom; Halogen atoms such as fluorine, chlorine and bromine; An alkyl group having 1 to 20 carbon atoms, and the like, which may be different from each other, may be partially different, or may be all the same.

Specific examples of R ⁹ to R ¹² include, for example, a hydrogen atom; Halogen atoms such as fluorine, chlorine and bromine; An alkyl group having 1 to 20 carbon atoms; A cycloalkyl group such as a cyclohexyl group; Substituted or unsubstituted aromatic hydrocarbon groups such as a phenyl group, a trityl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, and an anthryl group; A benzyl group, a phenethyl group, and an aralkyl group in which an alkyl group is substituted with an aryl group, and the like, which may be different from each other, may be partially different, or may be all the same.

Specific examples of the case where R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² are combined to form a bivalent hydrocarbon group include alkylidene groups such as ethylidene group, propylidene group and isopropylidene group, .

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the ring formed may be monocyclic or polycyclic, may be polycyclic with a bridge, may be a ring having a double bond, Or a combination of these rings. These rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2.1] hept-2-ene, 2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hepta- ] Hept-2-ene;

Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (synonym: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene; Tricyclo [4.4.0.1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene or partial hydrogenation products thereof (or cyclopentadiene and cyclo Adduct of hexene) tricyclo [4.4.0.1 ^2,5 ] undec-3-ene; 2.2.1] hept-2-ene, 5-cyclohexylbicyclo [2.2.1] hept-2-ene, 3-cyclic olefins such as 2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene;

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-en (simply referred to as tetracyclododecene), 8-methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] car-3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-methylidene tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodeca-3-ene, 8-vinyl-tetracyclo [4,4.0.1 ^2,5 .1 ^{7 , 10]} dodeca-3-ene, 8-propenyl tetracyclo ^{[4.4.0.1 2,5 .1 7, 10]} 4 ring cyclic olefin such as dodeca-3-ene;

8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca- 3-ene, 8-cyclohexenyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodeca-3-ene; Tetracyclo [7.4.1 ^3,6 .0 ^1,9 .0 ^2,7 ] tetradeca-4,9,11,13-tetraene (1,4-methano-1,4,4a, 9a-tetra also referred to as dihydro-fluorene), tetracyclo [8.4.1 ^4,7 .0 ^1,10 .0 ^{3, 8-pentamethyl} -5,10,12,14- deca-tetraene (1,4-meth furnace 1, 4,4a, 5,10,10a-hexahydroanthracene); ^Pentacyclo [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] decene, 4-decene, penta-cyclo penta ^{[7.4.0.0 2,7 .1 3,6 .1 10,13]} ; Cyclo hepta ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3,8 .0 12,16] -5- eicosene, heptacyclo cyclo [8.7.0.1 ^2,9 .0 ^3,8 .1 ^4,7 .0 ^12,17 .1 ^13,16 ] -14-eicosene; Cyclic olefins such as tetrameric cyclopentadiene and the like.

Among them, an alkyl substituted norbornene (e.g., bicyclo [2.2.1] hept-2-ene substituted with at least one alkyl group), an alkylidene substituted norbornene (e.g., substituted with at least one alkylidene group Ethylidene-2-norbornene, or alternatively, 5-ethylidene-bicyclo [2.2.1] hepta- Ethylidene norbornene) is particularly preferable.

[alpha -olefin monomer (B)]

Examples of the? -Olefin monomer (B) derived from C4-C12? -Olefins include C4-C12? -Olefins and C4-C12? -Olefins having at least one substituent such as a halogen atom , C4-C12? -Olefins are preferable, and C6-C10? -Olefins are more preferable.

The? -Olefin of C4 to C12 is not particularly limited, and examples thereof include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and the like. Among them, 1-hexene, 1-octene and 1-decene are preferable.

[Conditions for Polymerization Process]

The conditions of the polymerization process are not particularly limited as long as the desired copolymer can be obtained, and known conditions can be used, and the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted. The amount of use of each component is exemplified as follows.

The amount of the? -olefin monomer (B) to be added is preferably 1 part by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, based on 100 parts by mass of the cyclic olefin monomer (A).

The amount of the titanocene catalyst used is preferably 0.00001 mass parts or more and 0.1 mass parts or less, more preferably 0.0001 mass parts or more and 0.05 mass parts or less, based on 100 mass parts of the cyclic olefin monomer (A).

The amount of the alkylaluminoxane to be used is preferably 0.0001 part by mass or more and 5 parts by mass or less, more preferably 0.01 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the cyclic olefin monomer (A).

The amount of the chain transfer agent to be used is preferably 0.0001 part by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the cyclic olefin monomer (A).

[ Example ]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. Unless otherwise stated, " part " representing quantity refers to " part by mass ".

[Production of Copolymer]

Each of the monomers listed in Table 1 and the cocatalyst shown in Table 2 were added to a glass reactor maintained in a nitrogen atmosphere and maintained at a polymerization temperature, and then the catalysts listed in Table 2 were added. The catalyst and the cocatalyst were respectively added to the reactor while dissolved in toluene. With the polymerization temperature and the polymerization time shown in Table 3, the inside of the reactor was stirred and polymerization was continued, and then 1 part by mass of 2-propanol was added to terminate the reaction. Subsequently, the resulting polymerization reaction solution was poured into a large amount of hydrochloric acid-acidified methanol to completely precipitate the polymer. After filtration to remove the polymer, the copolymer was recovered by drying under reduced pressure at 60 占 폚 or more for one day. The mass of the obtained copolymer was measured (" Quantity " in Table 3). The ratio of the obtained copolymer to the amount of the used catalyst was calculated ("g (copolymer) / g (catalyst)" in Table 3).

The types of catalysts and promoters used are as follows. Here, t-Bu represents a tert-butyl group and Flu represents a fluorenediyl group.

Catalyst A: (t-BuNSiMe ₂ Flu) TiMe ₂

Cocatalyst A: Methyl isobutylaluminoxane solution represented by MMAO-3A toluene solution ([(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] _n at 6.5 mass% (as content of Al atoms) (Containing 6 mol% of trimethylaluminum based on the total Al)

Cocatalyst B: 9.0 mass% (content of Al atoms) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% of trimethylaluminum based on total Al)

Cocatalyst C: Triisobutyl aluminum

Cocatalyst D: Dimethylanilinium tetrakis (pentafluorophenyl) borate

The number average molecular weight, Tg, of each copolymer is shown in Table 3.

The values of " part " in Table 1, Table 2, and Table 3 are values for 100 parts of 2-norbornene. Further, in Table 2, for the co-catalyst A and the co-catalyst B, the value of "part" is a value as a toluene solution.

As shown in Table 3, according to the present invention, the ratio of the copolymer obtained to the amount of the catalyst used is high.

Claims (5)

Polymerizing at least a cyclic olefin monomer (A) derived from norbornene and an alpha -olefin monomer (B) derived from an alpha -olefin of C4 to C12 in the presence of a titanocene catalyst to obtain a copolymer ,
Wherein the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the titanocene catalyst and the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less. The method according to claim 1,
Wherein the polymerization is carried out in the presence of a cocatalyst comprising a alkylaluminoxane and a chain transfer agent together with the titanocene catalyst. 3. The method of claim 2,
Wherein the chain transfer agent is alkylaluminum. The method of claim 3,
Wherein the alkyl aluminum is trimethyl aluminum. 5. The method according to any one of claims 1 to 4,
Wherein the copolymer has a glass transition temperature (Tg) of 170 DEG C or higher.