WO2015178144A1 - Method for producing cyclic olefin copolymer - Google Patents

Method for producing cyclic olefin copolymer Download PDF

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Publication number
WO2015178144A1
WO2015178144A1 PCT/JP2015/061987 JP2015061987W WO2015178144A1 WO 2015178144 A1 WO2015178144 A1 WO 2015178144A1 JP 2015061987 W JP2015061987 W JP 2015061987W WO 2015178144 A1 WO2015178144 A1 WO 2015178144A1
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Prior art keywords
copolymer
group
cyclic olefin
catalyst
olefin
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PCT/JP2015/061987
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French (fr)
Japanese (ja)
Inventor
敬之 八重樫
鈴木　健
善道 岡野
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ポリプラスチックス株式会社
株式会社ダイセル
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Publication of WO2015178144A1 publication Critical patent/WO2015178144A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings

Definitions

  • the present invention relates to a method for producing a cyclic olefin copolymer.
  • Cyclic olefin polymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used for optical materials such as optical disk substrates, optical films, and optical fibers. It is used for various purposes including fields.
  • a typical COC is a copolymer of a cyclic olefin and ethylene, but the glass transition temperature of the copolymer can be changed by the copolymer composition of the cyclic olefin and ethylene.
  • a Tg exceeding 200 ° C. which is difficult with COP, can be realized, but it has a hard and brittle property, has low mechanical strength, and is easy to handle. And there was a problem that workability was bad.
  • Copolymerization of cyclic olefin and specific ⁇ -olefin is very different from copolymerization of cyclic olefin and ethylene.
  • a chain transfer reaction caused by the specific ⁇ -olefin occurs in the copolymerization of the cyclic olefin and the specific ⁇ -olefin. It was difficult to obtain. Therefore, it has been said that a copolymer of a cyclic olefin and a specific ⁇ -olefin is not suitable for a molding material (for example, see Non-Patent Document 1).
  • Patent Document 1 a high molecular weight product composed of a cyclic olefin and a specific ⁇ -olefin is obtained with a specific Ti-based catalyst, Tg is 245 to 262 ° C., low moisture absorption, and a linear expansion coefficient is less than 80 ppm. It is described that a film having excellent physical properties was obtained. However, since the polymerization method disclosed in Patent Document 1 uses a large amount of catalyst and promoter, it is difficult to save resources and the cost for obtaining a copolymer is high. Remained to impair the transparency of the film. Patent Document 1 describes that 92 to 164 g of copolymer can be obtained per 1 g of catalyst.
  • Patent Document 2 discloses a film having excellent punching characteristics, but Tg is less than 170 ° C. Moreover, in patent document 2, since a catalyst and a co-catalyst are used in large quantities, it is difficult to save resources, the cost for obtaining the copolymer is expensive, and the transparency and thermal stability of the film are impaired. There was a problem. Patent Document 2 describes that 127 to 275 g of a copolymer can be obtained per 1 g of the catalyst.
  • JP 2009-298999 A Japanese Patent No. 5017222
  • the present invention has been made in view of the above situation, and is a copolymer that can obtain a larger amount of a cyclic olefin copolymer having a smaller catalyst amount, excellent mechanical properties, and suitable for ordinary molding processing. It aims at providing the manufacturing method of a polymer.
  • the present inventors combined a non-crosslinked ketimido half-titanocene catalyst with a promoter composed of an alkylaluminoxane, thereby using a smaller amount of the above-mentioned half-titanocene catalyst, having excellent mechanical properties and being suitable for ordinary molding processing. It has been found that more cyclic olefin copolymers having a suitable molecular weight can be obtained, and the present invention has been completed. More specifically, the present invention provides the following.
  • a ligand-optimized titanocene catalyst is used in combination with an alkylaluminoxane cocatalyst, so that a smaller amount of catalyst, excellent mechanical properties, and a molecular weight cyclic olefin copolymer suitable for ordinary molding processing are used. It is possible to provide a method for producing a copolymer capable of obtaining more polymer.
  • the amount of catalyst used is small, the amount of cocatalyst can be reduced accordingly. Therefore, the amount of cyclic olefin copolymer per batch can be increased while maintaining the molecular weight range at a low cost with a smaller amount of catalyst and cocatalyst, and resource saving can also be realized.
  • a molded product such as a film obtained from this copolymer is likely to be improved in transparency and mechanical properties.
  • the method for producing a copolymer according to the present invention comprises at least a cyclic olefin monomer (A) derived from norbornene and C4 to C12 in the presence of an uncrosslinked ketimido half-titanocene catalyst and a co-catalyst comprising an alkylaluminoxane. And a polymerization step of polymerizing the ⁇ -olefin monomer (B) derived from the ⁇ -olefin to obtain a copolymer, and the amount of the copolymer obtained in the polymerization step is based on 1 g of the half titanocene catalyst.
  • the number average molecular weight of the copolymer is 20,000 or more and 200,000 or less.
  • the polymerization step may be performed in the presence of a chain transfer agent together with the co-catalyst comprising the half titanocene catalyst and the alkylaluminoxane.
  • the copolymer obtained by the method for producing a copolymer according to the present invention comprises a structural unit derived from a cyclic olefin monomer (A) derived from norbornene and an ⁇ -olefin monomer derived from a C4 to C12 ⁇ -olefin. (B) derived structural units.
  • the amount of the copolymer obtained in the polymerization step included in the production method is 1000 g or more, preferably 2000 g or more, more preferably 3000 g or more per 1 g of titanocene catalyst used in the polymerization step.
  • 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.
  • Tg glass transition temperature
  • a number average molecular weight means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography.
  • the glass transition temperature (Tg) of the copolymer in the present invention is 170 ° C. or higher, preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and particularly preferably 260 ° C. or higher.
  • Tg glass transition temperature
  • the transparent film obtained from the copolymer has sufficient heat resistance, and can be suitably used, for example, as a substrate for ITO deposition.
  • the glass transition temperature is 260 ° C.
  • the transparent film obtained from the copolymer has further sufficient heat resistance, so that, for example, deformation, cracking, contact with molten lead-free solder, Since melting or the like hardly occurs, it can be suitably used as a lead-free solder member.
  • the upper limit of the glass transition temperature of the copolymer is not particularly limited, but mechanical strength due to ⁇ -olefin copolymerization is reduced because the structural unit derived from ⁇ -olefin in the copolymer decreases as the glass transition temperature increases.
  • the glass transition temperature is preferably 350 ° C. or less, and more preferably 330 ° C. or less, because the improvement effect tends to be small.
  • the glass transition temperature employ adopts the value measured on the conditions of the temperature increase rate of 20 degree-C / min by DSC method (method of JISK7121).
  • Non-crosslinked ketimido half-titanocene catalyst The non-crosslinked ketimido type half titanocene catalyst is not particularly limited, and known ones can be used.
  • the said half titanocene catalyst can be used individually by 1 type or in combination of 2 or more types.
  • Examples of the non-crosslinked ketimido half-titanocene catalyst include those represented by the following formula (1).
  • R 1 is a substituent represented by the following formula (2)
  • R 2 is a ketimido group represented by the following formula (3) or (4) or a phenoxy group represented by the following formula (5).
  • R 3 and R 4 independently represent a halogen atom or an alkyl group.
  • R 5 represents an alkyl group, and n is an integer from 0 to 5.
  • R 6 and R 7 independently represent an alkyl group or a phenyl group.
  • R 8 and R 9 independently represent an alkyl group or a phenyl group.
  • R 10 , R 11 , R 12 , R 13 , and R 14 independently represent a hydrogen atom, an alkyl group, or a phenyl group.
  • R 3 and R 4 include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group, with chlorine atom being preferred. .
  • R 5 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group.
  • a tert-butyl group is preferred.
  • R 6 and R 7 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group. And a tert-butyl group is preferable.
  • R 8 and R 9 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and neopentyl group. Examples thereof include a phenyl group, and a tert-butyl group and a phenyl group are preferable.
  • R 10 , R 11 , R 12 , R 13 , and R 14 include hydrogen atoms and carbon such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups. Examples thereof include an alkyl group of 1 to 4 and a phenyl group. R 10 and R 14 are preferably isopropyl groups, and R 12 and R 13 are preferably hydrogen atoms.
  • the cocatalyst used in the present invention comprises an alkylaluminoxane.
  • the above promoters can be used alone or in combination of two or more.
  • the alkylaluminoxane is not particularly limited, and examples thereof include compounds represented by the following formula (8) or (9).
  • the alkylaluminoxane represented by the following formula (8) or (9) is a product obtained by the reaction of trialkylaluminum and water.
  • R represents an alkyl group having 1 to 4 carbon atoms
  • n represents an integer of 0 to 40, preferably 2 to 30.
  • alkylaluminoxane examples include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of methylaluminoxane is substituted with another alkyl group.
  • modified methylaluminoxane for example, a modified methylaluminoxane 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 as an alkyl group after substitution is preferable.
  • a modified methylaluminoxane in which a part of the group is substituted with an isobutyl group is more preferable.
  • alkylaluminoxane examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferable.
  • Alkylaluminoxane can be prepared by a known method. Moreover, as an alkylaluminoxane, you may use a commercial item. Examples of commercially available products of alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.) and methylaluminoxane solution (manufactured by Albemarle).
  • Cyclic olefin monomer (A) Examples of the cyclic olefin monomer (A) derived from norbornene include norbornene and substituted norbornene, and norbornene is preferable.
  • the said cyclic olefin monomer (A) can be used individually by 1 type or in combination of 2 or more types.
  • the substituted norbornene is not particularly limited, and examples of the substituent that the substituted norbornene has include a halogen atom, a monovalent or divalent hydrocarbon group.
  • Specific examples of the substituted norbornene include those represented by the following general formula (I).
  • R 1 to R 12 may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, R 9 or R 10 and R 11 or R 12 may form a ring with each other.
  • 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.
  • R 1 to R 8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , May be partially different or all may be the same.
  • R 9 to R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and tolyl Group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group and the like substituted or unsubstituted aromatic hydrocarbon group; benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group These may be different from each other, may be partially different, or all may be the same.
  • R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group
  • alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.
  • the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge.
  • a ring having a double bond, or a ring composed of a combination of these rings may be used.
  • these rings may have a substituent such as a methyl group.
  • 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] hepta- 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.
  • Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: 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 a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;
  • Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene also simply referred to 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 ] dodec-3-ene
  • 8-methylidenetetracyclo 4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
  • alkyl-substituted norbornene eg, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups
  • alkylidene-substituted norbornene eg, bicyclo substituted with one or more alkylidene groups
  • [2.2.1] hept-2-ene) preferably 5-ethylidene-bicyclo
  • hept-2-ene common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene Is particularly preferred.
  • ⁇ -olefin monomer (B) examples include C4 to C12 ⁇ -olefin and a C4 to C12 ⁇ -olefin having at least one substituent such as a halogen atom. Examples thereof include olefins, and C4 to C12 ⁇ -olefins are preferable, and C6 to C10 ⁇ -olefins are more preferable.
  • the C4 to C12 ⁇ -olefin is not particularly limited.
  • Examples include ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Of these, 1-hexene, 1-octene and 1-decene are preferable.
  • the conditions for the polymerization step are not particularly limited as long as the desired copolymer is obtained, and known conditions can be used, and the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted. Moreover, the usage-amount of each component is illustrated as follows.
  • the addition amount of the ⁇ -olefin monomer (B) is preferably 1 part by mass or more and 500 parts by mass or less, and preferably 10 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferred.
  • the amount of the non-crosslinked ketimido half-titanocene catalyst used is preferably 0.00001 parts by mass or more and 0.1 parts by mass or less, based on 100 parts by mass of the cyclic olefin monomer (A). More preferably, the amount is 0.05 parts by mass or less.
  • the amount of the alkylaluminoxane used is preferably 0.0001 parts by mass or more and 5 parts by mass or less, and 0.01 parts by mass or more and 3 parts by mass or less based on Al with respect to 100 parts by mass of the cyclic olefin monomer (A). It is more preferable.
  • part representing an amount means “part by mass”.
  • the obtained polymerization reaction solution was poured into a large amount of hydrochloric acid methanol to completely precipitate the polymer, filtered and washed, and then dried under reduced pressure at 60 ° C. for 1 day or more to obtain a copolymer. .
  • the mass of the obtained copolymer was measured (“Yield” in Table 3).
  • the ratio of the obtained copolymer to the amount of catalyst used was calculated (“g (copolymer) / g (catalyst)” in Table 3).
  • t-Bu represents a tert-butyl group
  • Flu represents a fluorenyl group
  • Cp represents a cyclopentadienyl group.
  • Catalyst A (t-BuNSiMe 2 Flu) TiMe 2
  • Cocatalyst 6.5% by mass (as Al atom content) MMAO-3A in toluene solution (manufactured by Tosoh Finechem Co., Ltd.)
  • the values of “parts” in Tables 1, 2, and 3 are values for 100 parts of 2-norbornene. Moreover, about the promoter in Table 2, the value of "part” is a value as a toluene solution.
  • the proportion of the copolymer obtained is high with respect to the amount of catalyst used.

Abstract

　Provided is a method for producing a copolymer that makes it possible to obtain more of a cyclic olefin copolymer having excellent mechanical properties and a molecular weight suitable for ordinary molding by a smaller amount of catalyst. 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 α-olefin monomer derived from a C4-C12 α-olefin (B) in the presence of an uncrosslinked ketimide-type half-titanocene catalyst and a cocatalyst made from alkyl aluminoxane; the amount of copolymer obtained in this polymerization step is 1000 g or higher per gram of this half-titanocene catalyst, and the number-average molecular weight of the copolymer is from 20,000 to 200,000.

Description

環状オレフィン共重合体の製造方法Method for producing cyclic olefin copolymer
　本発明は、環状オレフィン共重合体の製造方法に関する。 The present invention relates to a method for producing a cyclic olefin copolymer.
　環状オレフィン重合体及び環状オレフィン共重合体（それぞれ「ＣＯＰ」及び「ＣＯＣ」等とも呼ばれる。）は、低吸湿性及び高透明性を有し、光ディスク基板、光学フィルム、光学ファイバー等の光学材料の分野をはじめ、様々な用途に使用されている。代表的なＣＯＣとして環状オレフィンとエチレンとの共重合体があるが、共重合体のガラス転移温度が環状オレフィンとエチレンとの共重合組成で変えることが可能なため、ＣＯＰよりガラス転移温度（Ｔｇ）の高い共重合体として製造することができ、ＣＯＰでは困難な２００℃超のＴｇを実現することも可能であるが、硬くて脆い性質を有しており、機械的強度が低く、ハンドリング性及び加工性が悪いという問題点があった。 Cyclic olefin polymers and cyclic olefin copolymers (also referred to as “COP” and “COC”, respectively) have low hygroscopicity and high transparency, and are used for optical materials such as optical disk substrates, optical films, and optical fibers. It is used for various purposes including fields. A typical COC is a copolymer of a cyclic olefin and ethylene, but the glass transition temperature of the copolymer can be changed by the copolymer composition of the cyclic olefin and ethylene. ) And a Tg exceeding 200 ° C., which is difficult with COP, can be realized, but it has a hard and brittle property, has low mechanical strength, and is easy to handle. And there was a problem that workability was bad.
　また、高Ｔｇ重合体は種々存在するが、これらは、極性基を持っているため、吸湿性及び誘電特性に限界がある。そのため、極性基を有さず、オレフィン系骨格からなり、光学特性、誘電特性、及び機械的強度に優れた高Ｔｇ重合体が求められている。 Also, there are various high Tg polymers, but these have polar groups and thus have limitations in hygroscopicity and dielectric properties. Therefore, there is a demand for a high Tg polymer that does not have a polar group, has an olefinic skeleton, and is excellent in optical properties, dielectric properties, and mechanical strength.
　高ＴｇＣＯＣの機械的強度を改善する方法の１つとして、環状オレフィンとエチレン以外のα－オレフィン（以下、「特定α－オレフィン」という）とを共重合させる方法がある。環状オレフィンと特定α－オレフィンとの共重合については、種々の研究がなされている。 As one method for improving the mechanical strength of high TgCOC, there is a method of copolymerizing a cyclic olefin and an α-olefin other than ethylene (hereinafter referred to as “specific α-olefin”). Various studies have been made on the copolymerization of a cyclic olefin and a specific α-olefin.
　環状オレフィンと特定α－オレフィンとの共重合は、環状オレフィンとエチレンとの共重合とは大きく異なる。環状オレフィンとエチレンとの共重合で高分子量体が得られる条件では、環状オレフィンと特定α－オレフィンとの共重合において、特定α－オレフィンに起因する連鎖移動反応が生じるため、これまで高分子量体が得られにくかった。よって、環状オレフィンと特定α－オレフィンとの共重合体は、成形材料には適さないとされていた（例えば、非特許文献１を参照）。 Copolymerization of cyclic olefin and specific α-olefin is very different from copolymerization of cyclic olefin and ethylene. Under conditions where a high molecular weight product can be obtained by copolymerization of a cyclic olefin and ethylene, a chain transfer reaction caused by the specific α-olefin occurs in the copolymerization of the cyclic olefin and the specific α-olefin. It was difficult to obtain. Therefore, it has been said that a copolymer of a cyclic olefin and a specific α-olefin is not suitable for a molding material (for example, see Non-Patent Document 1).
　特許文献１には、特定のＴｉ系触媒により環状オレフィンと特定α－オレフィンからなる高分子量体が得られ、Ｔｇが２４５から２６２℃であり、低吸湿であり、線膨張係数が８０ｐｐｍ未満である優れた物性のフィルムが得られたことが記載されている。しかし、特許文献１で開示されている重合法では触媒及び助触媒を多量に使用するため、省資源化を図りにくく、共重合体を得るのにかかる費用が高価であるとともに、触媒及び助触媒が残存してフィルムの透明性を損なう問題があった。なお、特許文献１では、触媒１ｇ当たり９２－１６４ｇの共重合体が得られることが記載されている。 In Patent Document 1, a high molecular weight product composed of a cyclic olefin and a specific α-olefin is obtained with a specific Ti-based catalyst, Tg is 245 to 262 ° C., low moisture absorption, and a linear expansion coefficient is less than 80 ppm. It is described that a film having excellent physical properties was obtained. However, since the polymerization method disclosed in Patent Document 1 uses a large amount of catalyst and promoter, it is difficult to save resources and the cost for obtaining a copolymer is high. Remained to impair the transparency of the film. Patent Document 1 describes that 92 to 164 g of copolymer can be obtained per 1 g of catalyst.
　特許文献２には、打抜き特性に優れたフィルムが開示されているが、Ｔｇは１７０℃未満である。また、特許文献２では、触媒及び助触媒を多量に使用するため、省資源化を図りにくく、共重合体を得るのにかかる費用が高価であるとともに、フィルムの透明性や熱安定性が損なわれる問題があった。なお、特許文献２では、触媒１ｇ当たり１２７－２７５ｇの共重合体が得られることが記載されている。 Patent Document 2 discloses a film having excellent punching characteristics, but Tg is less than 170 ° C. Moreover, in patent document 2, since a catalyst and a co-catalyst are used in large quantities, it is difficult to save resources, the cost for obtaining the copolymer is expensive, and the transparency and thermal stability of the film are impaired. There was a problem. Patent Document 2 describes that 127 to 275 g of a copolymer can be obtained per 1 g of the catalyst.
特開２００９－２９８９９９号公報JP 2009-298999 A 特許第５０１７２２２号公報Japanese Patent No. 5017222
　本発明は、上記の状況に鑑みてなされたものであり、より少ない触媒量で、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができる共重合体の製造方法を提供することを目的とする。 The present invention has been made in view of the above situation, and is a copolymer that can obtain a larger amount of a cyclic olefin copolymer having a smaller catalyst amount, excellent mechanical properties, and suitable for ordinary molding processing. It aims at providing the manufacturing method of a polymer.
　本発明者らは、非架橋のケチミド型ハーフチタノセン触媒とアルキルアルミノキサンからなる助触媒とを組み合わせることで、より少ない量の上記ハーフチタノセン触媒を用いて、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができることを見出し、本発明を完成するに至った。より具体的には、本発明は以下のものを提供する。 The present inventors combined a non-crosslinked ketimido half-titanocene catalyst with a promoter composed of an alkylaluminoxane, thereby using a smaller amount of the above-mentioned half-titanocene catalyst, having excellent mechanical properties and being suitable for ordinary molding processing. It has been found that more cyclic olefin copolymers having a suitable molecular weight can be obtained, and the present invention has been completed. More specifically, the present invention provides the following.
　（１）　非架橋のケチミド型ハーフチタノセン触媒とアルキルアルミノキサンからなる助触媒との存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４～Ｃ１２のα－オレフィンから誘導されるα－オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、前記重合工程において得られる前記共重合体の量は、前記ハーフチタノセン触媒１ｇ当たり１０００ｇ以上であり、かつ、前記共重合体の数平均分子量は２０，０００以上２００，０００以下である、共重合体の製造方法。 (1) In the presence of a non-crosslinked ketimido half-titanocene catalyst and a promoter composed of an alkylaluminoxane, at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin derived from C4 to C12 α-olefin A polymerization step of polymerizing the olefin monomer (B) to obtain a copolymer, and the amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the half titanocene catalyst, and the copolymer The method for producing a copolymer, wherein the number average molecular weight of the polymer is 20,000 or more and 200,000 or less.
　（２）　前記共重合体のガラス転移温度（Ｔｇ）は、１７０℃以上である（１）に記載の製造方法。 (2) The production method according to (1), wherein the glass transition temperature (Tg) of the copolymer is 170 ° C. or higher.
　本発明によれば、リガンドを最適化したチタノセン触媒をアルキルアルミノキサンからなる助触媒と併用することで、より少ない触媒量で、力学特性に優れ、かつ通常の成形加工に適した分子量の環状オレフィン共重合体をより多く得ることができる共重合体の製造方法を提供することができる。本発明では、使用する触媒の量が少ないため、それに応じて助触媒の量も低減することができる。よって、より少量の触媒及び助触媒で安価に、分子量の範囲を保ちながら、１バッチ当たりの環状オレフィン共重合体量を増やすことができ、省資源化を実現することもできる。また、得られる共重合体に残存する触媒及び助触媒が少ないため、この共重合体から得られるフィルム等の成形体は、透明性及び機械物性が向上しやすい。 According to the present invention, a ligand-optimized titanocene catalyst is used in combination with an alkylaluminoxane cocatalyst, so that a smaller amount of catalyst, excellent mechanical properties, and a molecular weight cyclic olefin copolymer suitable for ordinary molding processing are used. It is possible to provide a method for producing a copolymer capable of obtaining more polymer. In the present invention, since the amount of catalyst used is small, the amount of cocatalyst can be reduced accordingly. Therefore, the amount of cyclic olefin copolymer per batch can be increased while maintaining the molecular weight range at a low cost with a smaller amount of catalyst and cocatalyst, and resource saving can also be realized. Moreover, since there are few catalysts and cocatalysts remaining in the obtained copolymer, a molded product such as a film obtained from this copolymer is likely to be improved in transparency and mechanical properties.
　以下、本発明の実施形態について詳細に説明する。なお、本発明は以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment.
　本発明に係る共重合体の製造方法は、非架橋のケチミド型ハーフチタノセン触媒とアルキルアルミノキサンからなる助触媒との存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４～Ｃ１２のα－オレフィンから誘導されるα－オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、上記重合工程において得られる上記共重合体の量は、上記ハーフチタノセン触媒１ｇ当たり１０００ｇ以上であり、かつ、上記共重合体の数平均分子量は２０，０００以上２００，０００以下である。本発明に係る共重合体の製造方法によれば、より少ない触媒量でも、分子量の範囲を保ちながら、１バッチで高分子量の環状オレフィン共重合体をより多く得ることができる。なお、本発明に係る共重合体の製造方法において、重合工程は、上記ハーフチタノセン触媒及びアルキルアルミノキサンからなる助触媒とともに、連鎖移動剤の存在下で行ってもよい。 The method for producing a copolymer according to the present invention comprises at least a cyclic olefin monomer (A) derived from norbornene and C4 to C12 in the presence of an uncrosslinked ketimido half-titanocene catalyst and a co-catalyst comprising an alkylaluminoxane. And a polymerization step of polymerizing the α-olefin monomer (B) derived from the α-olefin to obtain a copolymer, and the amount of the copolymer obtained in the polymerization step is based on 1 g of the half titanocene catalyst. The number average molecular weight of the copolymer is 20,000 or more and 200,000 or less. According to the method for producing a copolymer according to the present invention, a higher amount of a high-molecular-weight cyclic olefin copolymer can be obtained in one batch while keeping the molecular weight range even with a smaller amount of catalyst. In the method for producing a copolymer according to the present invention, the polymerization step may be performed in the presence of a chain transfer agent together with the co-catalyst comprising the half titanocene catalyst and the alkylaluminoxane.
［共重合体］
　本発明に係る共重合体の製造方法により得られる共重合体は、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）由来の構造単位と、Ｃ４～Ｃ１２のα－オレフィンから誘導されるα－オレフィンモノマー（Ｂ）由来の構造単位と、を含む。
　上記製造方法に含まれる重合工程において得られる上記共重合体の量は、上記重合工程で用いられるチタノセン触媒１ｇ当たり１０００ｇ以上であり、好ましくは２０００ｇ以上であり、より好ましくは３０００ｇ以上である。 [Copolymer]
The copolymer obtained by the method for producing a copolymer according to the present invention comprises a structural unit derived from a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer derived from a C4 to C12 α-olefin. (B) derived structural units.
The amount of the copolymer obtained in the polymerization step included in the production method is 1000 g or more, preferably 2000 g or more, more preferably 3000 g or more per 1 g of titanocene catalyst used in the polymerization step.
　本発明における共重合体の数平均分子量は、好ましくは２０，０００以上２００，０００以下であり、より好ましくは３０，０００以上、１５０，０００以下である。上記数平均分子量が２０，０００以上であると、得られる共重合体は、ガラス転移温度（Ｔｇ）が過度に低くなりにくい。上記数平均分子量が２００，０００以下であると、得られる共重合体の溶液は、粘度が過度に高くなりにくい。なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィにより測定されたポリスチレン換算の数平均分子量をいう。 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 is unlikely to have an excessively low glass transition temperature (Tg). When the number average molecular weight is 200,000 or less, the resulting copolymer solution is unlikely to have an excessively high viscosity. In addition, in this specification, a number average molecular weight means the number average molecular weight of polystyrene conversion measured by gel permeation chromatography.
　本発明における共重合体のガラス転移温度（Ｔｇ）は、１７０℃以上であり、好ましくは２００℃以上、より好ましくは２３０℃以上、特に好ましくは２６０℃以上である。上記ガラス転移温度が１７０℃以上であると、上記共重合体から得られる透明フィルムは、十分な耐熱性を有し、よって、例えば、ＩＴＯ蒸着用の基板として好適に用いることができる。特に、上記ガラス転移温度が２６０℃以上であると、上記共重合体から得られる透明フィルムは、更に十分な耐熱性を有するため、例えば、溶融した鉛フリー半田に接しても、変形、亀裂、融解等が生じにくいため、鉛フリー半田用部材として好適に用いることができる。また、上記共重合体のガラス転移温度の上限は特に限定されないが、ガラス転移温度が高くなると共重合体中のα－オレフィン由来の構造単位が少なくなるため、α－オレフィン共重合による機械的強度の改善効果が小さくなる傾向にあることから、上記ガラス転移温度は、３５０℃以下であることが好ましく、３３０℃以下であることがより好ましい。なお、本明細書において、ガラス転移温度は、ＤＳＣ法（ＪＩＳ　Ｋ　７１２１記載の方法）によって昇温速度２０℃／分の条件で測定した値を採用する。 The glass transition temperature (Tg) of the copolymer in the present invention is 170 ° C. or higher, preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and particularly preferably 260 ° C. or higher. When the glass transition temperature is 170 ° C. or higher, the transparent film obtained from the copolymer has sufficient heat resistance, and can be suitably used, for example, as a substrate for ITO deposition. In particular, when the glass transition temperature is 260 ° C. or higher, the transparent film obtained from the copolymer has further sufficient heat resistance, so that, for example, deformation, cracking, contact with molten lead-free solder, Since melting or the like hardly occurs, it can be suitably used as a lead-free solder member. The upper limit of the glass transition temperature of the copolymer is not particularly limited, but mechanical strength due to α-olefin copolymerization is reduced because the structural unit derived from α-olefin in the copolymer decreases as the glass transition temperature increases. The glass transition temperature is preferably 350 ° C. or less, and more preferably 330 ° C. or less, because the improvement effect tends to be small. In addition, in this specification, the glass transition temperature employ | adopts the value measured on the conditions of the temperature increase rate of 20 degree-C / min by DSC method (method of JISK7121).
［非架橋のケチミド型ハーフチタノセン触媒］
　非架橋のケチミド型ハーフチタノセン触媒としては、特に限定されず、公知のものを使用することができる。上記ハーフチタノセン触媒は、１種単独で又は２種以上組み合わせて使用することができる。
　非架橋のケチミド型ハーフチタノセン触媒としては、例えば、下記式（１）で表されるものが挙げられる。 [Non-crosslinked ketimido half-titanocene catalyst]
The non-crosslinked ketimido type half titanocene catalyst is not particularly limited, and known ones can be used. The said half titanocene catalyst can be used individually by 1 type or in combination of 2 or more types.
Examples of the non-crosslinked ketimido half-titanocene catalyst include those represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１は下記式（２）で表される置換基を、Ｒ２は下記式（３）若しくは（４）で表されるケチミド基又は下記式（５）で表されるフェノキシ基を、Ｒ３及びＲ４は独立に、ハロゲン原子又はアルキル基を示す。）
Figure JPOXMLDOC01-appb-C000001
 (In the formula, R 1 is a substituent represented by the following formula (2), R 2 is a ketimido group represented by the following formula (3) or (4) or a phenoxy group represented by the following formula (5). R 3 and R 4 independently represent a halogen atom or an alkyl group.)
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ５はアルキル基を示し、ｎは０から５までの整数である。）
Figure JPOXMLDOC01-appb-C000002
 (In the formula, R 5 represents an alkyl group, and n is an integer from 0 to 5.)
　－Ｎ＝Ｃ（Ｒ６）（Ｒ７）　（３）
（式中、Ｒ６及びＲ７は独立にアルキル基又はフェニル基を示す。） -N = C (R 6 ) (R 7 ) (3)
(In the formula, R 6 and R 7 independently represent an alkyl group or a phenyl group.)
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ８及びＲ９は独立にアルキル基又はフェニル基を示す。）
Figure JPOXMLDOC01-appb-C000003
 (In the formula, R 8 and R 9 independently represent an alkyl group or a phenyl group.)
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、及びＲ１４は独立に水素原子、アルキル基、又はフェニル基を示す。）
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R 10 , R 11 , R 12 , R 13 , and R 14 independently represent a hydrogen atom, an alkyl group, or a phenyl group.)
　Ｒ３及びＲ４の具体例としては、フッ素原子、塩素原子、臭素原子等のハロゲン原子；メチル基、エチル基、プロピル基等の炭素数１～４のアルキル基が挙げられ、塩素原子が好ましい。 Specific examples of R 3 and R 4 include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group, with chlorine atom being preferred. .
　Ｒ５の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基等の炭素数１～５のアルキル基が挙げられ、ｔｅｒｔ－ブチル基が好ましい。 Specific examples of R 5 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group. A tert-butyl group is preferred.
　Ｒ６及びＲ７の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基等の炭素数１～５のアルキル基が挙げられ、ｔｅｒｔ－ブチル基が好ましい。 Specific examples of R 6 and R 7 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group. And a tert-butyl group is preferable.
　Ｒ８及びＲ９の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基等の炭素数１～５のアルキル基やフェニル基等が挙げられ、ｔｅｒｔ－ブチル基やフェニル基等が好ましい。 Specific examples of R 8 and R 9 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and neopentyl group. Examples thereof include a phenyl group, and a tert-butyl group and a phenyl group are preferable.
　Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、及びＲ１４の具体例としては、水素原子や、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等の炭素数１～４のアルキル基や、フェニル基等が挙げられ、Ｒ１０及びＲ１４はイソプロピル基であり、Ｒ１２及びＲ１３は水素原子であることが好ましい。 Specific examples of R 10 , R 11 , R 12 , R 13 , and R 14 include hydrogen atoms and carbon such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl groups. Examples thereof include an alkyl group of 1 to 4 and a phenyl group. R 10 and R 14 are preferably isopropyl groups, and R 12 and R 13 are preferably hydrogen atoms.
　非架橋のケチミド型ハーフチタノセン触媒の具体例としては、ＣｐＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）、（ｔ－ＢｕＣ５Ｈ４）ＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）、下記式（６）又は（７）で表される化合物等が挙げられ（式中、Ｃｐはシクロペンタジエニル基を、ｔ－Ｂｕはｔｅｒｔ－ブチル基を示す。）、好ましくはＣｐＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）及び（ｔ－ＢｕＣ５Ｈ４）ＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）である。 Specific examples of the non-crosslinked ketimido half-titanocene catalyst include CpTiCl 2 (N═C (t-Bu) 2 ), (t-BuC 5 H 4 ) TiCl 2 (N═C (t-Bu) 2 ), Examples include compounds represented by the following formula (6) or (7) (wherein Cp represents a cyclopentadienyl group and t-Bu represents a tert-butyl group), preferably CpTiCl 2 (N = C (t-Bu) 2 ) and (t-BuC 5 H 4 ) TiCl 2 (N = C (t-Bu) 2 ).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
［アルキルアルミノキサンからなる助触媒］
　本発明において用いられる助触媒は、アルキルアルミノキサンからなる。上記助触媒は、１種単独で又は２種以上組み合わせて使用することができる。
　アルキルアルミノキサンとしては、特に限定されず、例えば、下記式（８）又は（９）で表される化合物が挙げられる。下記式（８）又は（９）で表されるアルキルアルミノキサンは、トリアルキルアルミニウムと水との反応により得られる生成物である。 [Promoter made of alkylaluminoxane]
The cocatalyst used in the present invention comprises an alkylaluminoxane. The above promoters can be used alone or in combination of two or more.
The alkylaluminoxane is not particularly limited, and examples thereof include compounds represented by the following formula (8) or (9). The alkylaluminoxane represented by the following formula (8) or (9) is a product obtained by the reaction of trialkylaluminum and water.
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒは炭素数１～４のアルキル基、ｎは０～４０、好ましくは２～３０の整数を示す。）
Figure JPOXMLDOC01-appb-C000007
 (In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 40, preferably 2 to 30.)
　アルキルアルミノキサンとしては、メチルアルミノキサン及びメチルアルミノキサンのメチル基の一部を他のアルキル基で置換した修飾メチルアルミノキサンが挙げられる。修飾メチルアルミノキサンとしては、例えば、置換後のアルキル基として、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等の炭素数２～４のアルキル基を有する修飾メチルアルミノキサンが好ましく、特に、メチル基の一部をイソブチル基で置換した修飾メチルアルミノキサンがより好ましい。アルキルアルミノキサンの具体例としては、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサン、ブチルアルミノキサン、イソブチルアルミノキサン、メチルエチルアルミノキサン、メチルブチルアルミノキサン、メチルイソブチルアルミノキサン等が挙げられ、中でも、メチルアルミノキサン及びメチルイソブチルアルミノキサンが好ましい。 Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl group of methylaluminoxane is substituted with another alkyl group. As the modified methylaluminoxane, for example, a modified methylaluminoxane 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 as an alkyl group after substitution is preferable. A modified methylaluminoxane in which a part of the group is substituted with an isobutyl group is more preferable. Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferable.
　アルキルアルミノキサンは、公知の方法で調製することができる。また、アルキルアルミノキサンとしては、市販品を用いてもよい。アルキルアルミノキサンの市販品としては、例えば、ＭＭＡＯ－３Ａ、ＴＭＡＯ－２００シリーズ、ＴＭＡＯ－３４０シリーズ（いずれも東ソー・ファインケム（株）製）やメチルアルミノキサン溶液（アルベマール社製）等が挙げられる。 Alkylaluminoxane can be prepared by a known method. Moreover, as an alkylaluminoxane, you may use a commercial item. Examples of commercially available products of alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.) and methylaluminoxane solution (manufactured by Albemarle).
［環状オレフィンモノマー（Ａ）］
　ノルボルネンから誘導される環状オレフィンモノマー（Ａ）としては、例えば、ノルボルネン及び置換ノルボルネンが挙げられ、ノルボルネンが好ましい。上記環状オレフィンモノマー（Ａ）は、１種単独で又は２種以上組み合わせて使用することができる。 [Cyclic olefin monomer (A)]
Examples of the cyclic olefin monomer (A) derived from norbornene include norbornene and substituted norbornene, and norbornene is preferable. The said cyclic olefin monomer (A) can be used individually by 1 type or in combination of 2 or more types.
　上記置換ノルボルネンは特に限定されず、この置換ノルボルネンが有する置換基としては、例えば、ハロゲン原子、１価又は２価の炭化水素基が挙げられる。置換ノルボルネンの具体例としては、下記一般式（Ｉ）で示されるものが挙げられる。 The substituted norbornene is not particularly limited, and examples of the substituent that the substituted norbornene has include a halogen atom, a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１～Ｒ１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、
　Ｒ９とＲ１０、Ｒ１１とＲ１２は、一体化して２価の炭化水素基を形成してもよく、
　Ｒ９又はＲ１０と、Ｒ１１又はＲ１２とは、互いに環を形成していてもよい。
　また、ｎは、０又は正の整数を示し、
　ｎが２以上の場合には、Ｒ５～Ｒ８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。
　ただし、ｎ＝０の場合、Ｒ１～Ｒ４及びＲ９～Ｒ１２の少なくとも１個は、水素原子ではない。）
Figure JPOXMLDOC01-appb-C000008
 (Wherein R 1 to R 12 may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group;
R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent 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 in each repeating unit.
However, when n = 0, at least one of R 1 to R 4 and R 9 to R 12 is not a hydrogen atom. )
　一般式（Ｉ）で示される置換ノルボルネンについて説明する。一般式（Ｉ）におけるＲ１～Ｒ１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものである。 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.
　Ｒ１～Ｒ８の具体例としては、例えば、水素原子；フッ素、塩素、臭素等のハロゲン原子；炭素数１以上２０以下のアルキル基等を挙げることができ、これらはそれぞれ異なっていてもよく、部分的に異なっていてもよく、また、全部が同一であってもよい。 Specific examples of R 1 to R 8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , May be partially different or all may be the same.
　また、Ｒ９～Ｒ１２の具体例としては、例えば、水素原子；フッ素、塩素、臭素等のハロゲン原子；炭素数１以上２０以下のアルキル基；シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、エチルフェニル基、イソプロピルフェニル基、ナフチル基、アントリル基等の置換又は無置換の芳香族炭化水素基；ベンジル基、フェネチル基、その他アルキル基にアリール基が置換したアラルキル基等を挙げることができ、これらはそれぞれ異なっていてもよく、部分的に異なっていてもよく、また、全部が同一であってもよい。 Specific examples of R 9 to R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and tolyl Group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group and the like substituted or unsubstituted aromatic hydrocarbon group; benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group These may be different from each other, may be partially different, or all may be the same.
　Ｒ９とＲ１０、又はＲ１１とＲ１２とが一体化して２価の炭化水素基を形成する場合の具体例としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基等のアルキリデン基等を挙げることができる。 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, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.
　Ｒ９又はＲ１０と、Ｒ１１又はＲ１２とが、互いに環を形成する場合には、形成される環は単環でも多環であってもよく、架橋を有する多環であってもよく、二重結合を有する環であってもよく、またこれらの環の組み合わせからなる環であってもよい。また、これらの環はメチル基等の置換基を有していてもよい。 When R 9 or R 10 and R 11 or R 12 form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.
　一般式（Ｉ）で示される置換ノルボルネンの具体例としては、５－メチル－ビシクロ［２．２．１］ヘプタ－２－エン、５，５－ジメチル－ビシクロ［２．２．１］ヘプタ－２－エン、５－エチル－ビシクロ［２．２．１］ヘプタ－２－エン、５－ブチル－ビシクロ［２．２．１］ヘプタ－２－エン、５－エチリデン－ビシクロ［２．２．１］ヘプタ－２－エン、５－ヘキシル－ビシクロ［２．２．１］ヘプタ－２－エン、５－オクチル－ビシクロ［２．２．１］ヘプタ－２－エン、５－オクタデシル－ビシクロ［２．２．１］ヘプタ－２－エン、５－メチリデン－ビシクロ［２．２．１］ヘプタ－２－エン、５－ビニル－ビシクロ［２．２．１］ヘプタ－２－エン、５－プロペニル－ビシクロ［２．２．１］ヘプタ－２－エン等の２環の環状オレフィン； 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] hepta- 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2. 1] Hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [ 2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 5- Bicyclic such as propenyl-bicyclo [2.2.1] hept-2-ene Jo olefin;
トリシクロ［４．３．０．１２，５］デカ－３，７－ジエン（慣用名：ジシクロペンタジエン）、トリシクロ［４．３．０．１２，５］デカ－３－エン；トリシクロ［４．４．０．１２，５］ウンデカ－３，７－ジエン若しくはトリシクロ［４．４．０．１２，５］ウンデカ－３，８－ジエン又はこれらの部分水素添加物（又はシクロペンタジエンとシクロヘキセンの付加物）であるトリシクロ［４．４．０．１２，５］ウンデカ－３－エン；５－シクロペンチル－ビシクロ［２．２．１］ヘプタ－２－エン、５－シクロヘキシル－ビシクロ［２．２．１］ヘプタ－２－エン、５－シクロヘキセニルビシクロ［２．２．１］ヘプタ－２－エン、５－フェニル－ビシクロ［２．２．１］ヘプタ－２－エンといった３環の環状オレフィン； Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: 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 a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;
テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン（単にテトラシクロドデセンともいう）、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－エチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－メチリデンテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－ビニルテトラシクロ［４，４．０．１２，５．１７，１０］ドデカ－３－エン、８－プロペニル－テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エンといった４環の環状オレフィン； Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene (also simply referred to 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 ] dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-vinyltetracyclo [4,4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] tetracyclic olefins such as dodec-3-ene;
８－シクロペンチル－テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－シクロヘキシル－テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－シクロヘキセニル－テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－フェニル－シクロペンチル－テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン；テトラシクロ［７．４．１３，６．０１，９．０２，７］テトラデカ－４，９，１１，１３－テトラエン（１，４－メタノ－１，４，４ａ，９ａ－テトラヒドロフルオレンともいう）、テトラシクロ［８．４．１４，７．０１，１０．０３，８］ペンタデカ－５，１０，１２，１４－テトラエン（１，４－メタノ－１，４，４ａ，５，１０，１０ａ－へキサヒドロアントラセンともいう）；ペンタシクロ［６．６．１．１３，６．０２，７．０９，１４］－４－ヘキサデセン、ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］－４－ペンタデセン、ペンタシクロ［７．４．０．０２，７．１３，６．１１０，１３］－４－ペンタデセン；ヘプタシクロ［８．７．０．１２，９．１４，７．１１１，１７．０３，８．０１２，１６］－５－エイコセン、ヘプタシクロ［８．７．０．１２，９．０３，８．１４，７．０１２，１７．１１３，ｌ６］－１４－エイコセン；シクロペンタジエンの４量体等の多環の環状オレフィンを挙げることができる。 8-cyclopentyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene; tetracyclo [7.4.1 3,6 . 0 1,9 . 0 2,7 ] tetradeca-4,9,11,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 4,7 . 0 1,10 . 0 3,8 ] pentadeca-5,10,12,14-tetraene (also referred to as 1,4-methano-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] -4-pentadecene, pentacyclo [7.4.0.0 2,7. 1 3,6 . 1 10,13] -4-pentadecene; heptacyclo [8.7.0.1 2,9. 1 4,7 . 1 11, 17 . 0 3,8 . 0 12,16 ] -5-eicosene, heptacyclo [8.7.0.1 2,9 . 0 3,8 . 1 4,7 . 0 12,17 . 1 13,16 ] -14-eicosene ; and polycyclic cyclic olefins such as cyclopentadiene tetramer.
　中でも、アルキル置換ノルボルネン（例えば、１個以上のアルキル基で置換されたビシクロ［２．２．１］ヘプタ－２－エン）、アルキリデン置換ノルボルネン（例えば、１個以上のアルキリデン基で置換されたビシクロ［２．２．１］ヘプタ－２－エン）が好ましく、５－エチリデン－ビシクロ［２．２．１］ヘプタ－２－エン（慣用名：５－エチリデン－２－ノルボルネン、又は、単にエチリデンノルボルネン）が特に好ましい。 Among these, alkyl-substituted norbornene (eg, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornene (eg, bicyclo substituted with one or more alkylidene groups). [2.2.1] hept-2-ene), preferably 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene Is particularly preferred.
［α－オレフィンモノマー（Ｂ）］
　Ｃ４～Ｃ１２のα－オレフィンから誘導されるα－オレフィンモノマー（Ｂ）としては、例えば、Ｃ４～Ｃ１２のα－オレフィンや、ハロゲン原子等の少なくとも１種の置換基を有するＣ４～Ｃ１２のα－オレフィンが挙げられ、Ｃ４～Ｃ１２のα－オレフィンが好ましく、Ｃ６～Ｃ１０のα－オレフィンがより好ましい。 [Α-olefin monomer (B)]
Examples of the α-olefin monomer (B) derived from a C4 to C12 α-olefin include C4 to C12 α-olefin and a C4 to C12 α-olefin having at least one substituent such as a halogen atom. Examples thereof include olefins, and C4 to C12 α-olefins are preferable, and C6 to C10 α-olefins are more preferable.
　Ｃ４～Ｃ１２のα－オレフィンは特に限定されないが、例えば、１－ブテン、１－ペンテン、１－へキセン、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－へキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－へキセン、３－エチル－１－ヘキセン、１－オクテン、１－デセン、１－ドデセン等が挙げられる。中でも、１－ヘキセン、１－オクテン、１－デセンが好ましい。 The C4 to C12 α-olefin is not particularly limited. For example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 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- Examples include ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Of these, 1-hexene, 1-octene and 1-decene are preferable.
［重合工程の条件］
　重合工程の条件は、所望の共重合体が得られる限り、特に限定されず、公知の条件を用いることができ、重合温度、重合圧力、重合時間等は適宜調整される。また、各成分の使用量は、以下のとおりに例示される。
　α－オレフィンモノマー（Ｂ）の添加量は、環状オレフィンモノマー（Ａ）１００質量部に対し、１質量部以上５００質量部以下であることが好ましく、１０質量部以上３００質量部以下であることがより好ましい。
　非架橋のケチミド型ハーフチタノセン触媒の使用量は、環状オレフィンモノマー（Ａ）１００質量部に対し、０．００００１質量部以上０．１質量部以下であることが好ましく、０．０００１量部以上０．０５質量部以下であることがより好ましい。
　アルキルアルミノキサンの使用量は、環状オレフィンモノマー（Ａ）１００質量部に対し、Ａｌ基準で０．０００１質量部以上５質量部以下であることが好ましく、０．０１質量部以上３質量部以下であることがより好ましい。 [Conditions for polymerization process]
The conditions for the polymerization step are not particularly limited as long as the desired copolymer is obtained, and known conditions can be used, and the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted. Moreover, the usage-amount of each component is illustrated as follows.
The addition amount of the α-olefin monomer (B) is preferably 1 part by mass or more and 500 parts by mass or less, and preferably 10 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferred.
The amount of the non-crosslinked ketimido half-titanocene catalyst used is preferably 0.00001 parts by mass or more and 0.1 parts by mass or less, based on 100 parts by mass of the cyclic olefin monomer (A). More preferably, the amount is 0.05 parts by mass or less.
The amount of the alkylaluminoxane used is preferably 0.0001 parts by mass or more and 5 parts by mass or less, and 0.01 parts by mass or more and 3 parts by mass or less based on Al with respect to 100 parts by mass of the cyclic olefin monomer (A). It is more preferable.
　以下、実施例を示し、本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。特に断らない限り、量を表す「部」は「質量部」を意味する。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” representing an amount means “part by mass”.
［共重合体の作製］
　乾燥し、窒素雰囲気下に保ったガラス反応器に、表１に記載された各モノマー、及び表２に記載された助触媒を加え、重合温度に保ったのち、表２に記載された触媒を加えた。なお、触媒及び助触媒は、それぞれトルエンに溶解させた状態で反応器に加えた。表３に示す重合温度及び重合時間で、反応器内を撹拌して重合を継続した後、２－プロパノール１質量部を添加して反応を終了させた。次いで、得られた重合反応液を多量の塩酸酸性メタノールに注いで重合体を完全に析出させ、濾別及び洗浄を行った後、６０℃で１日間以上減圧乾燥して共重合体を得た。得られた共重合体の質量を測定した（表３中の「収量」）。使用した触媒量に対する得られた共重合体の割合を算出した（表３中の「ｇ（共重合体）／ｇ（触媒）」）。 [Production of copolymer]
Each monomer listed in Table 1 and the promoter described in Table 2 were added to a glass reactor that had been dried and kept under a nitrogen atmosphere, and after maintaining the polymerization temperature, the catalysts listed in Table 2 were used. added. The catalyst and the cocatalyst were each added to the reactor in a state dissolved in toluene. At the polymerization temperature and 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 complete the reaction. Next, the obtained polymerization reaction solution was poured into a large amount of hydrochloric acid methanol to completely precipitate the polymer, filtered and washed, and then dried under reduced pressure at 60 ° C. for 1 day or more to obtain a copolymer. . The mass of the obtained copolymer was measured (“Yield” in Table 3). The ratio of the obtained copolymer to the amount of catalyst used was calculated (“g (copolymer) / g (catalyst)” in Table 3).
　なお、使用した触媒及び助触媒の種類は下記のとおりである。ここで、ｔ－Ｂｕはｔｅｒｔ－ブチル基を、Ｆｌｕはフルオレニル基を、Ｃｐはシクロペンタジエニル基を示す。
　触媒Ａ：（ｔ－ＢｕＮＳｉＭｅ２Ｆｌｕ）ＴｉＭｅ２
　触媒Ｂ：ＣｐＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）
　触媒Ｃ：（ｔ－ＢｕＣ５Ｈ４）ＴｉＣｌ２（Ｎ＝Ｃ（ｔ－Ｂｕ）２）
　助触媒：６．５質量％（Ａｌ原子の含有量として）ＭＭＡＯ－３Ａのトルエン溶液（東ソー・ファインケム（株）製） The types of catalyst and cocatalyst used are as follows. Here, t-Bu represents a tert-butyl group, Flu represents a fluorenyl group, and Cp represents a cyclopentadienyl group.
Catalyst A: (t-BuNSiMe 2 Flu) TiMe 2
Catalyst B: CpTiCl 2 (N = C (t-Bu) 2 )
Catalyst C: (t-BuC 5 H 4 ) TiCl 2 (N = C (t-Bu) 2 )
Cocatalyst: 6.5% by mass (as Al atom content) MMAO-3A in toluene solution (manufactured by Tosoh Finechem Co., Ltd.)
　各共重合体の数平均分子量、Ｔｇを表３に示した。 The number average molecular weight and Tg of each copolymer are shown in Table 3.
　表１、表２、及び表３中の「部」の値は、２－ノルボルネン１００部に対する値である。また、表２中の助触媒について、「部」の値はトルエン溶液としての値である。 The values of “parts” in Tables 1, 2, and 3 are values for 100 parts of 2-norbornene. Moreover, about the promoter in Table 2, the value of "part" is a value as a toluene solution.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表３に示されるとおり、本発明によれば、使用した触媒量に対して得られる共重合体の割合が高い。 As shown in Table 3, according to the present invention, the proportion of the copolymer obtained is high with respect to the amount of catalyst used.

Claims (2)

  1. 　非架橋のケチミド型ハーフチタノセン触媒とアルキルアルミノキサンからなる助触媒との存在下で、少なくとも、ノルボルネンから誘導される環状オレフィンモノマー（Ａ）とＣ４～Ｃ１２のα－オレフィンから誘導されるα－オレフィンモノマー（Ｂ）とを重合させて共重合体を得る重合工程を含み、
    　前記重合工程において得られる前記共重合体の量は、前記ハーフチタノセン触媒１ｇ当たり１０００ｇ以上であり、かつ、前記共重合体の数平均分子量は２０，０００以上２００，０００以下である、共重合体の製造方法。     An α-olefin monomer derived from at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin of C4 to C12 in the presence of a non-crosslinked ketimido half-titanocene catalyst and a promoter comprising an alkylaluminoxane. A polymerization step of polymerizing (B) to obtain a copolymer,
    The amount of the copolymer obtained in the polymerization step is 1000 g or more per 1 g of the half titanocene catalyst, and the copolymer has a number average molecular weight of 20,000 or more and 200,000 or less. Manufacturing method.
  2. 　前記共重合体のガラス転移温度（Ｔｇ）は、１７０℃以上である請求項１に記載の製造方法。 The manufacturing method according to claim 1, wherein a glass transition temperature (Tg) of the copolymer is 170 ° C or higher.
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