TW201609842A - Method for producing cyclic olefin copolymer - Google Patents

Abstract

Provided is a method for producing a copolymer that makes it possible to obtain, using a smaller amount of catalyst, more of a cyclic olefin copolymer having excellent mechanical properties and a molecular weight suitable for ordinary molding. A method for producing a copolymer, including a polymerization step for obtaining a copolymer by polymerizing at least a cyclic olefin monomer derived from norbornene (A) and an [alpha]-olefin monomer derived from a C4-C12 [alpha]-olefin (B) in the presence of a titanocene catalyst, the amount of copolymer obtained in this polymerization step being 1000 g or higher per gram of titanocene catalyst, and the number-average molecular weight of the copolymer being from 20,000 to 200,000.

Description

Method for producing cyclic olefin copolymer

This invention relates to a process for the manufacture of cyclic olefinic copolymers.

A cyclic olefin polymer and a cyclic olefin copolymer (also referred to as "COP" and "COC", respectively), which have low hygroscopicity and high transparency, and are used for opticals such as optical disk substrates, optical films, and optical fibers. A wide variety of uses, such as the field of materials. A representative COC has a copolymer of a cyclic olefin and ethylene, and since the glass transition temperature of the copolymer can change the copolymerization composition of the cyclic olefin and ethylene, the glass transition temperature (Tg) can be made higher than the COP. Although the copolymer can achieve a Tg of more than 200 ° C which is difficult to achieve by COP, it has a hard and brittle property, and has low mechanical strength, and has problems in handling property and workability.

Further, although there are various high Tg polymers, these have a polar group, so the hygroscopicity and dielectric properties are limited. Therefore, a high Tg polymer which is composed of an olefin skeleton and has excellent optical properties, dielectric properties, and mechanical strength without a polar group is required.

One method for improving the mechanical strength of high TgCOC is a method of copolymerizing a cyclic olefin and an α-olefin other than ethylene (hereinafter referred to as "specific α-olefin"). There have been various studies on the copolymerization of a cyclic olefin with a specific ?-olefin.

The copolymerization of a cyclic olefin with a specific ?-olefin and the copolymerization of a cyclic olefin with ethylene are greatly different. In the copolymerization of a cyclic olefin and ethylene The conditions of the high molecular weight body are the copolymerization of a cyclic olefin and a specific α-olefin, and since a chain transfer reaction due to a specific α-olefin occurs, it has hitherto been difficult to obtain a high molecular weight body. Therefore, the copolymer of a cyclic olefin and a specific α-olefin is not suitable for a molding material (see, for example, Non-Patent Document 1).

Patent Document 1 discloses that a high-molecular weight compound composed of a cyclic olefin and a specific α-olefin is obtained by a specific Ti-based catalyst, and has a Tg of 245 to 262 ° C, low moisture absorption, and a linear expansion coefficient of less than 80 ppm. Excellent physical film. However, in the polymerization method disclosed in Patent Document 1, since a large amount of catalyst and a catalyst are used, it is difficult to plan and save resources, and it takes a high cost to obtain a copolymer, and a catalyst and a catalyst remain. The problem of the transparency of the film is impaired. Further, Patent Document 1 discloses that a copolymer of 92 to 164 g per 1 g of the catalyst equivalent can be obtained.

Patent Document 2 discloses a film having excellent puncture characteristics, but has a Tg of less than 170 °C. Further, in Patent Document 2, since a large amount of catalyst and a promoter are used, it is difficult to plan and save resources, and it takes a high cost to obtain a copolymer, and the transparency and thermal stability of the film are impaired. Further, Patent Document 2 discloses that a copolymer of 127 to 275 g per 1 g of the catalyst equivalent can be obtained.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-298999

[Patent Document 2] Japanese Patent No. 5017222

[Non-patent literature]

[Non-Patent Document 1] Jung, H. Y., Polyhedron, 2005, Vol. 24, p. 1269-1273

The present invention has been made in view of the above circumstances, and provides a copolymer of a cyclic olefin copolymer having a molecular weight which is excellent in mechanical properties and which is excellent in mechanical properties and which can be obtained by a small amount of catalyst. The method is the goal.

The present inventors have found that a smaller amount of a titanocene catalyst can be used to obtain a cyclic olefin copolymer having a higher molecular weight and suitable for a general molding process, and the present invention has been completed. More specifically, the present invention provides the following.

(1) A method for producing a copolymer comprising: a cyclic olefin monomer (A) derived from norbornene and a ?-olefin derived from a C4 to C12 in the presence of a titanocene catalyst; The polymerization step of polymerizing the olefin monomer (B) to obtain a copolymer, wherein the amount of the above-mentioned copolymer obtained by the above polymerization step is 1000 g or more per 1 g of the above-mentioned titanocene catalyst equivalent, and the number of the above-mentioned copolymers is average The molecular weight is 20,000 or more and 200,000 or less.

(2) The production method according to (1), wherein the polymerization step is carried out together with the above-mentioned titanocene catalyst in the presence of a promoter and a chain transfer agent composed of an alkyl aluminoxane.

(3) The production method according to (2), wherein the chain transfer agent is an aluminum alkyl.

(4) The production method according to (3), wherein the alkyl aluminum is methyl aluminum.

(5) The production method according to any one of (1) to (4) wherein the glass transition temperature (Tg) of the above copolymer is 170 °C or higher.

According to the present invention, it is possible to provide a method for producing a copolymer of a cyclic olefin copolymer having a molecular weight which is excellent in the amount of catalyst and which is excellent in mechanical properties and which is suitable for usual molding. In particular, the effect of the present invention can be further enhanced by controlling the amount of the chain transfer agent. In the present invention, since the amount of the catalyst used is small, the amount of the catalyst can be reduced accordingly. Therefore, it is possible to use a small amount of a catalyst and a catalyst to be inexpensive, and it is possible to increase the amount of the cyclic olefin copolymer per batch while maintaining the molecular weight range, thereby realizing resource saving. Further, since the catalyst and the promoter which remain in the obtained copolymer are small, it is easy to improve the transparency and mechanical properties of the molded article such as a film obtained from the copolymer.

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

The method for producing a copolymer of the present invention comprises at least a norbornene-derived cyclic olefin monomer (A) and a C4 to C12 α-olefin-derived α-olefin in the presence of a titanocene catalyst. The polymerization step of polymerizing the monomer (B) to obtain a copolymer, wherein the amount of the above-mentioned copolymer obtained by the above polymerization step is 1000 g or more per 1 g of the above-mentioned titanocene catalyst equivalent, and the number of the above-mentioned copolymer The average molecular weight is 20,000 or more and 200,000 or less. According to the method for producing a polymer of the present invention, even in a range of a small amount of catalyst, a high molecular weight cyclic olefin copolymer can be obtained in one batch while maintaining a molecular weight range. In particular, 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 method for producing the copolymer of the present invention, the polymerization step, together with the titanocene catalyst, in the alkane It is preferred to carry out the presence of a cocatalyst and a chain transfer agent composed of an aluminoxane.

[copolymer]

The copolymer obtained by the method for producing a copolymer of the present invention comprises an architectural unit derived from a cyclic olefin (A) derived from norbornene and an α-olefin derived from an α-olefin derived from C4 to C12. The structural unit of body (B).

The amount of the above-mentioned copolymer obtained in the polymerization step of the above production method is preferably 1000 g or more per gram of the titanocene catalyst equivalent used in the above polymerization step, and more preferably 2,000 g or more.

The number average molecular weight of the copolymer of the present invention is preferably 20,000 or more and 200,000 or less, more preferably 30,000 or more, and still more preferably 150,000 or less. When the number average molecular weight is 20,000 or more, the glass transition temperature (Tg) of the obtained copolymer does not easily become too low. When the number average molecular weight is 200,000 or less, the viscosity of the solution of the obtained copolymer is not easily increased. Further, in the present specification, the number average molecular weight means a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography.

The glass transition temperature (Tg) of the copolymer of the present invention is preferably 170 ° C or higher, more preferably 200 ° C or higher, more preferably 230 ° C or higher, and particularly preferably 260 ° C or higher. When the above glass transition temperature is above 170 ° C, the above copolymerization Since the transparent film obtained by the composition has sufficient heat resistance, it can be suitably used, for example, as a substrate for ITO vapor deposition. In particular, when the glass transition temperature is 260 ° C or higher, the transparent film obtained from the above-mentioned copolymer has more sufficient heat resistance, so that, for example, even if it is in contact with molten lead-free solder, deformation or cracking is unlikely to occur. , melting, etc., so it can be used well in lead-free solder components. Further, the upper limit of the glass transition temperature of the above-mentioned copolymer is not particularly limited, but since the glass transition temperature becomes high, the structural unit derived from the α-olefin in the copolymer becomes small, so that the α-olefin is used. The effect of improving the mechanical strength of the copolymerization tends to be small, and the glass transition temperature is preferably 350 ° C or lower, more preferably 330 ° C or lower. In addition, in the present specification, the glass transition temperature is a value measured by a DSC method (method described in JIS K 7121) at a temperature increase rate of 20 ° C /min.

[Mico-titanium catalyst]

The titanocene catalyst is not particularly limited, and a conventional one can be used. The titanocene catalyst may be used alone or in combination of two or more.

The titanocene catalyst may, for example, be represented by the following formula (1).

R ¹ to R ³ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopentyl group or a cyclohexyl group; An aryl group such as a biphenyl group, a phenyl group having the above alkyl group as a substituent, a biphenyl group, a naphthyl group, or a naphthyl group having the above 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 or an iodine atom. Atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, having the above halogen atom as The alkyl group of the substituent; a phenyl group, a biphenyl group, a naphthyl group, or the like having the above halogen atom or an alkyl group as a substituent.

R ⁶ to R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a fluorenyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent. Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and octyl group. Cyclopentyl, cyclohexyl and the like. Further, specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and the above aryl group having the above alkyl group as a substituent. Further, specific examples of the mercapto 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, and a t-butyl group. An alkyl group having 1 to 12 carbon atoms such as a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group or a cyclohexyl group is used as a substituent fluorenyl group.

Specific examples of the titanocene catalyst represented by the formula (1) include (isopropyl decylamine) dimethyl-9-decyldecane dimethyl titanium and (isobutylguanamine) dimethyl. -9-decyldecane dimethyltitanium, (t-butylammonium) dimethyl-9-decyldecane dimethyltitanium, (isopropyl decylamine) dimethyl-9-decyl decane dimethyl Titanium, (isobutylguanamine) dimethyl-9-(3,6-dimethylindenyl)decane titanium dichloride, (t-butyl decylamine) dimethyl-9-decyl decane Titanium dichloride, (isopropyl decylamine) dimethyl-9-(3,6-dimethylindenyl)decane titanium dichloride, (isobutylguanamine) dimethyl-9-(3 ,6-dimethylindenyl)decane titanium dichloride, (t-butyl decylamine) dimethyl-9-(3,6-dimethylindenyl)decane dimethyl titanium, (isopropyl Indoleamine) dimethyl-9-(3,6-dimethylindenyl)decane titanium dichloride, (isobutylguanamine) dimethyl-9-(3,6-dimethylindenyl) Decane titanium dichloride, (t-butyl decylamine) dimethyl-9-(3,6-dimethylindenyl)decane dimethyl titanium, (isopropyl decylamine) dimethyl 9-[ 3,6-di(t-butyl)decyl]decane titanium dichloride, (isobutylguanamine) dimethyl 9-[3,6-di(t-butyl)decyl]decane dichloride Titanium, (T-butymidine) dimethyl 9-[3,6-di(t-butyl)indolyl]decane dimethyltitanium, (isopropyl decylamine) dimethyl 9-[2,7- Di(t-butyl)decyl]decane titanium dichloride, (isobutylguanamine) dimethyl 9-[2,7-di(t-butyl)decyl]decane titanium dichloride, ( Tert-butyl decylamine) dimethyl 9-[2,7-di(t-butyl)decyl]decane dimethyltitanium, (isopropyl decylamine) dimethyl 9-(2,3, 6,7-tetramethylindenyl)decane titanium dichloride, (isobutylguanamine) dimethyl 9-(2,3,6,7-tetramethylindenyl)decane titanium dichloride, ( Tert-butyl decylamine) dimethyl 9-(2,3,6,7-tetramethylindenyl)decane dimethyltitanium or the like. (t-BuNSiMe ₂ Flu)TiMe ₂ is preferred as (t-butyramine) dimethyl 9-decyldecane dimethyltitanium. (t-BuNSiMe ₂ Flu) TiMe ₂ is a titanium complex represented by the following formula (2), and can be easily synthesized, for example, according to the description of "Macrornolecules, Vol. 31, p. 3184, 1998".

[Chemical 2]

In the formula, Me represents a methyl group and t-Bu is a tertiary butyl group.

[Assistant catalyst composed of alkyl aluminoxane]

The cocatalyst used in the present invention is composed of an alkyl aluminoxane. The above-mentioned auxiliary catalysts may be used alone or in combination of two or more.

The alkyl aluminoxane is not particularly limited, and examples thereof include compounds represented by the following formula (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) is a product obtained by a reaction of a trialkylaluminum with water.

In the formula, R represents an alkyl group having 1 to 4 carbon atoms, n is 0 to 40, and preferably 2 to 30 is an integer. )

The alkyl aluminoxane may be a modified methyl aluminoxane in which a part of a methyl group of methyl aluminoxane and methyl aluminoxane is substituted with an alkyl group. The modified methylaluminoxane may, for example, be a substituted methyl group, and a modified methyl aluminum oxide having a carbon number of 2 to 4 such as an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. Alkane is preferred, and a modified methylaluminoxane in which a part of the methyl group is substituted with an isobutyl group is more preferred. Specific examples of the alkyl aluminoxane include methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, and methyl ethyl aluminoxane. Methyl butyl aluminoxane, methyl isobutyl aluminoxane, etc., of which methyl aluminoxane and methyl isobutyl aluminoxane are preferred.

The alkyl aluminoxane can be produced by a known method. Further, as the alkyl aluminoxane, a commercially available product can also be used. For the commercially available product of the alkyl aluminoxane, for example, MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by TOSHO FINECHEM Co., Ltd.) or methylaluminoxane solution (manufactured by ALBEMARLE Co., Ltd.) Wait.

[chain transfer agent]

The chain transfer agent used in the present invention is a compound having a chain transfer energy. The chain transfer agent may be used alone or in combination of two or more.

The chain transfer agent is not particularly limited, and a conventional compound having a chain transfer energy can be used, and examples thereof include an aluminum alkyl group. The alkyl aluminum compound is, for example, a compound represented by the following formula (5).

(R ¹⁰ ) _z AlX _3-z (5)

In the formula, R ¹⁰ represents an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, an X-based halogen atom or a hydrogen atom, and an z-number of 1-3.

An alkyl group having 1 to 15 carbon atoms, and examples thereof include methyl group, ethyl group, and n-propyl group. Base, isopropyl, n-butyl, isobutyl, n-octyl and the like.

Specific examples of the aluminum alkyl include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-second butyl aluminum, and tri-n-octyl aluminum. Alkyl aluminum halide; alkyl aluminum halide such as dimethyl aluminum chloride or diisobutyl aluminum chloride; alkyl aluminum hydride such as diisobutyl aluminum hydride; dimethyl methoxy aluminum Alkyl aluminum alkoxide.

For other chain transfer agents, a polymeric Chain Shuttling agent known as a metal diazonium catalyst can also be used. Examples of the chain Shuttling agent include the above-mentioned alkyl aluminum and alkyl zinc. The alkyl zinc may, for example, be a compound represented by the following formula (6).

(R ¹¹ ) _z ZnX _2-y (6)

In the formula, R ¹¹ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8, an X-based halogen atom or a hydrogen atom, and y is an integer of 0 to 2.

The alkyl group having 1 to 15 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or an n-octyl group.

Specific examples of the alkyl zinc include dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-second butyl zinc aluminum, and di-n-octyl zinc. Or an alkyl zinc; an alkyl zinc halide such as methyl zinc chloride or isobutyl zinc chloride; an alkyl zinc hydride such as isobutyl zinc hydride; or an alkyl alkane such as methyl methoxy zinc Zinc oxide; zinc halide such as zinc chloride.

The aluminum alkyl or the alkyl zinc may be directly introduced into the polymerization system, or may be contained in a state of being contained in the alkyl aluminoxane. Further, it may be an alkyl aluminum which is a raw material remaining after the production of the alkyl aluminoxane and which is left after the production. Further, an aluminum alkyl and an alkyl zinc may also be used in combination.

[Ring olefin monomer (A)]

The norbornene-derived cyclic olefin monomer (A) may, for example, be norbornene or substituted norbornene, preferably norbornene. The above-mentioned cyclic olefin monomer (A) may be used alone 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 formula (I).

In the formula, R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated. A divalent hydrocarbon group is formed, and R ⁹ or R ¹⁰ , R ¹¹ or R ¹² may form a ring with each other.

Further, n is 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each of the overlapping 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. Wherein R of formula (I), ¹ ~ R ^12, may be the same, or different, selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and the group consisting of.

Specific examples of R ¹ to R ⁸ include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; and an alkyl group having 1 or more and 20 or less carbon atoms; these may be different or partially different, and further, They can all be the same.

Further, specific examples of R ⁹ to R ¹² include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; an alkyl group having 1 or more and 20 or less carbon atoms; a cycloalkyl group such as a cyclohexyl group; and a phenyl group and toluene. a substituted or unsubstituted aromatic hydrocarbon group such as a group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group or a fluorenyl group; a benzyl group, a phenethyl group, an aralkyl group substituted with an aryl group other alkyl groups, etc. The items may be different or partially different, and may be all the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ^{12 are} integrated to form a divalent hydrocarbon group include, for example, a subunit such as an ethylene group, a propylene group or an isopropylidene group.

When R ⁹ or R ¹⁰ , R ¹¹ or R ¹² forms a ring with each other, the ring formed may be a single ring or a polycyclic ring, or may be a bridged polycyclic ring or a double bond bonding ring. It may also be a ring composed of a combination of the rings. Further, the rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the formula (I) include 5-methylbicyclo[2.2.1]hept-2-ene and 5,5-dimethylbicyclo[2.2.1]heptane-2. - alkene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-butylbicyclo[2.2.1]hept-2-ene, 5-ethylenebicyclo[2.2.1]hept-2- Alkene, 5-hexylbicyclo[2.2.1]hept-2-ene, 5-octylbicyclo[2.2.1]hept-2-ene, 5-octadecylbicyclo[2.2.1]hept-2-ene , 5-propenylbicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, 5-propenylbicyclo[2.2.1]hept-2-ene, etc. 2-ring cyclic olefin; tricyclo[4.3.0.1 ^2,5 ]癸-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]癸-3- Alkene; tricyclo[4.4.0.1 ^2,5 ]indole-3,7-diene, or tricyclo[4.4.0.1 ^2,5 ]indole-3,8-diene, or such partial hydrogen additions ( Or a tricyclo[4.4.0.1 ^2,5 ]non-3-ene of an adduct of cyclopentadiene and cyclohexene; 5-cyclopentyltricyclo[2.2.1]hept-2-ene, 5 -cyclohexylbicyclo[2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenylbicyclo[2.2.1]hept-2-ene, etc. a 3-ring cyclic olefin; a tetracyclic ring [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene (may also be referred to simply as tetracyclododecene), 8 -methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3 - alkene, 8-methylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-ethylenetetracycline [4.4.0.1 ^2,5 .1 ^7,10 ]Dodeca-3-ene, 8-vinyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-propenyltetracyclo[4.4.0.1 ^2,5 . ^1,7,10 ] 4-ring cyclic olefin such as dodecene-3-ene; 8-cyclopentyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8 -cyclohexyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-cyclohexenyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]12 carbon 3-ene, 8-phenylcyclopentyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene; tetracyclo[7.4.1 ^3,6 .0 ^1,9 . 0 ^2,7 ]tetradecyl-4,9,11,13-tetraene (also known as 1,4-methyl-1,4,4a,9a-tetrahydroanthracene), tetracyclic [8.4.1] ^4,7 .0 ^1,10 .0 ^3,8 ] fifteen carbon-5,10,12,14-tetraene (also known as 1,4-methylene-1,4,4a,5,10, 10a-hexahydroindole); pentacyclic [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14 ]-4-hexadecene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ]-4-pentadecenyl, pentacyclic [7.4.0.0 ^2,7 .1 ^3,6 .1 ^10,13 ]-4-pentadecene; seven rings [8.7.0.1 ^2,9 .1 ^{4 ,7} .1 ^11,17 .0 ^3,8 0 ^12,16 ]-5-Eicosene, seven rings [8.7.0.1 ^2,9 .0 ^3,8 .1 ^7,7 .0 ^12,17 .1 ^13,16 ]-14- a polycyclic cyclic olefin such as a tetraene; a tetramer of cyclopentadiene.

Wherein, a norbornene is substituted with an alkyl group (for example, a bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), and an alkylene group is substituted with norbornene (for example, It is preferred to use at least one alkylene-substituted bicyclo[2.2.1]hept-2-ene), and 5-ethylenebicyclo[2.2.1]hept-2-ene (common name: 5-A-4- Base-2-norbornene, or only ethylidene norbornene is particularly preferred.

[α-olefin monomer (B)]

The α-olefin monomer (B) derived from the α-olefin of C4 to C12 may, for example, be a C4-C12 α-olefin having at least one substituent such as an α-olefin of C4 to C12 or a halogen atom. The α-olefin of C4 to C12 is preferred, and the α-olefin of C6 to C10 is more preferred.

The α-olefin of C4 to C12 is not particularly limited, and is, for example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3 -ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, and the like. Among them, 1-hexene, 1-octene and 1-decene are preferred.

[Conditions of the polymerization step]

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

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

The amount of the ferrocene-based catalyst to be used is preferably from 0.00001 parts by mass to 0.1 parts by mass, and more preferably from 0.0001 part by mass to 0.05 part by mass, based on 100 parts by mass of the cyclic olefin monomer (A).

The amount of the alkyl aluminoxane used is 100 parts by mass of the cyclic olefin monomer (A). 0.0001 mass part or more and 5 mass parts or less are preferable, and it is preferably 0.01 mass part or more and 3 mass parts or less.

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 per 100 parts by mass of the cyclic olefin monomer (A), and more preferably 0.01 part by mass or more and 5 parts by mass or less.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention should not be limited to the examples. As long as there is no special mention, the "part" indicating the quantity refers to the "quality department".

[Production of co-polymer]

In the glass reactor under the nitrogen atmosphere, the monomer described in the first table and the catalyst described in the second table are added, and after the polymerization temperature is maintained, the catalyst described in the second table is added. .

Further, the catalyst and the co-catalyst were respectively added to the reactor in a state of being dissolved in toluene. After the polymerization was continued in the stirred reactor at the polymerization temperature and the polymerization time shown in Table 3, 1 part by mass of 2-propanol was added to complete the reaction. Next, the obtained polymerization reaction liquid was poured into a large amount of acidic methanolic hydrochloric acid to completely precipitate the polymer, and after filtration and washing, the mixture was dried under reduced pressure at 60 ° C for 1 day or more to obtain a copolymer. The mass of the obtained copolymer (the "yield" in Table 3) was measured. The ratio of the obtained copolymer to the amount of the catalyst to be used was calculated ("g (copolymer) / g (catalyst)" in the third table).

Furthermore, the types of catalysts and helpers used are as follows. Here, t-Bu means a third butyl group, and a Flu-based fluorenyl group.

Catalyst A: (t-BuNSiMe ₂ Flu) TiMe ₂

Auxiliary catalyst A: 6.5 mass% (content of Al atom) MMAO-3A toluene solution ([(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] _n represents methyl isobutyl aluminoxane Solution, TOSHO FINECHEM (share) system, and further, 6 mol% of trimethylaluminum for all Al)

Catalyst B: 9.0% by mass (as a content of Al atoms) TMAO-211 toluene solution (methoaluminoxane solution, manufactured by TOSHO FINECHEM), further containing 26 mol% of trimethylaluminum for all Al )

Catalyst C: Triisobutylaluminum

Promoter D: dimethylanilinium tetrakis(pentafluorophenyl)borate

The number average molecular weight and Tg of each of the copolymers are shown in Table 3.

The values of "portions" in the first table, the second table, and the third table are values for 100 parts of 2-norbornene. Further, regarding the catalyst A and the catalyst B in the second table, the value of "part" is the value of the toluene solution.

As shown in the third table, according to the present invention, the ratio of the copolymer obtained with respect to the amount of the catalyst used is high.

Claims (5)

A method for producing a copolymer comprising: a cyclic olefin monomer (A) derived from norbornene and an α-olefin derived α-olefin monomer derived from a C4 to C12 in the presence of a titanocene catalyst (B) a polymerization step of polymerizing to obtain a copolymer, wherein the amount of the above-mentioned copolymer obtained by the above polymerization step is 1000 g or more per 1 g of the above-mentioned titanocene catalyst equivalent, and the number average molecular weight of the above-mentioned copolymer is 20,000. Above 200,000. The production method according to the first aspect of the invention, wherein the polymerization step is carried out together with the above-mentioned titanocene catalyst in the presence of a promoter and a chain transfer agent composed of an alkyl aluminoxane. A method of producing a second aspect of the invention, wherein the chain transfer agent is an aluminum alkyl. A method of producing a third aspect of the invention, wherein the alkyl aluminum is methyl aluminum. The production method according to any one of claims 1 to 4, wherein the glass transition temperature (Tg) of the above copolymer is 170 ° C or higher.