WO2015178143A1 - Procédé de production d'un copolymère d'oléfine cyclique - Google Patents

Procédé de production d'un copolymère d'oléfine cyclique Download PDF

Info

Publication number
WO2015178143A1
WO2015178143A1 PCT/JP2015/061986 JP2015061986W WO2015178143A1 WO 2015178143 A1 WO2015178143 A1 WO 2015178143A1 JP 2015061986 W JP2015061986 W JP 2015061986W WO 2015178143 A1 WO2015178143 A1 WO 2015178143A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
copolymer
catalyst
cyclic olefin
dimethyl
Prior art date
Application number
PCT/JP2015/061986
Other languages
English (en)
Japanese (ja)
Inventor
敬之 八重樫
恵市 小佐野
善道 岡野
直人 奥山
Original Assignee
ポリプラスチックス株式会社
株式会社ダイセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社, 株式会社ダイセル filed Critical ポリプラスチックス株式会社
Priority to JP2016521003A priority Critical patent/JP6685223B2/ja
Priority to KR1020167031265A priority patent/KR102331299B1/ko
Priority to CN201580021148.6A priority patent/CN106232641B/zh
Publication of WO2015178143A1 publication Critical patent/WO2015178143A1/fr

Links

Classifications

    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only 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
    • 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
    • C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond

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 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 suitable for ordinary molding processing, and completed the present invention. It came to do. More specifically, the present invention provides the following.
  • 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 present invention it is possible to provide a method for producing a copolymer capable of obtaining a larger amount of a cyclic olefin copolymer having a lower catalyst amount, excellent mechanical properties, and suitable for ordinary molding processing. it can.
  • the effect of the present invention can be further improved by controlling the amount of the chain transfer agent.
  • 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 an ⁇ -olefin monomer (B) derived from a C4 to C12 ⁇ -olefin in the presence of a titanocene catalyst.
  • 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 from 20,000 to 200,000.
  • the polymerization step comprises a co-catalyst comprising an alkylaluminoxane together with a titanocene catalyst. It is preferably carried out in the presence of a chain transfer agent.
  • 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, 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).
  • titanocene catalyst It does not specifically limit as a titanocene catalyst, A well-known thing can be used.
  • a titanocene catalyst can be used individually by 1 type or in combination of 2 or more types.
  • As a titanocene catalyst what is represented by following formula (1) is mentioned, for example.
  • 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, alkyl group such as pentyl group, hexyl group, cyclopentyl group, cyclohexyl group; phenyl group, biphenyl group And aryl groups such as a phenyl group or 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 are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom, and specifically includes a fluorine atom, a chlorine atom, a bromine atom, iodine Halogen atoms such as atoms; 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, cyclohexyl group, the above halogen atom
  • aryl groups having a phenyl group, a biphenyl group, a naphthyl group, the above halogen atom or an alkyl group as a substituent.
  • R 6 to R 13 each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent. It may be a silyl group. Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, and cyclopentyl. Group, cyclohexyl group and the like.
  • aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and these aryl groups having the above alkyl group as a substituent.
  • silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl
  • a silyl group having an alkyl group having 1 to 12 carbon atoms such as a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group as a substituent.
  • titanocene catalyst represented by the general formula (1) examples include (isopropylamide) dimethyl-9-fluorenylsilane titanium dimethyl, (isobutylamide) dimethyl-9-fluorenylsilane titanium dimethyl, (t-butylamide).
  • T-Butylamido dimethyl-9-fluorenylsilane titanium dimethyl ((t-BuNSiMe 2 Flu) TiMe 2 ) is preferred.
  • (T-BuNSiMe 2 Flu) TiMe 2 is a titanium complex represented by the following formula (2). For example, it can be easily synthesized based on the description of “Macromolecules, Vol. 31, 3184, 1998”. Can do.
  • Me represents a methyl group
  • t-Bu represents a tert-butyl group
  • 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 (3) or (4).
  • the alkylaluminoxane represented by the following formula (3) or (4) 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).
  • the chain transfer agent used in the present invention is a compound having chain transfer ability.
  • a chain transfer agent can be used individually by 1 type or in combination of 2 or more types.
  • the chain transfer agent is not particularly limited, and a known compound having chain transfer ability can be used, and examples thereof include alkylaluminum.
  • alkylaluminum include a compound represented by the following general formula (5). (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.)
  • alkyl group having 1 to 15 carbon atoms examples 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.
  • alkylaluminum examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trin-octylaluminum; dimethylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.
  • Chain Shutting agents known for polymerization with metallocene catalysts can also be used.
  • chain shuffling agent examples include the above-described alkyl aluminum and alkyl zinc.
  • alkyl zinc the compound shown by following General formula (6) is mentioned, for example. (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.)
  • alkyl group having 1 to 15 carbon atoms examples 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.
  • alkyl zinc examples include dialkyl zinc such as dimethyl zinc, diethyl zinc, diisopropyl zinc, di n-butyl zinc, diisobutyl zinc, disec-butyl zinc aluminum, di n-octyl zinc; methyl zinc chloride, isobutyl zinc chloride Alkyl zinc halides such as isobutyl zinc hydride; alkyl zinc alkoxides such as methyl zinc methoxide; zinc halides such as zinc chloride.
  • Alkyl aluminum or alkyl zinc may be charged directly into the polymerization system or may be charged in the state of being contained in the alkyl aluminoxane. Moreover, the alkylaluminum of the raw material used when manufacturing an alkylaluminoxane and remaining after manufacture may be sufficient. Alkyl aluminum and alkyl zinc may be used in combination.
  • 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 titanocene catalyst used is preferably 0.00001 parts by mass or more and 0.1 parts by mass or less, and 0.0001 parts by mass or more and 0.05 parts by mass or less with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferably.
  • 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.
  • the amount of the chain transfer agent used is preferably 0.0001 parts by mass to 10 parts by mass and more preferably 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the cyclic olefin monomer (A). More preferred.
  • 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.
  • Cocatalyst B 9.0% by mass (a
  • the values of “parts” in Tables 1, 2, and 3 are values for 100 parts of 2-norbornene. Moreover, about the promoter A and the promoter B 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

　Cette invention concerne un procédé de production d'un copolymère qui permet d'obtenir, à l'aide d'une plus petite quantité de catalyseur, une plus grande quantité d'un copolymère d'oléfine cyclique présentant d'excellentes propriétés mécaniques et un poids moléculaire se prêtant au moulage classique. Un procédé de production d'un copolymère selon l'invention est en outre décrit, ledit procédé comprenant une étape de polymérisation pour obtenir un copolymère par polymérisation d'au moins un monomère d'oléfine cyclique dérivé du norbornène (A) et d'un monomère d'α-oléfine dérivé d'une alpha-oléfine C4-C12 (B) en présence d'un catalyseur de titanocène, la quantité de copolymère obtenue dans cette étape de polymérisation étant de 1000 g ou plus par gramme de catalyseur de titanocène, et le poids moléculaire moyen en nombre du copolymère étant de 20 000 à 200 000.
PCT/JP2015/061986 2014-05-23 2015-04-20 Procédé de production d'un copolymère d'oléfine cyclique WO2015178143A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2016521003A JP6685223B2 (ja) 2014-05-23 2015-04-20 環状オレフィン共重合体の製造方法
KR1020167031265A KR102331299B1 (ko) 2014-05-23 2015-04-20 환상 올레핀 공중합체의 제조방법
CN201580021148.6A CN106232641B (zh) 2014-05-23 2015-04-20 环状烯烃共聚物的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-107144 2014-05-23
JP2014107144 2014-05-23

Publications (1)

Publication Number Publication Date
WO2015178143A1 true WO2015178143A1 (fr) 2015-11-26

Family

ID=54553819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/061986 WO2015178143A1 (fr) 2014-05-23 2015-04-20 Procédé de production d'un copolymère d'oléfine cyclique

Country Status (5)

Country Link
JP (1) JP6685223B2 (fr)
KR (1) KR102331299B1 (fr)
CN (1) CN106232641B (fr)
TW (1) TWI667263B (fr)
WO (1) WO2015178143A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104676A (ja) * 2016-12-26 2018-07-05 ポリプラスチックス株式会社 環状オレフィン重合用の触媒組成物の製造方法、及び環状オレフィン樹脂組成物の製造方法
WO2019026839A1 (fr) * 2017-08-01 2019-02-07 ポリプラスチックス株式会社 Copolymère et procédé de production de copolymère
JP2020007413A (ja) * 2018-07-04 2020-01-16 ポリプラスチックス株式会社 メタロセン触媒の触媒活性の検定方法、オレフィンモノマー重合用の触媒組成物の製造方法、及びポリマーの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685715B (zh) * 2020-12-31 2024-05-03 江苏博睿光电股份有限公司 一种可交联热塑性环烯烃共聚物及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132523A (ja) * 1991-11-11 1993-05-28 Idemitsu Kosan Co Ltd 環状オレフイン系重合体の製造方法
JPH08268927A (ja) * 1995-03-28 1996-10-15 Tokuyama Corp 環状オレフィンの精製方法および重合方法
JP2000119328A (ja) * 1998-10-16 2000-04-25 Teijin Ltd 触媒残渣の少ない環状オレフィン系重合体、その用途並びにその製造法
JP2000204120A (ja) * 1999-01-18 2000-07-25 Mitsui Chemicals Inc ノルボルネン系重合体の製造方法
JP2007119660A (ja) * 2005-10-31 2007-05-17 Nippon Zeon Co Ltd 環状オレフィン付加共重合体、その製造方法、及び成形用材料
JP2009298999A (ja) * 2008-05-14 2009-12-24 Kaneka Corp 環状オレフィン付加共重合体、光学用フィルム及び液晶またはｅｌ表示素子用透明導電性フィルム
WO2014014195A1 (fr) * 2012-07-19 2014-01-23 (주)제이브이엠 Système de gestion de médicaments et procédé de gestion de médicaments associé

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5017222B2 (ja) 2007-09-25 2012-09-05 富士フイルム株式会社 環状オレフィン系共重合体、フィルム、これを用いた偏光板および液晶表示装置
KR101588368B1 (ko) * 2013-03-11 2016-01-25 포리프라스틱 가부시키가이샤 노보넨계 중합체 용액

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132523A (ja) * 1991-11-11 1993-05-28 Idemitsu Kosan Co Ltd 環状オレフイン系重合体の製造方法
JPH08268927A (ja) * 1995-03-28 1996-10-15 Tokuyama Corp 環状オレフィンの精製方法および重合方法
JP2000119328A (ja) * 1998-10-16 2000-04-25 Teijin Ltd 触媒残渣の少ない環状オレフィン系重合体、その用途並びにその製造法
JP2000204120A (ja) * 1999-01-18 2000-07-25 Mitsui Chemicals Inc ノルボルネン系重合体の製造方法
JP2007119660A (ja) * 2005-10-31 2007-05-17 Nippon Zeon Co Ltd 環状オレフィン付加共重合体、その製造方法、及び成形用材料
JP2009298999A (ja) * 2008-05-14 2009-12-24 Kaneka Corp 環状オレフィン付加共重合体、光学用フィルム及び液晶またはｅｌ表示素子用透明導電性フィルム
WO2014014195A1 (fr) * 2012-07-19 2014-01-23 (주)제이브이엠 Système de gestion de médicaments et procédé de gestion de médicaments associé

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104676A (ja) * 2016-12-26 2018-07-05 ポリプラスチックス株式会社 環状オレフィン重合用の触媒組成物の製造方法、及び環状オレフィン樹脂組成物の製造方法
JP7150428B2 (ja) 2016-12-26 2022-10-11 ポリプラスチックス株式会社 環状オレフィン重合用の触媒組成物の製造方法、及び環状オレフィン樹脂組成物の製造方法
WO2019026839A1 (fr) * 2017-08-01 2019-02-07 ポリプラスチックス株式会社 Copolymère et procédé de production de copolymère
JP6491804B1 (ja) * 2017-08-01 2019-03-27 ポリプラスチックス株式会社 共重合体及び共重合体の製造方法
JP2020007413A (ja) * 2018-07-04 2020-01-16 ポリプラスチックス株式会社 メタロセン触媒の触媒活性の検定方法、オレフィンモノマー重合用の触媒組成物の製造方法、及びポリマーの製造方法
JP7101063B2 (ja) 2018-07-04 2022-07-14 ポリプラスチックス株式会社 メタロセン触媒の触媒活性の検定方法、オレフィンモノマー重合用の触媒組成物の製造方法、及びポリマーの製造方法

Also Published As

Publication number Publication date
KR102331299B1 (ko) 2021-11-25
JPWO2015178143A1 (ja) 2017-04-20
CN106232641A (zh) 2016-12-14
KR20170012223A (ko) 2017-02-02
JP6685223B2 (ja) 2020-04-22
CN106232641B (zh) 2020-12-01
TW201609842A (zh) 2016-03-16
TWI667263B (zh) 2019-08-01

Similar Documents

Publication Publication Date Title
EP0719803B1 (fr) Procédé de préparation d'un copolymère statistique d'un cyclooléfine
JP6491804B1 (ja) 共重合体及び共重合体の製造方法
JP6685223B2 (ja) 環状オレフィン共重合体の製造方法
JP2018145425A (ja) 環状オレフィン樹脂組成物、その製造方法、及び成形品
JP6358852B2 (ja) 環状オレフィン共重合体の製造方法
KR101588368B1 (ko) 노보넨계 중합체 용액
WO2020204187A1 (fr) Procede de production de polymere de cycloolefine
KR101876950B1 (ko) 성형체
JP7125569B2 (ja) 環状オレフィン共重合体の製造方法、及びノルボルネン単量体とエチレンとの共重合用の触媒組成物
CA2170703A1 (fr) Methode de preparation de copolymere de cycloolefine de type aleatoire
JP7426543B2 (ja) 環状オレフィン共重合体、樹脂組成物及びフィルム状又はシート状の成形品
JP7383852B1 (ja) 環状オレフィン共重合体、及び環状オレフィン共重合体の製造方法
JP2023042441A (ja) ノルボルナン骨格含有重合体の製造方法、及びノルボルナン骨格含有重合体
JP2022030194A (ja) 環状オレフィン共重合体、及び環状オレフィン共重合体の製造方法
JP2023112594A (ja) 樹脂組成物、及びフィルム
WO2023149506A1 (fr) Copolymère d'oléfine cyclique et procédé de production de copolymère d'oléfine cyclique
JP2022060007A (ja) 環状オレフィン共重合体、成形品、及び環状オレフィン共重合体の製造方法
JPH04189806A (ja) エチレン―環状オレフィンランダム共重合体及びその製造法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15796693

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016521003

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167031265

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15796693

Country of ref document: EP

Kind code of ref document: A1