WO2015178143A1 - Method for producing cyclic olefin copolymer - Google Patents
Method for producing cyclic olefin copolymer Download PDFInfo
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- 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
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- cyclic olefin
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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
- C08F4/659—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
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- 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
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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
- 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
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- 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.
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Abstract
Description
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, per 1 g of titanocene catalyst used in the polymerization step.
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。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。
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。 [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.
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(3)又は(4)で表される化合物が挙げられる。下記式(3)又は(4)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 (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) is a product obtained by the reaction of trialkylaluminum and water.
本発明において用いられる連鎖移動剤は、連鎖移動能を有する化合物である。連鎖移動剤は、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。 [Chain transfer agent]
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.
(R10)zAlX3-z (5)
(式中、R10は炭素数が1~15、好ましくは1~8のアルキル基であり、Xはハロゲン原子又は水素原子であり、zは1~3の整数である。) The chain transfer agent is not particularly limited, and a known compound having chain transfer ability can be used, and examples thereof include alkylaluminum. Examples of the 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.)
(R11)zZnX2-y (6)
(式中、R11は炭素数が1~15、好ましくは1~8のアルキル基であり、Xはハロゲン原子又は水素原子であり、yは0~2の整数である。) As other chain transfer agents, Chain Shutting agents known for polymerization with metallocene catalysts can also be used. Examples of the chain shuffling agent include the above-described alkyl aluminum and alkyl zinc. As 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.)
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.
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。)
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. )
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.
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。
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質量部以上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。
連鎖移動剤の使用量は、環状オレフィンモノマー(A)100質量部に対し、0.0001質量部以上10質量部以下であることが好ましく、0.01質量部以上5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 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.
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).
触媒A:(t-BuNSiMe2Flu)TiMe2
助触媒A:6.5質量%(Al原子の含有量として)MMAO-3Aトルエン溶液([(CH3)0.7(iso-C4H9)0.3AlO]nで表されるメチルイソブチルアルミノキサンの溶液、東ソー・ファインケム(株)製、なお全Alに対して6mol%のトリメチルアルミニウムを含有する)
助触媒B:9.0質量%(Al原子の含有量として)TMAO-211トルエン溶液(メチルアルミノキサンの溶液、東ソー・ファインケム(株)製、なお全Alに対して26mol%のトリメチルアルミニウムを含有する)
助触媒C:トリイソブチルアルミニウム
助触媒D:ジメチルアニリウムテトラキス(ペンタフルオロフェニル)ボレート The types of catalyst and cocatalyst used are as follows. Here, t-Bu represents a tert-butyl group, and Flu represents a fluorenyl group.
Catalyst A: (t-BuNSiMe 2 Flu) TiMe 2
Cocatalyst A: 6.5% by mass (as Al atom content) MMAO-3A toluene solution ([(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n represented by n (A solution of isobutylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., containing 6 mol% of trimethylaluminum based on the total Al)
Cocatalyst B: 9.0% by mass (as Al atom content) TMAO-211 toluene solution (methylaluminoxane solution, manufactured by Tosoh Finechem Co., Ltd., containing 26 mol% of trimethylaluminum with respect to the total Al )
Cocatalyst C: Triisobutylaluminum Cocatalyst D: Dimethylanilium tetrakis (pentafluorophenyl) borate
Claims (5)
- チタノセン触媒の存在下で、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。 Polymerization in which at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer (B) derived from a C4 to C12 α-olefin are polymerized to obtain a copolymer in the presence of a titanocene catalyst. Including steps,
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. Production method. - 前記重合工程は、前記チタノセン触媒とともに、アルキルアルミノキサンからなる助触媒と連鎖移動剤との存在下で行われる、請求項1に記載の製造方法。 The production method according to claim 1, wherein the polymerization step is performed in the presence of a co-catalyst composed of an alkylaluminoxane and a chain transfer agent together with the titanocene catalyst.
- 前記連鎖移動剤は、アルキルアルミニウムである請求項2に記載の製造方法。 The method according to claim 2, wherein the chain transfer agent is an alkylaluminum.
- 前記アルキルアルミニウムは、トリメチルアルミニウムである請求項3に記載の製造方法。 The method according to claim 3, wherein the alkylaluminum is trimethylaluminum.
- 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から4のいずれか1項に記載の製造方法。 The glass transition temperature (Tg) of the copolymer is 170 ° C or higher, The production method according to any one of claims 1 to 4.
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WO2019026839A1 (en) * | 2017-08-01 | 2019-02-07 | ポリプラスチックス株式会社 | Copolymer and production method for copolymer |
JP2020007413A (en) * | 2018-07-04 | 2020-01-16 | ポリプラスチックス株式会社 | Method for testing catalytic activity of metallocene catalyst, method for producing catalyst composition for olefin monomer polymerization, and method for producing polymer |
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