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
  • 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
  • C08F32/00—Homopolymers and copolymers of cyclic compounds having 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
  • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F32/02—Homopolymers and copolymers of cyclic compounds having 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
  • C08F32/04—Homopolymers and copolymers of cyclic compounds having 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

Definitions

• the present invention relates to a method for producing a cyclic olefin polymer.
• Cyclic olefin polymers such as cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used in various applications including the field of optical materials such as optical disc substrates, optical films, and optical fibers. It is used.
• As a typical cyclic olefin copolymer there is a copolymer of cyclic olefin and ethylene widely used as a transparent resin.
• the glass transition temperature of the copolymer of cyclic olefin and ethylene can be changed according to the copolymer composition of cyclic olefin and ethylene. Therefore, it is possible to produce a copolymer whose glass transition temperature (Tg) is adjusted in a wide temperature range.
• a copolymer having a high Tg generally has good heat resistance (for example, see Non-Patent Document 1).
• copolymers of cyclic olefins and ethylene copolymers of cyclic olefins and ⁇ -olefins other than ethylene are known.
• a copolymer of cyclic olefin and ethylene has a good balance between heat resistance and mechanical properties.
• mechanical properties may be deteriorated.
• copolymerizing a cyclic olefin and an ⁇ -olefin other than ethylene it is possible to improve the balance between heat resistance and mechanical properties, which are issues with a copolymer of a cyclic olefin and ethylene.
• synthesis of a cyclic olefin polymer such as a cyclic olefin homopolymer and a cyclic olefin copolymer is generally performed using a catalyst typified by a metallocene-based transition metal catalyst.
• a metallocene-based transition metal catalyst Not only metallocene-based transition metal catalysts and half-metallocene-based transition metal catalysts but also metallocene-based transition metal catalysts are generally expensive, so reducing the amount of catalyst used reduces the cost of the entire production of the cyclic olefin polymer. Therefore, development of a catalyst that can produce a large amount of a cyclic olefin polymer with a small amount of a catalyst is an important issue.
• a method for synthesizing a cyclic olefin copolymer with a small amount of a catalyst at least a cyclic olefin monomer (A) derived from norbornene and a C4-C12 ⁇ -olefin are used in the presence of a metallocene-based transition metal catalyst.
• a method including a polymerization step of polymerizing an ⁇ -olefin monomer (B) to obtain a copolymer has been proposed (see Patent Documents 1 and 2).
• the present invention has been made in view of the above problems, and when a cyclic olefin polymer is produced using a transition metal complex catalyst such as a metallocene catalyst, the yield is expected to be consistent with the polymerization conditions, and is stable. It is an object of the present invention to provide a method for producing a cyclic olefin polymer, which can produce a cyclic olefin polymer by heating.
• the present inventors have proposed a method for producing a cyclic olefin polymer by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity in the presence of a transition metal catalyst.
• a hybrid adsorbent consisting of a mixture of alumina and zeolite
• epoxide impurities in the monomer are reduced, and as a result, the content of epoxide impurities in the total mass of the polymerization solution used for polymerization is reduced.
• the inventors have found that the above problem can be solved by setting the ratio (mass ppm / mass ppm) of the amount to the catalyst content to 6 or less, and completed the present invention. More specifically, the present invention provides the following.
• a method for producing a cyclic olefin polymer by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity, Contacting a crude norbornene-based compound containing epoxide impurities with an adsorbent to obtain a purified norbornene-based compound; Polymerizing a monomer containing a purified norbornene-based compound in the presence of a transition metal complex catalyst,
• the norbornene-based compound is composed of norbornene and the following formula (I): (Wherein, R 1 to R 12 may be the same or different and each is selected from the group consisting of a hydrogen atom, a halogen atom, and a saturated aliphatic hydrocarbon group, an aralkyl group, and an aromatic hydrocarbon group.
• At least one compound selected from the group consisting of substituted norbornenes represented by The epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond in 2,3-epoxynorbornane and / or the substituted norbornene represented by the formula (I) is oxidized
• the adsorbent is a hybrid adsorbent consisting of a mixture of activated alumina and zeolite, The ratio (mass ppm / mass ppm) of the content of the epoxide impurity and the content of the catalyst to the total mass of the polymerization solution used for the polymerization is 6 or less,
• the production method wherein the total mass of the polymerization solution is the total mass of the raw materials used for producing the cyclic olefin polymer.
• the ratio (mass ppm / mass ppm) of the content of the ketone impurity derived from the norbornene-based compound to the content of the catalyst relative to the total mass of the polymerization solution used for the polymerization is 2 or less, (1) Or the method for producing a cyclic olefin polymer according to (2).
• a cyclic olefin polymer when a cyclic olefin polymer is produced using a transition metal complex catalyst such as a metallocene catalyst, a cyclic olefin polymer can be produced stably with an expected yield suitable for the polymerization conditions.
• a method for making the polymer can be provided.
• a cyclic olefin polymer is produced by polymerizing a monomer containing a norbornene-based compound containing an epoxide impurity.
• the manufacturing method is Contacting a crude norbornene-based compound containing epoxide impurities with an adsorbent to obtain a purified norbornene-based compound; Polymerizing a monomer containing a purified norbornene-based compound in the presence of a transition metal complex catalyst.
• the amount of epoxide impurities in the monomer subjected to polymerization is significantly reduced by treating a crude norbornene-based compound with a specific adsorbent described below as an adsorbent to obtain a purified norbornene-based compound. can do.
• the ratio (mass ppm / mass ppm) of the content of the epoxide impurity and the content of the catalyst to the total mass of the polymerization solution used for the polymerization can be set to a low value of 6 or less.
• the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst in the polymerization solution used for the polymerization is equal to or less than the above-mentioned predetermined amount, a decrease in the activity of the transition metal complex catalyst is suppressed. It is considered that the cyclic olefin polymer can be stably produced at a desired yield.
• the “total mass of the polymerization solution used for the polymerization” is the total mass of the raw materials used for producing the cyclic olefin polymer.
• the “total mass of the polymerization solution used for polymerization” is the mass of “the monomer containing the purified norbornene-based compound”, the mass of “the transition metal complex catalyst”, and the catalyst together with the transition metal complex catalyst. It is the sum of the mass of the "promoter” and the mass of the "solvent” that constitute the composition.
• the mass of the other material is also included in the “total mass of the polymerization solution subjected to polymerization”.
• the norbornene-based compound contained in the monomer is at least one compound selected from the group consisting of norbornene and a substituted norbornene represented by the following formula (I).
• Such norbornene compounds correspond to monoene compounds.
• the monomer used for producing the cyclic olefin polymer contains an epoxide impurity derived from a norbornene-based compound.
• Epoxide impurities are generated by oxidation of norbornene-based compounds.
• the epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond in 2,3-epoxynorbornane and / or the substituted norbornene represented by the above formula (I) is oxidized.
• adsorbent used for the purification of the crude norbornene compound a hybrid adsorbent composed of a mixture of activated alumina and zeolite is used.
• epoxide impurities can be easily removed satisfactorily while preventing generation of impurities that may adversely affect the activity of the transition metal complex catalyst.
• the content of epoxide impurities in the monomer subjected to polymerization is preferably 200 ppm by mass or less based on the mass of the norbornene-based compound.
• obtaining a purified norbornene-based compound by bringing a crude norbornene-based compound containing an epoxide impurity into contact with an adsorbent is also referred to as a “purification step”.
• Polymerizing a monomer containing a purified norbornene-based compound in the presence of a transition metal complex catalyst is also referred to as a “polymerization step”.
• the steps included in the method for producing a cyclic olefin polymer will be described.
• ⁇ Purification process> In the purification step, a crude norbornene-based compound containing an epoxide impurity is brought into contact with an adsorbent to obtain a purified norbornene-based compound.
• the object of purification in the purification step is a crude monomer product containing a norbornene-based compound to be subjected to polymerization in the polymerization step described below. More specifically, at least a crude norbornene-based compound among the crude monomer products is purified.
• the crude norbornene-based compound is a norbornene-based compound that contains an epoxide impurity and has not been treated with an adsorbent described below.
• the norbornene-based compound is at least one compound selected from the group consisting of norbornene and substituted norbornene. As the norbornene-based compound, norbornene is preferable.
• the epoxide impurity is an epoxy compound in which the carbon-carbon unsaturated double bond in 2,3-epoxynorbornane and / or the substituted norbornene represented by the formula (I) is oxidized.
• the amount of the epoxide impurity in the crude norbornene-based compound is determined by the ratio (mass ppm / mass ppm) of the content of the epoxide impurity and the content of the catalyst to the total mass of the polymerization solution to be subjected to the polymerization by the purification using the adsorbent. There is no particular limitation as long as it can be reduced to 6 or less.
• the amount of the epoxide impurity in the crude norbornene-based compound is 200 mass ppm or more, 300 mass ppm or more, or 500 mass ppm or more with respect to the mass of the norbornene-based compound. It may be 1500 ppm by mass or more.
• the amount of the epoxide impurity in the crude norbornene-based compound is preferably 5000 mass ppm or less, more preferably 3000 mass ppm or less, or 2000 mass ppm or less in that the crude norbornene-based compound is easily purified. .
• R 1 to R 12 in the 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. These may be different from each other, may be partially different, or may be all 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, a tolyl group; Substituted or unsubstituted aromatic hydrocarbon groups such as an ethylphenyl group, an isopropylphenyl group, a naphthyl group, and an anthryl group; a benzyl group, a 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 may be all the same.
• a halogen atom such as fluorine, chlorine, and bromine
• a cycloalkyl group such as a
• the formed ring may be a monocyclic or polycyclic ring, or may be a cross-linked polycyclic ring. Alternatively, the ring may be a combination of these rings. These rings may have a substituent such as a methyl group.
• the saturated aliphatic hydrocarbon ring that can be formed by bonding two groups selected from R 9 to R 12 to each other include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
• the aromatic hydrocarbon ring which can be formed by combining two groups selected from R 9 to R 12 include a benzene ring and a naphthalene ring.
• substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hepta-2-ene and 5,5-dimethyl-bicyclo [2.2.1] hepta- 2-ene, 5-ethyl-bicyclo [2.2.1] hepta-2-ene, 5-butyl-bicyclo [2.2.1] hepta-2-ene, 5-hexyl-bicyclo [2.2.
• Bicyclic cyclic olefins such as hepta-2-ene, 5-octyl-bicyclo [2.2.1] hepta-2-ene and 5-octadecyl-bicyclo [2.2.1] hepta-2-ene ; Tricyclo [4.3.0.1 2,5 ] dec-3-ene; 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.
• tricyclic olefins such as hepta-2-ene; 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] dodeca-3-ene, 8-ethyl tetracyclo [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 .
• alkyl-substituted norbornenes for example, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornenes are preferable.
• the crude norbornene-based compound may be brought into contact with the adsorbent alone.
• the monomer contains a monomer other than the norbornene-based compound together with the norbornene-based compound, a mixture containing the crude norbornene-based compound and another monomer may be brought into contact with the adsorbent.
• the other monomer is not particularly limited as long as it is a monomer compound copolymerizable with the norbornene-based compound, and is typically an ⁇ -olefin.
• the ⁇ -olefin may be substituted with at least one substituent such as a halogen atom.
• ⁇ -olefins are preferably C2-C12 ⁇ -olefins.
• the ⁇ -olefin of C2 to C12 is not particularly limited.
• 1-hexene, 1-octene and 1-decene are preferred.
• the monomer preferably contains, together with the norbornene-based compound, at least one selected from the group consisting of ethylene, 1-hexene, and 1-octene. More preferably, the monomer comprises a norbornene-based compound and at least one selected from the group consisting of ethylene, 1-hexene, and 1-octene.
• the amount of norbornene in the monomer should be 30 mol% or more and less than 70 mol% in order to obtain a cyclic olefin polymer having a good balance between mechanical properties and thermal properties. preferable.
• norbornene is used in combination with 1-octene, 1-hexene, or a mixture thereof, a cyclic olefin having good mechanical properties is easily obtained, so that the glass transition temperature of the cyclic olefin polymer can be increased.
• the amount of norbornene in the monomer is preferably at least 70 mol%.
• adsorbent By contacting the crude norbornene-based compound contained in the monomer described above, a treatment for reducing epoxide impurities contained in the crude norbornene-based compound is performed.
• a hybrid adsorbent composed of a mixture of activated alumina and zeolite is used.
• the hybrid adsorbent is typically in powder or pellet form, preferably in pellet form.
• the activated alumina site and the zeolite site are inseparably complexed in the particles constituting the powder or the pellet.
• the hybrid adsorbent has both adsorption sites as activated alumina and adsorption sites as zeolite in the same particle.
• the hybrid adsorbent may be a mixture of activated alumina in powder or pellet form and zeolite in powder or pellet form as long as desired adsorption hardening for epoxide impurities is obtained.
• the activated alumina portion and the hybrid adsorbent in which the zeolite portion is inseparably compounded are powdered or pelletized activated alumina and powdered or pelletized zeolite mixed.
• the adsorption performance of the epoxide impurity and the below-described ketone impurity and aldehyde impurity is better than that of the mixture.
• the content of activated alumina and the content of zeolite are preferably 20% by mass or more and 80% by mass or less, respectively, based on the sum of the mass of activated alumina and the mass of zeolite. , 30% by mass or more and 70% by mass or less.
• hybrid adsorbents can be used as the hybrid adsorbent.
• a commercially available product may be used.
• Examples of commercially available hybrid adsorbents include, for example, AZ-300 (manufactured by UOP or Union Showa). In the commercial product AZ-300, the activated alumina site and the zeolite site are inseparably compounded.
• Activated alumina is porous aluminum oxide particles having an adsorption ability.
• Activated aluminum can be produced by transferring alumina hydroxide to porous aluminum oxide with low crystallinity.
• the pore diameter of the activated alumina site in the hybrid adsorbent is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 80 nm or less from the viewpoint of the ability to adsorb epoxide impurities.
• the pore diameter of the zeolite site in the hybrid adsorbent is preferably 0.2 nm or more and 1 nm or less, more preferably 0.5 nm or more and 1 nm or less from the viewpoint of the ability to adsorb epoxide impurities.
• Preferred zeolites include zeolite X, zeolite Y, and zeolite A. Among these, zeolite X is preferred.
• the shape of the hybrid adsorbent is not particularly limited, and is preferably a pellet as described above.
• the shape of the pellet is not particularly limited.
• the shape of the pellet of the agent is preferably spherical or substantially spherical.
• the hybrid adsorbent Before the hybrid adsorbent is used in the purification step, the hybrid adsorbent may be subjected to an activation treatment by heating for the purpose of increasing the adsorbing ability or the like.
• the activation treatment is usually performed under an inert gas atmosphere.
• the heating temperature in the activation treatment is preferably from 100 ° C to 650 ° C, more preferably from 200 ° C to 600 ° C, further preferably from 300 ° C to 600 ° C, particularly preferably from 400 ° C to 600 ° C.
• the heating time is preferably from 0.1 to 100 hours, more preferably from 0.5 to 50 hours, even more preferably from 1 to 25 hours.
• the entire amount of the crude norbornene-based compound used for producing the cyclic olefin polymer may be subjected to treatment with the adsorbent, and a part of the crude norbornene-based compound used for producing the cyclic olefin polymer is treated with the adsorbent. May be provided.
• the purified norbornene-based compound and the remaining crude norbornene-based compound not treated with the adsorbent are mixed and subjected to polymerization.
• Crude norbornene-based compound treated with an adsorbent as long as a polymerization solution having a ratio (mass ppm / mass ppm) of the epoxide impurity content to the catalyst content to the total mass of the polymerization solution (mass ppm / mass ppm) of 6 or less can be prepared. Is not particularly limited. Since the amount of the epoxide impurity in the monomer subjected to the polymerization is easily reduced to a desired amount or less, it is preferable that the entire amount of the crude norbornene-based compound used in the production of the cyclic olefin polymer is subjected to the treatment with the adsorbent. .
• the crude norbornene-based compound usually comes in contact with the adsorbent in a liquid state.
• a liquid may be a melt of a crude norbornene-based compound or a mixture containing a crude norbornene-based compound and another monomer, and may be a crude norbornene-based compound or a crude norbornene-based compound and another monomer. May be dissolved in a solvent.
• the kind of the solvent for dissolving the crude norbornene-based compound or the crude norbornene-based compound and another monomer is not particularly limited as long as the adsorption of the epoxide impurity by the adsorbent is not hindered.
• Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane, and chlorobenzene. .
• the concentration of the crude norbornene-based compound in the solution or the melt is not particularly limited.
• the concentration of the crude norbornene-based compound in the solution or the melt is preferably from 1% by mass to 100% by mass, more preferably from 10% by mass to 100% by mass.
• the contact between the crude norbornene-based compound and the adsorbent may be performed by a batch method or a continuous method.
• the method for bringing the crude norbornene-based compound into contact with the adsorbent is not particularly limited. For example, after charging a liquid containing a crude norbornene-based compound and an adsorbent in a container, the liquid containing the crude norbornene-based compound in the container, and the adsorbent are allowed to stand or stir for a predetermined time. You may.
• the contact between the crude norbornene compound and the adsorbent under stirring is preferable in that the contact efficiency between the two is good.
• the contact between the crude norbornene-based compound and the adsorbent under standing is preferable in that it is easy to prevent impurities derived from the adsorbent from being mixed into the monomer and the cyclic olefin polymer due to abrasion of the adsorbent or the like.
• a liquid containing a crude norbornene-based compound may be passed through a container such as a column filled with an adsorbent.
• a circulating treatment is performed in which the liquid containing the crude norbornene-based compound that has flowed out of the vessel such as the column is again flowed into the vessel such as the column. You may.
• the contact time between the crude norbornene-based compound and the adsorbent is preferably 0.01 hours or more and 50 hours or less, from the viewpoint of achieving a balance between a large treatment amount of the crude norbornene-based compound and a high removal efficiency of epoxide impurities. 1 hour or more and 40 hours or less, more preferably 1 hour or more and 30 hours or less.
• the amount of the adsorbent is preferably not less than 1 part by mass, more preferably not less than 10 parts by mass, and more preferably not less than 20 parts by mass with respect to 100 parts by mass of the crude norbornene-based compound, from the viewpoint of easy removal of the epoxide impurity part. More preferred.
• the upper limit of the amount of the adsorbent is not particularly limited, but is preferably 80 parts by mass or less based on 100 parts by mass of the crude norbornene-based compound from the viewpoint of suppressing the cost of the adsorbent and not requiring an excessively large apparatus for the purification treatment. , 60 parts by mass or less, more preferably 40 parts by mass or less.
• the content of aldehyde impurities derived from the norbornene-based compound in the monomer subjected to polymerization is preferably 50 mass ppm or less, more preferably 30 mass ppm or less, based on the mass of the norbornene-based compound. It is more preferably at most 20 mass ppm.
• the content of ketone impurities derived from the norbornene-based compound in the monomer subjected to polymerization is preferably 50 mass ppm or less, more preferably 30 mass ppm or less, based on the mass of the norbornene-based compound. It is more preferably at most 20 mass ppm.
• the aldehyde impurity and the ketone impurity are impurities that can be generated due to oxidation of the norbornene-based compound. There is a possibility that these impurities may be factors in lowering the polymerization yield when producing a cyclic olefin polymer.
• the method for reducing the aldehyde impurity amount and the ketone impurity amount is not particularly limited.
• the amount of aldehyde impurities and the amount of ketone impurities contained in the purified norbornene-based compound tend to be low.
• the amounts of aldehyde impurities and ketone impurities can be reduced.
• the purified norbornene-based compound obtained by performing the treatment described above is then provided to a “polymerization step”.
• the purified norbornene-based compound is a solution
• the purified norbornene-based compound may be subjected to the polymerization step as it is, or may be subjected to the polymerization step in a state of being isolated from the solution.
• a monomer containing the purified norbornene-based compound obtained in the above purification step is polymerized in the presence of a transition metal complex catalyst to produce a cyclic olefin polymer.
• the monomer may be supplied all at once in the polymerization apparatus, may be supplied in several divided portions, or may be supplied continuously.
• the method of the polymerization reaction is not particularly limited, and may be a batch type or a continuous type.
• the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst relative to the total mass of the polymerization solution is 6 or less, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. It is adjusted as follows. By the ratio of the content of the epoxide impurity and the content of the catalyst to the total mass of the polymerization solution provided to the polymer is within the above range, in a yield expected according to the polymerization conditions, stably Cyclic olefin polymers can be produced.
• the lower limit of the ratio between the content of the epoxide impurity and the content of the catalyst relative to the total mass in the polymerization solution is not particularly limited, but may be 0.1 or more, and may be 1 or more from the viewpoint of easiness of the purification operation. May be.
• the polymerization reaction in the polymerization step may be living polymerization or non-living polymerization.
• non-living polymerization which is a chain polymerization in which a chain transfer reaction is intentionally repeated repeatedly, is generally preferred.
• the chain transfer agent is not particularly limited, and a known compound having a chain transfer ability can be used.
• Typical chain transfer agents generally include alkyl aluminum compounds, alkyl zinc compounds or hydrogen.
• the alkylaluminum compound may be contained in the aluminoxane, or may be appropriately added.
• Whether the polymerization has proceeded by non-living polymerization or living polymerization can be determined by the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the obtained polymer.
• Mw weight average molecular weight
• Mn number average molecular weight
• a polymer having a molecular weight distribution of 1.1 or less is produced by living polymerization, and a polymer having a molecular weight distribution of more than 1.1 is produced by non-living polymerization.
• the molecular weight distribution often exceeds 1.5 and is about 2.
• transition metal complex catalyst is not particularly limited as long as it can catalyze a polymerization reaction of a monomer containing a norbornene-based compound.
• Preferred transition metal complex catalysts include metallocene catalysts.
• the metallocene catalyst (a) for example, a transition metal complex containing a ligand containing a cyclopentadiene ring and a transition metal of Group IV of the periodic table is preferable.
• the metallocene catalyst (a) preferably contains a metal atom selected from the group consisting of Ti, Zr, and Hf as a central metal.
• a transition metal complex represented by the following formula (1) is preferable. (Cp) (ZR 01 m ) n (A) r ML p L ′ q (1)
• (ZR 01 m ) n is a divalent group that binds Cp and A.
• Z is C, Si, Ge, N, or P.
• R 01 is a hydrogen atom, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a linear group.
• An aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be branched or may have a cyclic skeleton and may have an unsaturated bond.
• the plurality of R 01 may be the same or different.
• Cp is a cyclopentadienyl group which may have a substituent or a cyclic group containing a cyclopentadiene ring which may have a substituent.
• A is the same group as Cp, or is -O-, -S-, or -N (R 02 )-.
• R 02 is a hydrogen atom, a linear or branched chain, or may have a cyclic skeleton, and may have an unsaturated bond and has 1 to 20 carbon atoms.
• M is a metal atom selected from the group consisting of Ti, Zr, and Hf.
• L represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a branched chain even if linear.
• L may include one or more Si atoms or Ge atoms. When L is plural, plural Ls may be the same or different, and are preferably the same.
• R 03 is a hydrogen atom, a heteroatom-containing aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a cyclic skeleton, may have a cyclic skeleton, and may have an unsaturated bond.
• R 03 When a plurality of R 03 are present, they may be the same or different.
• the plurality of L's may be the same or different.
• m is 1 or 2. More specifically, when Z is N or P, m is 1, and when Z is C, Si, or Ge, m is 2.
• n is an integer of 0 or more and 4 or less.
• r is 0 or 1.
• n is 0.
• p is an integer of 0 or more and 3 or less.
• q is an integer of 0 or more and 3 or less.
• p + q is equal to the oxidation state of the metal M minus 2 (the oxidation state of the metal M-2) when r is 1.
• p + q is equal to the oxidation state of the metal M minus 1 (the oxidation state of the metal M-1) when r is 0.
• p + q is less than 4.
• the divalent crosslinking group is more preferably Si (CH 3 ) 2 , SiPh 2 , CH 2 , (CH 2 ) 2 , (CH 2 ) 3 , C (CH 3 ) 2 , or CPh 2 .
• Ph is a phenyl group.
• m is 1 or 2
• n is an integer of 0 or more and 4 or less.
• the ligand Cp that ⁇ -bonds to the metal M is a cyclopentadienyl group that may have a substituent or a cyclic group that includes a cyclopentadiene ring that may have a substituent.
• Cp include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, and 4-tert-butylcyclopentane.
• A is the same group as Cp, or is -O-, -S-, or -N (R 02 )-.
• A is preferably the same group as Cp.
• the metal M is Ti, Zr or Hf.
• L is preferably a group selected from the group consisting of a methyl group, an ethyl group, an n-butyl group, a sec-butyl group, a phenyl group, a benzyl group, and —CH 2 Si (CH 3 ) 3 .
• a methyl group is more preferred.
• N is an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less.
• transition metal complex represented by the formula (1) when n is 0 and r is 0, specific examples include CpdMCl 2 (O-2,6- (t-Bu) 2 -C 6 H 3 ), CpdMMe 2 (O-2,6- (t-Bu) 2 -C 6 H 3 ), CpdMMeCl (O-2,6- (t-Bu) 2 -C 6 H 3 ), tet-CpdMCl 2 (O-2,6- (t-Bu) 2 -C 6 H 3 ), tet-CpdMMe 2 (O-2,6- (t-Bu) 2 -C 6 H 3 ), tet-CpdMMeCl (O- 2,6- (t-Bu) 2 -C 6 H 3 ), CpdMCl 2 (O-2,6- (i-Pr) 2 -C 6 H 3 ), CpdMMe 2 (O-2,6- (i -Pr) 2 -C 6 H 3)
• Me is a methyl group
• t-Bu is a tert-butyl group
• i-Pr is an iso-propyl group
• Cpd is a cyclopentadienyl group
• tet-Cpd is tetramethyl A cyclopentadienyl group.
• M is as described for equation (1).
• Zr, Ti, or Hf is preferable, and Ti is more preferable.
• n is 0, specific examples of when r is 1, (Me 3 Cpd) 2 MCl 2, (Me 3 Cpd) 2 MMe 2, ( Me 3 Cpd) 2 MMeCl, ( Me 3 Cpd) 2 MPh 2, (Me 3 Cpd) 2 MBz 2, (Me 4 Cpd) 2 MCl 2, (Me 4 Cpd) 2 MMe 2, (Me 5 Cpd) 2 MCl 2, (Me 5 Cpd) 2 MPh 2, (Me 5 Cpd) 2 MBz 2, (EtMe 4 Cpd) 2 MCl 2, [(Ph) Me 4 Cpd] 2 MCl 2, (Et 5 Cpd) 2 MCl 2, (Ind) 2 MCl 2 , (Ind) 2 MMeCl, (Ind) 2 MPh 2 , (Ind) 2 MMe 2 , (Ind) 2 MMeCl, (H 4 Ind) 2
• Me is a methyl group
• Et is an ethyl group
• Cpd is a cyclopentadienyl group
• Ind is an indenyl group
• H 4 Ind is 4,5,6,7, -tetrahydro It is an indenyl group
• Ph is a phenyl group
• Bz is a benzyl group.
• M is as described for equation (1). As M, Zr, Ti, or Hf is preferable, and Zr is more preferable.
• transition metal complex represented by the formula (1) when n is 1 or 2 and r is 1, specific examples include Me 2 C (Cp) (Ind) MCl 2 and Me 2 C (Cp ) (Ind) MMe 2 , Me 2 C (Cp) (Ind) MPh 2 , Me 2 C (Cp) (Ind) MBz 2 , Me 2 C (Cp) (Ind) MMeCl, Ph 2 C (Cp) (Ind) ) MCl 2 , Ph 2 C (Cp) (Ind) MMe 2 , Ph 2 C (Cp) (Ind) MPh 2 , Ph 2 C (Cp) (Ind) MBz 2 , Ph 2 C (Cp) (Ind) MMeCl , Me 2 Si (Me 4 Cpd) 2 MCl 2 , Me 2 Si (Me 4 Cpd) 2 MMe 2 , Me 2 Si (Me 4 Cpd) 2 MPh 2 , Me 2 Si (Me 4
• Me is a methyl group
• Cpd is a cyclopentadienyl group
• tet-Cpd is a tetramethylcyclopentadienyl group
• Ind is an indenyl group
• H 4 Ind is 4,5 , 6,7, -tetrahydroindenyl group
• Flu is a fluorenyl group
• Ph is a phenyl group
• Bz is a benzyl group.
• M is as described for equation (1).
• Zr, Ti, or Hf is preferable, and Zr is more preferable.
• Me 2 C (Flu) (Cpd) ZrCl 2 , Me 2 C (Flu) (Cpd) ZrMe 2 , Me 2 C (Flu) ( Cpd) ZrPh 2 , Me 2 C (Flu) (Cpd) ZrBz 2 , Ph 2 C (Flu) (Cpd) ZrCl 2 , Ph 2 C (Flu) (Cpd) ZrMe 2 , Ph 2 C (Flu) (Cpd) ZrPh 2 and Ph 2 C (Flu) (Cpd) ZrBz 2 are preferably used for copolymerization of a norbornene-based compound described below with ethylene, and more preferably used for copolymerization of norbornene and ethylene.
• metallocene compound represented by the formula (1) examples include a compound represented by the following formula (a1).
• R a1 , R a2 , R a3 , and R a4 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
• R a1 and R a2 are each bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond.
• Ra3 binds to a nitrogen atom by a CN bond, an ON bond, a Si-N bond, or an NN bond.
• R a5 and R a6 are each independently an organic substituent having 1 to 20 carbon atoms or an inorganic substituent which may contain a hetero atom, and p and q are each independently 0 or more and 4 or less. Is an integer. When each of R a5 and R a6 is plural, the plurality of R a5 and R a6 may be different groups. When two of the plurality of R a5 , or two of the plurality of R a6 are bonded to adjacent positions on the aromatic ring, the two groups are bonded to each other to form a ring; Is also good.
• M is a Group IV transition metal of the periodic table, and is preferably Ti, Zr, or Hf.
• the metal atom M in the formula (a1) can take an arbitrary coordination form with a ligand having a fluorene skeleton in a range of 1 to 5 hapto number.
• R a1 , R a2 , R a3 , and R a4 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
• the type of the hetero atom is not particularly limited as long as the object of the present invention is not hindered.
• Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a halogen atom.
• R a1 and R a2 are each bonded to a silicon atom by a C—Si bond, an O—Si bond, a Si—Si bond, or an N—Si bond.
• R a1 and R a2 bonded to the silicon atom by Si-Si bonds, -SiR a7 3, -Si (OR a7) R a7 2, -Si (OR a7) 2 R a7, and -Si A group represented by ( ORa7 ) 3 ;
• each of the above Ra7 is a hydrocarbon group.
• Ra3 binds to a nitrogen atom by a CN bond, an ON bond, a Si-N bond, or an NN bond.
• each of the above Ra7 is a hydrocarbon group.
• R a1 and R a2 are the same group because the compound to be used as a ligand can be easily prepared and obtained.
• a hydrocarbon group containing no hetero atom is preferable because of excellent chemical stability.
• examples of such a hydrocarbon group include a linear or branched alkyl group, a linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond, and cycloalkyl.
• Groups, cycloalkylalkyl groups, aromatic hydrocarbon groups, and aralkyl groups are preferred.
• linear or branched alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group , N-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl groups.
• Preferred examples of the linear or branched unsaturated aliphatic hydrocarbon group which may have a double bond and / or a triple bond include specific examples of a linear or branched alkyl group. And a group in which one or more single bonds are replaced with a double bond and / or a triple bond. More preferred are a vinyl group, an allyl group, a 1-propenyl group, a 3-butenyl group, a 2-butenyl group, a 1-butenyl group, an ethenyl group, and a propargyl group.
• cycloalkyl group examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, Cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl, and cycloicosyl groups.
• cycloalkylalkyl group examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, and a cyclounyl group.
• Decylmethyl group cyclododecylmethyl group, cyclotridecylmethyl group, cyclotetradecylmethyl group, cyclopentadecylmethyl group, cyclohexadecylmethyl group, cycloheptadecylmethyl group, cyclooctadecylmethyl group, cyclononadecylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2 Cyclodecylethyl group, 2-cycloundecylethyl group, 2-cyclododecylethyl group, 2-cyclotridecylethyl group, 2-cyclotetradecylethyl group, 2-cyclopen
• aromatic hydrocarbon group examples include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethyl Phenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 2,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butyl
• aralkyl group examples include benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 2-phenylpropyl, 1-phenylpropyl, 2-phenyl-1-methylethyl, Phenyl-1-methylethyl group (cumyl group), 4-phenylbutyl group, 3-phenylbutyl group, 2-phenylbutyl group, 1-phenylbutyl group, 3-phenyl-2-methylpropyl group, 3-phenyl- 1-methylpropyl group, 2-phenyl-1-methylpropyl group, 2-methyl-1-phenylpropyl group, 2-phenyl-1,1-dimethylethyl group, 2-phenyl-2,2-dimethylethyl group, ⁇ -naphthylmethyl group, ⁇ -naphthylmethyl group, 2- ⁇ -naphthylethyl group, 2- ⁇ -naphthylethyl group
• an alkyl group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferable, and an alkyl group having 1 to 10 carbon atoms and a carbon atom number are preferable.
• An aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms and a phenyl group are further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
• an alkyl group having 1 to 20 carbon atoms a cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom having 7 to 20 carbon atoms. are preferred.
• Ra4 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aromatic carbon group having 6 to 20 carbon atoms.
• a hydrogen group and an aralkyl group having 7 to 20 carbon atoms are preferred.
• R a5 and R a6 are each independently an organic substituent having 1 to 20 carbon atoms or an inorganic substituent which may contain a hetero atom, and p and q are respectively It is independently an integer of 0 or more and 4 or less. When each of R a5 and R a6 is plural, the plurality of R a5 and R a6 may be different groups.
• Examples of the organic substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 2 to 20 carbon atoms.
• Examples thereof include an aliphatic acyl group, a benzoyl group, an ⁇ -naphthylcarbonyl group, a ⁇ -naphthylcarbonyl group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
• an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 2 to 6 carbon atoms are preferably an aliphatic acyl group, a benzoyl group, a phenyl group, a benzyl group, and a phenethyl group.
• the inorganic substituent is not particularly limited as long as it is an inorganic group which is conventionally known to be capable of substituting on an aromatic ring and does not inhibit the reaction of forming the metallocene compound represented by the above formula (a1). .
• Specific examples of the inorganic group include a halogen atom, a nitro group, and a cyano group.
• Such a ring is a condensed ring condensed with the aromatic ring contained in the fluorene skeleton in the formula (a1).
• the condensed ring may be an aromatic ring or an aliphatic ring, preferably an aliphatic ring.
• the condensed ring may have a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom in the ring.
• fluorene skeleton having a fused ring formed by two R a5 and / or two R a6 include a skeleton represented by the following formula.
• M is a transition metal of Group IV of the periodic table, preferably Ti, Zr, or Hf, and more preferably Ti.
• metallocene compound represented by the formula (a1) described above include a metallocene compound having the following structure.
• the metallocene compound represented by the above formula (a1) is preferably used for homopolymerization of a norbornene-based compound or copolymerization of a norbornene-based compound with 1-octene, 1-hexene, or a mixture thereof. And 1-octene, 1-hexene, or a mixture thereof.
• the solvent contained in the solution is not particularly limited.
• Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane, and chlorobenzene.
• the concentration of the metallocene catalyst (a) in the solution of the metallocene catalyst (a) is not particularly limited.
• the concentration of the metallocene catalyst (a) is, for example, preferably from 0.1 mmol / L to 0.5 mol / L, more preferably from 1 mmol / L to 0.25 mol / L.
• the metallocene catalyst (a) described above is preferably used as a catalyst composition as described below.
• the catalyst composition is typically produced by a method of mixing a solution of the metallocene catalyst (a) with at least one selected from the group consisting of aluminoxanes (b1) and ionic compounds (b2).
• the ionic compound (b2) is a compound that generates a cationic transition metal compound by reacting with the metallocene catalyst (a).
• the mixture of the solution of the metallocene catalyst (a) and one or more selected from the group consisting of the aluminoxane (b1) and the ionic compound (b2) for preparing the catalyst composition includes a polymerization reaction before the polymerization.
• the reaction may be performed in a separate device from the tank, or in the polymerization reaction tank before the polymerization or during the polymerization.
• aluminoxane (b1) As the aluminoxane (b1), various aluminoxanes conventionally used as cocatalysts in the polymerization of various olefins can be used without particular limitation. Typically, the aluminoxane is an organic aluminoxane. In the production of the catalyst composition, one type of aluminoxane (b1) may be used alone, or two or more types may be used in combination.
• an alkylaluminoxane is preferably used.
• the alkylaluminoxane include a compound represented by the following formula (b1-1) or (b1-2).
• the alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting a trialkylaluminum with 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 obtained by substituting a part of the methyl group of methylaluminoxane 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.
• Modified methylaluminoxane in which a part of the group is substituted with an isobutyl group is more preferred.
• alkylaluminoxane examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferable.
• the alkylaluminoxane can be prepared by a known method.
• a commercially available product may be used as the alkylaluminoxane.
• Commercially available alkylaluminoxanes include, for example, MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by Tosoh Finechem Co., Ltd.) and methylaluminoxane solution (Albemarle).
• the ionic compound (b2) is a compound that generates a cationic transition metal compound by reacting with the metallocene catalyst (a).
• examples of such an ionic compound include an anion of tetrakis (pentafluorophenyl) borate, an amine cation having an active proton such as (CH 3 ) 2 N (C 6 H 5 ) H + , and (C 6 H 5 ) 3 C +
• An ionic compound such as a trisubstituted carbonium cation, a carborane cation, a metal carborane cation, and a ferrocenium cation having a transition metal can be used.
• solvent The metallocene catalyst (a), aluminoxane (b1), and ionic compound (b2) described above are usually used in a state of being dissolved or suspended, preferably dissolved in a solvent.
• the type of the solvent is not particularly limited as long as the object of the present invention is not hindered.
• Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloroethane, and chlorobenzene. .
• the amount of the solvent used is not particularly limited as long as a catalyst composition having desired performance can be produced.
• the concentrations of the metallocene catalyst (a), the aluminoxane (b1), and the ionic compound (b2) are preferably 0.00000001 to 100 mol / L, more preferably 0.00000005 to 50 mol / L, and particularly preferably.
• An amount of solvent that is between 0.0000001 and 20 mol / L is used.
• the number of moles of transition metal elements in the metallocene catalyst (a) and M a, the number of moles of aluminum in the aluminoxane (b1) and M b1, ionic compounds (b2 the number of moles in the case of the M b2) of, as is (M b1 + M b2) / value of M a is preferably 1 to 200000 and more preferably 100 to 100,000, particularly preferably 1,000 to 80,000, catalyst It is preferable that liquids containing the raw materials of the composition are mixed.
• the temperature at which the liquid containing the raw material for the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100 ° C, more preferably -50 to 50 ° C.
• the polymerization conditions are not particularly limited as long as a desired cyclic olefin polymer is obtained, and known conditions can be used.
• the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted.
• the amount of each monomer component used is exemplified as follows.
• the addition amount of the other monomer to 1 mol of the norbornene-based compound is preferably from 0.001 mol to 30 mol, and more preferably from 0.01 mol to 20 mol.
• the amount of the catalyst composition used is derived from the amount of the transition metal complex catalyst used for its preparation.
• the amount of the catalyst composition used is preferably 0.00000001 mol or more and 0.005 mol or less, more preferably 0.0000000001 mol or more and 0.005 mol or less per 1 mol of the norbornene-based compound, as the amount of the transition metal complex catalyst used for the preparation. It is more preferably at most 0005 mol.
• the polymerization temperature is not particularly limited as long as the polymerization reaction proceeds at a desired rate.
• the polymerization temperature is typically from 0 ° C to 120 ° C, preferably from 10 ° C to 100 ° C, more preferably from 20 ° C to 90 ° C.
• the polymerization time is not particularly limited, and the polymerization is carried out until the desired yield is reached or the molecular weight of the polymer increases to a desired degree.
• the polymerization time varies depending on the temperature, the composition of the catalyst composition, and the monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and is preferably 0 to 80 hours. 2 hours or more and 10 hours or less are more preferable.
• the norbornene-based compound, or the polymerization system containing the norbornene-based compound and other monomers before adding the catalyst composition, aluminoxane, and alkyl aluminum
• one or more selected from compounds are present.
• the aluminoxane is as described in the method for producing the catalyst composition.
• the alkylaluminum compound those conventionally used for polymerization of olefins and the like can be used without particular limitation.
• the alkyl aluminum compound include a compound represented by the following general formula (II). (R 10 ) z AlX 3-z (II) (In the formula (II), 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 is there.)
• 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 compound examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and trin-octylaluminum; dimethylaluminum chloride; Dialkylaluminum halides such as diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.
• trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and trin-octylaluminum
• the alkyl aluminum compound acts as a chain transfer agent and promotes the chain polymerization catalyzed by the above-mentioned catalyst composition.
• the amount used when adding aluminoxane to the polymerization system is preferably from 10 mol to 1,000,000 mol, more preferably from 100 mol to 100,000 mol, as the number of mols of aluminum in the aluminoxane per mol of the transition metal complex catalyst. The following is more preferred.
• the amount used when the alkylaluminum compound is added to the polymerization system is preferably from 5 mol to 500,000 mol, and more preferably from 50 mol to 50,000 mol, as the number of mols of aluminum per mol of the transition metal complex catalyst. Is more preferred.
• At least a part, preferably all of the catalyst composition is continuously added to the polymerization system.
• continuously adding the catalyst composition continuous production of the cyclic olefin polymer becomes possible, and the production cost of the cyclic olefin polymer can be reduced.
• a crude norbornene-based compound containing an epoxide impurity is treated with a hybrid adsorbent composed of a mixture of activated alumina and zeolite to reduce epoxide impurities in a monomer.
• a hybrid adsorbent composed of a mixture of activated alumina and zeolite to reduce epoxide impurities in a monomer.
• the ratio (mass ppm / mass ppm) of the content of the epoxide impurity to the content of the catalyst with respect to the total mass of the polymerization solution to be subjected to the polymerization is set to 6 or less, whereby the expectation meeting the polymerization conditions is obtained. It is possible to stably produce a cyclic olefin polymer at a given yield.
• Examples 1 to 3 Comparative Example 1, Comparative Example 2, and Reference Example 1
• the epoxide impurity was 2,3-epoxynorbornane.
• the norbornene-based compound was norbornene.
• the contents of the glass container were allowed to stand at room temperature for 24 hours to perform an epoxide impurity adsorption treatment.
• adsorbents shown in Table 1 are as follows.
• AB1 Hybrid adsorbent composed of activated alumina and zeolite (AZ-300, manufactured by Union Showa)
• AB2 Molecular sieve (MS-4A)
• the impurities described in Table 1 are as follows.
• EP epoxide impurity (2,3-epoxynorbornane)
• AL aldehyde impurity derived from norbornene
• KE ketone impurity derived from norbornene
• the amount of impurities shown in Table 1 before the treatment with the adsorbent is the amount (ppm by mass) of each impurity with respect to the mass of the norbornene compound in the toluene solution of the norbornene compound.
• the amount (mass ppm) of each impurity relative to the mass of the norbornene-based compound in the toluene solution of the norbornene-based compound was measured using the following apparatus under the following conditions.
• Measurement mode Scan method Solvent waiting time: 5.5 min Scan range 15 to 650 m / z Ion source temperature: 230 ° C Quad temperature: 150 ° C
• Qualitative method Measure EP standard sample and judge from retention time and MS spectrum.
• Quantitative method A calibration curve was prepared from the EP standard sample and quantified. AL and KE were also quantified from the EP calibration curve, assuming that the sensitivity was about the same as the EP sensitivity.
• a toluene solution of a metallocene catalyst having a concentration of 7.3 mmol / L was prepared.
• the structure of the metallocene catalyst is as follows. Then, using a toluene solution of the metallocene catalyst, norbornene (2-norbornene) and 1-hexene were copolymerized according to the following method.
• a mixture of 2-norbornene and 1-hexene was added as a toluene solution having a concentration of 54% by mass to a dry 200 mL two-necked glass reactor kept under a nitrogen atmosphere.
• the molar ratio of the mixture was 36/64 as 2-norbornene / 1-hexene.
• MMAO-3A and TMAO-211 were added to the glass reactor so that the molar ratio of MMAO-3A / metallocene catalyst became 1250 and that of TMAO-211 / metallocene catalyst became 1100, respectively.
• polymerization was started by adding a toluene solution of a metallocene catalyst into the glass reactor.
• EP AL in a “polymerization solution” comprising 2-norbornene and 1-hexene as monomers, toluene as a solvent, two types of MAO as cocatalysts, and a metallocene catalyst.
• KE content ppm by mass
• the impurity content / catalyst content ratio (mass ppm / mass ppm) in the polymerization solution was determined based on the calculated value of the content (mass ppm) of the metallocene catalyst in the “polymerization solution”.
• Table 1 shows the ratio of impurity content / catalyst content (ppm by mass / ppm by mass) in the polymerization solution.
• MMAO-3A is a toluene containing methylisobutylaluminoxane represented by [(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n at an Al atom content of 6.5% by mass.
• Solution manufactured by Tosoh Finechem Co., Ltd.
• TMAO-211 is a toluene solution (manufactured by Tosoh Finechem Co., Ltd.) containing 9.0% by mass (as Al atom content) of methylaluminoxane at a concentration of 9.0% by mass as Al atom content.
• MMAO-3A contains 6 mol% of trimethylaluminum based on the total Al.
• TMAO-211 contains 26 mol% of trimethylaluminum based on the total Al.
• ND means that the impurity amount was below the detection limit
• Impurity ND means that the impurity amount was below the detection limit. Means that the ratio of / catalyst amount was not calculated.
• the use of the hybrid adsorbent (AB1) composed of a mixture of activated alumina and zeolite as the adsorbent allows the epoxy impurity (EP) to be satisfactorily converted from norbornene containing the epoxy impurity (EP). It can be seen that can be removed. According to Examples 1 to 3, if the ratio (mass ppm / mass ppm) of the content of the epoxide impurity (EP) and the content of the catalyst to the polymerization solution used for the polymerization is 6 or less. It can be seen that a cyclic olefin polymer can be obtained with a good yield.
• Comparative Example 1 Comparative Example 2, and Reference Example 1, when molecular sieve (AB2) is used as the adsorbent, the aldehyde impurity (AL) and the ketone impurity (KE) are treated during the treatment with the adsorbent. It can be seen that this can occur. According to a comparison between Example 1 and Reference Example 1 in which the amount of epoxy impurities (EP) in the toluene solution after the adsorbent treatment is close, the aldehyde impurities (AL) and the ketone impurities (KE) are cyclic olefins. It is presumed that this may be a factor in lowering the polymerization yield of the polymer.
• AB2 molecular sieve

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