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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • 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
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/08—Butenes
  • C08F210/10—Isobutene
  • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
• • 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
  • C08F2420/00—Metallocene catalysts
  • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor

Definitions

• the present invention relates to a method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene.
• 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 disk substrates, optical films, and optical fibers.
• As a typical cyclic olefin copolymer there is a copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin. Since 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, the coweight in which the glass transition temperature (Tg) is adjusted in a wide temperature range. Coagulation can be produced (see, eg, Non-Patent Document 1).
• Non-Patent Document 1 there is a problem that a copolymer of cyclic olefin and ethylene cannot be produced in high yield.
• a highly active catalyst As a countermeasure against this problem, it is conceivable to carry out polymerization using a highly active catalyst.
• a highly active catalyst for the purpose of increasing the production efficiency of the cyclic olefin copolymer, it is difficult to control the molecular weight of the produced copolymer, and an excessively high molecular weight copolymer is often used. can get.
• the present invention has been made in view of the above problems, and is obtained by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the formation of polyethylene-like impurities and an excessive increase in molecular weight. It is an object of the present invention to provide a method for producing a cyclic olefin copolymer capable of efficiently producing a cyclic olefin copolymer.
• the present inventors are N, O, S, or P with a ligand containing a cyclopentadiene ring when polymerizing a monomer containing a norbornene monomer and an ethylene in the presence of a metallocene catalyst.
• a metallocene catalyst having a structure in which a hetero atom is bonded to a transition metal of Group IV of the Periodic Table and sp2 carbon in combination with an alkyl metal compound.
• the present invention has been completed. More specifically, the present invention provides the following.
• a method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene At least, the norbornene monomer and ethylene are charged into the polymerization vessel as monomers, and It comprises polymerizing the monomers in the polymerization vessel in the presence of a metallocene catalyst and an alkyl metal compound.
• the alkyl metal compound comprises at least one of an alkylaluminum compound having at least one alkyl group attached to an Al atom and an alkylzinc compound having at least one alkyl group attached to a Zn atom.
• the metallocene catalyst has a ligand containing a cyclopentadiene ring and a structure in which a heteroatom N, O, S, or P is bonded to a Group IV transition metal of the Periodic Table and sp2 carbon. ,Production method.
• the metallocene catalyst has the following formula (a1): (In the formula ( a1 ), M is Ti, Zr, or Hf, and Ra1 to Ra5 may be the same or different, respectively, and may contain a hydrogen atom and a hetero atom. It is an organic substituent or an inorganic substituent having 1 to 20 atoms, and two adjacent groups on a 5-membered ring among Ra1 to Ra5 may be bonded to each other to form a ring. Is an organic substituent or a halogen atom having 1 to 20 carbon atoms which may contain a hetero atom, and L is the following formula (a1a) or formula (a1b) :.
• R a6 to Ra 8 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substituent. It is an atom, n1 is an integer of 0 to 3, and In the formula ( a1b ), Ra 9 and Ra 10 may be independently the same or different from each other, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substance. It is a substituent, and the two groups Ra 9 and Ra 10 may be bonded to each other to form a ring. ) The method for producing a cyclic olefin copolymer according to (1), which is a metallocene compound represented by.
• the alkylaluminum compound has at least one branched chain alkyl group having 2 or more and 8 or less carbon atoms bonded to the Al atom, and the alkyl zinc compound has 2 or more and 8 or less carbon atoms bonded to the Zn atom.
• a cyclic olefin copolymer is efficiently produced by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the generation of polyethylene-like impurities and the excessive increase in molecular weight. It is possible to provide a method for producing a cyclic olefin copolymer capable.
• a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene is produced.
• the manufacturing method is At least, the norbornene monomer and ethylene are charged into the polymerization vessel as monomers, and It comprises polymerizing the monomer in the polymerization vessel in the presence of a metallocene catalyst and an alkyl metal compound.
• charging the norbornene monomer and ethylene as monomers into the polymerization vessel is also referred to as a charging step.
• polymerizing the monomer in the polymerization vessel in the presence of a metallocene catalyst and an alkyl metal compound is also referred to as a polymerization step.
• the monomer in the polymerization vessel is polymerized in the presence of a metallocene catalyst and an alkyl metal compound.
• the metallocene catalyst used for the polymerization has a ligand containing a cyclopentadiene ring, a structure in which a heteroatom of N, O, S, or P is bonded to a transition metal of Group IV of the Periodic Table and sp2 carbon. Has.
• ethylene and a norbornene monomer are copolymerized in the presence of a highly active catalyst, a copolymer having an excessively high molecular weight can be obtained, or ethylene can easily be polymerized with each other, and polyethylene is used. It is easy for similar impurities to be generated.
• the norbornene monomer and ethylene are charged into the polymerization vessel as monomers.
• the polymerization vessel may be charged with a norbornene monomer and a monomer other than ethylene as long as the object of the present invention is not impaired.
• the total of the ratio of the constituent units derived from the norbornene monomer and the ratio of the constituent units derived from ethylene in the cyclic olefin copolymer is typically 80% by mass or more with respect to all the constituent units. It is preferable, 95% by mass or more is more preferable, and 98% by mass or more is further preferable.
• the norbornene monomer and other monomers other than ethylene are not particularly limited as long as they can be copolymerized with the norbornene monomer and ethylene.
• Typical examples of such other monomers include ⁇ -olefins.
• the ⁇ -olefin may be substituted with at least one substituent such as a halogen atom.
• C3 to C12 ⁇ -olefins are preferable.
• the ⁇ -olefins of C3 to C12 are not particularly limited, and are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1.
• 1-hexene, 1-octene, and 1-decene are preferable.
• the method of charging ethylene into the polymerization solution is not particularly limited as long as a desired amount of ethylene can be charged in the polymerization container.
• ethylene is charged into the polymerization vessel so that the charging pressure of ethylene in the polymerization vessel is 0.5 MPa or more.
• the ethylene charging pressure is preferably 0.55 MPa or more, more preferably 0.6 MPa or more.
• Increasing the ethylene charging pressure can reduce the amount of catalyst used per produced polymer.
• the ethylene charging pressure is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, still more preferably 3 MPa or less.
• a solvent may be charged in the polymerization vessel together with the norbornene monomer and ethylene.
• the solvent is not particularly limited as long as it does not inhibit the polymerization reaction.
• Preferred solvents include, for example, a hydrocarbon solvent and a halogenated hydrocarbon solvent, and a hydrocarbon solvent is preferable because it is excellent in handleability, thermal stability, and chemical stability.
• preferable solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and chloroform.
• hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and chloroform.
• halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.
• the lower limit of the concentration of the norbornene monomer is preferably, for example, 0.5% by mass or more, and more preferably 10% by mass or more.
• the upper limit for example, 50% by mass or less is preferable, and 35% by mass or less is more preferable.
• norbornene monomer examples include norbornene and substituted norbornene, and norbornene is preferable.
• the norbornene monomer can be used alone or in combination of two or more.
• the substituted norbornene is not particularly limited, and examples of the substituent contained in the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include compounds represented by the following general formula (I).
• R 1 to R 12 may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
• R 9 and R 10 and 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 indicates 0 or a positive integer.
• R 1 to R 12 in the general formula (I) may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
• R 1 to R 8 include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms, and the like, which may be different from each other. , 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 a trill.
• Substituent or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups and anthryl groups; benzyl groups, phenethyl groups and other alkyl groups substituted with aryl groups such as aralkyl groups. They can be different, partially different, or all identical.
• R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group
• a divalent hydrocarbon group include, for example, an alkylidene group such as an ethylidene group, a propyridene group, and an isopropylidene group. Can be mentioned.
• the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. , It may be a ring having a double bond, or it may be a ring composed of a combination of these rings. Further, 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] 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-ethylidene-bicyclo [2.2.
• Cyclic olefin of the ring Tetracyclo [4.4.0.1 2,5 . 17 and 10 ]
• Dodeca-3-ene also simply referred to as tetracyclododecene
• 8-methyltetracyclo 4.4.0.1 2,5 . 17 and 10
• Dodeca-3-ene, 8-ethyltetracyclo 4.4.0.1 2,5 . 1 7 , 10]
• Tetradeca-4,9,11,13-tetraene also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene
• tetracyclo 8.4.1, 4,7 . 0 1,10 1 .
• Pentadeca-5,10,12,14-tetraene also referred to as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene
• pentacyclo [6.6.1. 1 3, 6 . 0 2,7 . 09,14 ] -4-hexadecene
• pentacyclo [6.5.1.1 3,6 . 0 2,7 . 09,13 ] -4-pentadecene
• alkyl-substituted norbornene eg, bicyclo [2.2.1] hepta-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornene eg, bicyclo substituted with one or more alkylidene groups
• [2.2.1] hepta-2-ene) is preferred, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene). ) Is particularly preferable.
• the monomers in the polymerization vessel are polymerized in the presence of a metallocene catalyst and an alkyl metal compound that meet predetermined requirements, respectively.
• the temperature at the time of polymerization is not particularly limited. Since the yield of the cyclic olefin copolymer is good, the temperature at the time of polymerization is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, still more preferably 60 ° C. or higher. 70 ° C. or higher is particularly preferable.
• the temperature at the time of polymerization may be 80 ° C. or higher.
• the upper limit of the temperature at the time of polymerization is not particularly limited, and the upper limit of the temperature at the time of polymerization may be, for example, 200 ° C. or lower, 140 ° C. or lower, or 120 ° C. or lower.
• the metallocene catalyst has a ligand containing a cyclopentadiene ring and a structure in which a hetero atom of N, O, S, or P is bonded to a transition metal of Group IV of the Periodic Table and sp2 carbon.
• sp2 carbon refers to a carbon atom forming an sp2 hybrid orbital.
• a substituent may be bonded to the above heteroatom and sp2 carbon, but the heteroatom and the substituent bonded to sp2 carbon are not particularly limited as long as the object of the present invention is not impaired.
• Suitable examples of a cyclopentadiene-containing ligand contained in a metallocene catalyst include cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, n-butylcyclopentadiene, and the like.
• Ti As the periodic table Group IV transition metal in the metallocene catalyst, Ti, Zr, or Hf is preferable, and Ti is more preferable.
• metallocene catalyst examples include a metallocene compound represented by the following formula (a1).
• L is a group represented by the following formula (a1a) or the formula (a1b).
• M is Ti, Zr, or Hf, and Ti is particularly preferable in terms of easy availability and production of a metallocene catalyst, activity of the catalyst, and the like.
• R a1 to R a5 are organic substituents or inorganic substituents having 1 to 20 carbon atoms, which may be the same or different, and may contain a hydrogen atom and a hetero atom, respectively. Two groups adjacent to each other on the 5-membered ring of R a1 to R a5 may be bonded to each other to form a ring.
• X is an organic substituent having 1 to 20 carbon atoms or a halogen atom which may contain a hetero atom.
• R a6 to Ra 8 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substituent. It is an atom, and n1 is an integer of 0 to 3.
• Ra 9 and Ra 10 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substance. It is a substituent.
• the two groups R a9 and R a10 may be coupled to each other to form a ring.
• Ra1 to Ra5 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substituent. It is the basis.
• the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom when the organic substituent contains a hetero atom, the type of the hetero atom is not particularly limited as long as the object of the present invention is not impaired.
• 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, a halogen atom and the like.
• the organic substituent is not particularly limited as long as it is a group that does not inhibit the reaction for producing the metallocene compound represented by the above formula (a1).
• 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, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, and ⁇ -.
• Examples thereof include a mono-substituted amino group substituted with 20 hydrocarbon groups and a di-substituted amino group substituted with a hydrocarbon group having 1 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 an aliphatic acyl having 2 to 6 carbon atoms.
• a group, a benzoyl group, a phenyl group, a benzyl group, a phenethyl group, and a trialkylsilyl group having 3 to 10 carbon atoms are preferable.
• Isobutyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, phenyl group, trimethylsilyl group, and tert-butyldimethylsilyl group are more preferable.
• the inorganic substituent is not particularly limited as long as it is a group that does not inhibit the reaction for producing the metallocene compound represented by the above formula (a1).
• Specific examples of the inorganic substituent include a halogen atom, a nitro group, an unsubstituted amino group, a cyano group and the like.
• X is an organic substituent having 1 to 20 carbon atoms or a halogen atom which may contain a hetero atom.
• Specific examples and preferred examples of the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom as X are, as R a1 to Ra5 , 1 carbon atom which may contain a heteroatom. It is the same as the specific example and preferable example of 20 organic substituents.
• a halogen atom is preferable, a chlorine atom and a bromine atom are more preferable, and a chlorine atom is particularly preferable.
• R a6 to Ra 8 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substituent. It is an atom, and n1 is an integer of 0 to 3. n1 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. Specific examples and preferred examples of the above groups for R a6 to Ra 8 in the formula (a1a) are the same as the specific examples and preferred examples of the above groups for R a1 to R a5 .
• Preferred examples of the group represented by the formula (a1a) include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,6-diisopropylphenoxy group.
• Ra 9 and Ra 10 may be independently the same or different, and may contain a hydrogen atom, a hetero atom, an organic substituent having 1 to 20 carbon atoms, or an inorganic substance. It is a substituent.
• the two groups R a9 and R a10 may be coupled to each other to form a ring.
• Specific examples and preferred examples of organic substituents having 1 to 20 carbon atoms which may contain heteroatoms as R a9 and Ra 10 may contain heteroatoms as R a1 to R a5 . The same applies to specific examples and preferred examples of good organic substituents having 1 to 20 carbon atoms.
• a mono-substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms and a di-substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms are also preferable as the organic substituent.
• a suitable example of the hydrocarbon group having 1 to 20 carbon atoms bonded to the nitrogen atom is R a1 to.
• Preferred examples of organic substituents for R a5 include hydrocarbon groups.
• Specific examples of the inorganic substituents as Ra 9 and Ra 10 are the same as those of the specific examples of the inorganic substituents as Ra 1 to Ra 5 .
• Preferred examples of the group represented by the formula (a1b) include the following groups.
• Preferred specific examples of the metallocene compound represented by the above-described formula (a1) include the following metallocene compounds.
• M in the following formula is the same as M in the formula (a1).
• n-Bu is an n-butyl group
• tert-Bu is a tert-butyl group
• Si (Me) 3 is a trimethylsilyl group
• Si (Me) 2 tert-butyl is tert.
• -Butyldimethylsilyl group
• the monomer in the polymerization vessel is polymerized in the presence of a metallocene catalyst and an alkyl metal compound.
• the alkyl metal compound includes at least one of an alkyl aluminum compound having at least one alkyl group bonded to an Al atom and an alkyl zinc compound having at least one alkyl group bonded to a Zn atom.
• the alkyl metal compound may be used alone or in combination of two or more.
• alkylaluminum compound a compound conventionally used for polymerization of olefins and the like can be used without particular limitation.
• alkylaluminum compound examples include compounds represented by the following general formula (II).
• R 01 is an alkyl group having 1 to 15 carbon atoms
• X is a halogen atom or a hydrogen atom
• z1 is an integer of 1 to 3).
• the number of carbon atoms of the alkyl group as R 01 is 1 to 15, and 1 to 8 is more preferable, and 2 to 8 is further preferable, from the viewpoint that the desired effect can be easily obtained.
• Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-. Examples include octyl groups.
• alkylaluminum compound examples include trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trin-pentylaluminum, and trin-.
• Trialkylaluminum such as hexylaluminum, trin-heptylaluminum, trin-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride; dimethylaluminum hydride, diethylaluminum hydride, din-propyldimethyl Aluminum hydride, diisopropyldimethylaluminum hydride, din-butylaluminum hydride, diisobutylaluminum hydride, disec-butylaluminum hydride, din-pentyl aluminum hydride, din-hexyl aluminum hydride, din-heptyl aluminum hydride, din- Dialkylaluminum hydrides such as octylaluminum hydride; examples include dialkylaluminum alkoxides such as dimethylaluminum meth
• alkyl zinc compound a compound conventionally used for polymerization of olefins and the like can be used without particular limitation.
• alkyl zinc compound examples include compounds represented by the following general formula (III).
• R 02 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 z2 is an integer of 1 to 3).
• the number of carbon atoms of the alkyl group as R 02 is 1 to 15, and 1 to 8 is more preferable, and 2 to 8 is further preferable, from the viewpoint that a desired effect can be easily obtained.
• Preferred specific examples of the alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-. Examples include octyl groups.
• alkyl zinc compound examples include dimethyl zinc, diethyl zinc, din-propyl zinc, diisopropyl zinc, din-butyl zinc, diisobutyl zinc, disec-butyl zinc, din-pentyl zinc, and din-hexyl zinc.
• Dialkyl zinc such as di-n-heptyl zinc, di-n-octyl zinc
• alkyl zinc halides such as methyl zinc chloride, ethyl zinc chloride, isobutyl zinc chloride
• alkyl zinc hydride such as methyl zinc hydride, ethyl zinc hydride, isobutyl zinc hydride and the like.
• alkyl metal compounds one or more selected from the group consisting of trialkylaluminum, dialkylaluminum hydride, and dialkylzinc is preferable, and trialkylaluminum and / or dialkylaluminum hydride is more preferable.
• the amount of the alkyl metal compound used together with the metallocene catalyst is preferably 1 to 500,000 mol, more preferably 10 to 50,000 mol, as the total number of moles of aluminum and zinc with respect to 1 mol of the metallocene catalyst.
• the polymerization of the monomer is preferably carried out in the presence of the above-mentioned metallocene catalyst and co-catalyst.
• a compound generally used as a co-catalyst in the polymerization of olefins can be used without particular limitation.
• the co-catalyst include aluminoxane and ionic compounds.
• the polymerization of the monomer is particularly preferably carried out using at least one of aluminoxane and a borate compound as an ionic compound as an co-catalyst, and aluminoxane is used as a co-catalyst. It is more preferable to be polymerized.
• the monomer in the presence of a metallocene catalyst, an alkyl metal compound and at least one of an aluminoxane and a borate compound, and the monomer in the presence of a metallocene catalyst, an alkyl metal compound and an aluminoxane. It is more preferable to polymerize.
• the metallocene catalyst is preferably mixed with aluminoxane and / or an ionic compound to form a catalyst composition.
• the alkyl metal compound may be added to the catalyst composition or may be supplied to the polymerization vessel separately from the catalyst composition.
• the ionic compound is a compound that produces a cationic transition metal compound by reaction with a metallocene catalyst.
• the catalyst composition is preferably prepared using a solution of a metallocene catalyst.
• the solvent contained in the metallocene catalyst solution is not particularly limited.
• Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), mineral oil, benzene, toluene, and xylene, and chloroform.
• Examples thereof include halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.
• the amount of the solvent used is not particularly limited as long as the catalyst composition having the desired performance can be produced.
• the concentrations of the metallocene catalyst, aluminoxane, and the ionic compound are preferably 0.00000001 to 100 mol / L, more preferably 0.00000005 to 50 mol / L, and particularly preferably 0.0000001 to 20 mol / L.
• a quantity of solvent is used.
• the number of moles of the transition metal element in the metallocene catalyst is Ma
• the number of moles of aluminum in the aluminoxane is M b1
• the number of moles of the ionic compound is M b2 .
• the liquid containing the raw material of the catalyst composition is mixed so that the value of (M b1 + M b2 ) / Ma is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000. It is preferable to be.
• the temperature at which the liquid containing the raw material of the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100 ° C, more preferably -50 to 50 ° C.
• the mixing of the metallocene catalyst solution for preparing the catalyst composition with the aluminoxane and / or the ionic compound may be carried out in a device separate from the polymerization vessel before the polymerization, and the polymerization is carried out in the polymerization vessel. It may be done before or during polymerization.
• aluminoxan As the alkynexane, various aluminoxanes conventionally used as co-catalysts and the like in the polymerization of various olefins can be used without particular limitation.
• the aluminoxane is an organic aluminoxane.
• one type of aluminoxane may be used alone, or two or more types may be used in combination.
• an alkylaluminoxane is preferably used as the aluminoxane.
• the alkylaluminoxane include compounds represented by the following formulas (b1-1) or (b1-2).
• the alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting 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 in which a part of the methyl group of the methylaluminoxane is replaced with another alkyl group.
• modified methylaluminoxane for example, as the substituted alkyl group, 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 is preferable, and in particular, a modified methylaluminoxane is preferable.
• a modified methylaluminoxane in which a part of the methyl group is replaced with an isobutyl group is more preferable.
• the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxan, butylaluminoxane, isobutylaluminoxan, methylethylaluminoxan, methylbutylaluminoxane, methylisobutylaluminoxan and the like, and among them, methylaluminoxane and methylisobutylaluminoxan are preferable.
• Alkyl aluminoxane can be prepared by a known method. Further, as the alkylaluminoxane, a commercially available product may be used. Examples of commercially available products of alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), methylaluminoxane solution (manufactured by Albemarle Corporation), and the like. .. It is more preferable to use an alkylaluminoxane other than solid MAO because it is easy to suppress the formation of polyethylene-like impurities.
• the ionic compound is a compound that produces a cationic transition metal compound by reacting with a metallocene catalyst.
• ionic compounds include tetrakis (pentafluorophenyl) borate anions, amine cations having active protons such as dimethylphenylammonium cations ((CH 3 ) 2 N (C 6 H 5 ) H + ), (C 6 H). 5 )
• Ionic compounds containing ions such as trisubstituted carbonium cations such as 3C + , carborane cations, metal carborane cations, and ferrosenium cations with transition metals can be used.
• a suitable example of an ionic compound is borate.
• Preferred specific examples of borate are tetrakis (pentafluorophenyl) trityl borate, dimethylphenylammonium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-methyldinormaldecyl.
• Examples thereof include N-methyldialkylammonium tetrakis (pentafluorophenyl) borate such as ammonium tetrakis (pentafluorophenyl) borate.
• the aluminoxane or a plurality of phenolic hydroxyl groups are placed in the polymerization vessel before the metallocene catalyst or the catalyst composition containing the metallocene catalyst is added. It is preferable to have one or more selected from aromatic compounds having one or a plurality of halogen atoms on the aromatic ring and hindered phenol. In the above aromatic compound having a phenolic hydroxyl group and a halogen atom, the phenolic hydroxyl group and the halogen atom are bonded on the same aromatic ring which may be a monocyclic ring or a condensed ring.
• Hindered phenols are phenols having a bulky substituent at at least one of the two adjacent positions of the phenolic hydroxyl group.
• the bulky substituent include an alkyl group other than the methyl group such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl tree, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and an alkoxy group. , Aryloxy group, substituted amino group, alkylthio group, arylthio group and the like.
• hindered phenol examples include, for example, 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-.
• BHT 2,6-di-tert-butyl-p-cresol
• Hindered phenol contributes to the increase in yield of the cyclic olefin copolymer by reacting with the alkylaluminum compound in the polymerization system.
• hindered phenol is preferably used with alkylaluminum.
• the hindered phenol may be used by mixing with alkylaluminum in the polymerization machine. A mixture obtained by mixing alkylaluminum and hindered phenol before polymerization may be introduced into the polymerization machine.
• Aluminoxane is as described in the method for producing a catalyst composition.
• the amount used is preferably 1 to 1,000,000 mol as the number of moles of aluminum in the aluminoxane with respect to 1 mol of the metallocene catalyst. More preferably, 10 to 100,000 mol.
• the polymerization is preferably carried out in the presence of a metallocene catalyst, aluminoxane and hindered phenol, or in the presence of a metallocene catalyst, an ionic compound and hindered phenol.
• the polymerization conditions are not particularly limited as long as the cyclic olefin copolymer having desired physical properties can be obtained, and known conditions can be used.
• the amount of the catalyst composition used is derived from the amount of the metallocene compound used in its preparation.
• the amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, based on 1 mol of the norbornene monomer, as the mass of the metallocene compound used for the preparation thereof. preferable.
• the polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer is increased to a desired degree.
• the polymerization time varies depending on the temperature, the composition of the catalyst, and the composition of the monomer, but is typically 0.01 hours to 120 hours, preferably 0.1 hours to 80 hours, and 0.2 hours to 0.2 hours. 10 hours is more preferred.
• the catalyst composition is continuously added to the polymerization vessel.
• the cyclic olefin copolymer can be continuously produced, and the production cost of the cyclic olefin copolymer can be reduced.
• a cyclic olefin copolymer can be efficiently produced by copolymerizing a norbornene monomer and a monomer containing ethylene to suppress the formation of polyethylene-like impurities.
• the glass transition temperature of the obtained cyclic olefin copolymer is not particularly limited, but is preferably 185 ° C. or lower, more preferably 160 ° C. or lower, further preferably 130 ° C. or lower, even more preferably 120 ° C. or lower, and 100 ° C. or lower. Especially preferable.
• a sample of the cyclic olefin copolymer produced by the above method was measured by a differential scanning calorimeter (DSC) under a nitrogen atmosphere and a heating rate of 20 ° C./min according to the method described in JIS K7121.
• DSC differential scanning calorimeter
• the obtained DSC curve does not have a peak of melting point (melting enthalpy) derived from polyethylene-like impurities. This means that polyethylene-like impurities in the cyclic olefin copolymer are absent or very few.
• the peak of the melting point derived from the polyethylene-like impurities on the DSC curve is generally detected in the range of 100 ° C to 140 ° C. Ru.
• the cyclic olefin copolymer produced by the above method has a low content of polyethylene-like impurities and is excellent in transparency. Therefore, the cyclic olefin copolymer produced by the above method is required to have a high degree of transparency in terms of optical function and aesthetics, and is an optical film or an optical sheet, or a film or sheet for a packaging material. It is particularly preferably used as a material for the above.
• the total volume of the monomer solution immediately before applying ethylene pressure was 80 mL. After 15 minutes from the start of the polymerization, the ethylene supply was stopped, the pressure was carefully returned to normal pressure, and then isopropyl alcohol was added to the reaction solution to stop the reaction. Then, the polymerization solution was put into a mixed solvent of 300 mL of acetone, 200 mL of methanol or isopropyl alcohol, and 5 mL of hydrochloric acid to precipitate the copolymer. The copolymer was recovered by suction filtration, washed with acetone and methanol, and vacuum dried at 110 ° C. for 12 hours to obtain a copolymer of norbornene and ethylene. Table 1 shows the copolymer yield (g) per 1 g of the catalyst, which is calculated from the amount of the catalyst used and the amount of the copolymer obtained.
• Tg ⁇ Glass transition temperature (Tg)> The Tg of the cyclic olefin copolymer was measured by the DSC method (method described in JIS K7121).
• DSC device Differential scanning calorimetry (DSC-Q1000 manufactured by TA Instrument) Measurement atmosphere: Nitrogen temperature rise condition: 20 ° C / min
• the calorific value (mJ / mg) was calculated from the peak area of the melting point derived from the polyethylene-like impurities observed in the range of 100 ° C to 140 ° C. The larger the calculated calorific value, the higher the content of polyethylene-like impurities.
• ND in Table 1 indicates that the peak of the melting point derived from the polyethylene-like impurity is not detected on the DSC curve.
• Et is an ethyl group
• i Pr is an isopropyl group
• i Bu is an isobutyl group
• Oct is an octyl group.
• Example 20 and Comparative Example 2 Changing the amount of 2-norbornene charged to 45 mmol, changing the charged pressure of ethylene to 0.9 MPa gauge pressure, changing the amount of metallocene catalyst to 0.5 ⁇ mol, the type and amount of alkyl metal compound added, and A copolymer of norbornene and ethylene was obtained in the same manner as in Example 1 except that the amount of the co-catalyst added was changed to the amount shown in Table 2 and the solvent was changed to decalin. In Comparative Example 2, no alkyl metal compound was used. Table 2 shows the copolymer yield (g) per 1 g of the catalyst, which is calculated from the amount of the catalyst used and the amount of the copolymer obtained.
• Example 2 Similar to Example 1, the glass transition temperature and the molecular weight were measured, and the impurity thermal analysis and the turbidity test for confirming the polyethylene-like impurities were performed. As a result of the turbidity test, no turbidity was observed in any of the examples and comparative examples. Table 2 shows the measurement results of the glass transition temperature, molecular weight and impurity thermal analysis.
• a metallocene catalyst satisfying the above-mentioned predetermined requirements and an alkylaluminum satisfying the above-mentioned predetermined requirements According to the comparison between Examples 1 to 19 and Comparative Example 1, or the comparison between Example 20 and Comparative Example 2, a metallocene catalyst satisfying the above-mentioned predetermined requirements and an alkylaluminum satisfying the above-mentioned predetermined requirements. Copolymerizing a monomer containing norbornene monomer and polyethylene in the presence of a compound or an alkyl zinc compound in the presence of a metallocene catalyst alone. Therefore, it can be seen that a copolymer of norbornene and ethylene can be efficiently obtained while suppressing the formation of polyethylene-like impurities and the excessive increase in molecular weight.

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