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
  • C08F210/14—Monomers containing five or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a method for producing a cyclic olefin copolymer containing a structural unit derived from norbornene monomer and a structural unit derived from ethylene.
• Cyclic olefin homopolymers and cyclic olefin copolymers have low moisture absorption 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.
• 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 copolymerization composition of cyclic olefin and ethylene, the copolymer weight in which the glass transition temperature (Tg) is adjusted in a wide temperature range. Copolymerization can be produced (see, for example, Non-Patent Document 1).
• a low glass transition temperature is often desired for cyclic olefin copolymers because they can be easily processed into various molded products such as films and sheets. Further, in the polymerization for producing a cyclic olefin copolymer having a high glass transition temperature, the activity of the catalyst tends to decrease. Therefore, there is a tendency that the production efficiency of the cyclic olefin copolymer is lowered. Therefore, from this point as well, it is often desired to produce a cyclic olefin copolymer having a low glass transition temperature. In this respect, by increasing the ethylene charging pressure, it is easy to produce a cyclic olefin copolymer having a low glass transition temperature.
• the present invention has been made in view of the above problems, and even if a norbornene monomer and a monomer containing ethylene are polymerized under conditions where a high ethylene charging pressure is likely to generate polyethylene-like impurities, polyethylene is used. 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 having a low glass transition temperature (Tg) and excellent processability while suppressing the formation of such impurities.
• Tg glass transition temperature
• the present inventors have used a ligand containing a cyclopentadiene ring when polymerizing a monomer containing a norbornene monomer and ethylene in the presence of a metallocene catalyst at an ethylene charging pressure of 0.5 MPa or more. It was found that the above-mentioned problems can be solved by using a metallocene catalyst having 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. , 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 norbornene monomer and a structural unit derived from ethylene At least, the norbornene monomer and ethylene are charged as monomers in the polymerization vessel. Including polymerizing the monomers in the polymerization vessel in the presence of a metallocene catalyst, The pressure at which ethylene is charged into the polymerization vessel is 0.5 MPa or more.
• 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.
• a DSC curve obtained by measuring a sample of a cyclic olefin copolymer with a differential scanning calorimeter under a nitrogen atmosphere and a heating rate of 20 ° C./min according to the method described in JIS K7121 is obtained.
• the metallocene catalyst has the following formula (a1): (In the formula (a1), M is Ti, Zr, or Hf. R a1 to R a5 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. Two groups adjacent to each other on a 5-membered ring among R a1 to R a5 may be bonded to each other to form a ring. Is an organic substituent having 1 to 20 carbon atoms or a halogen atom which may contain a hetero atom. L is the following formula (a1a) or formula (a1b): It is a group represented by.
• R a6 to R a8 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. n1 is an integer of 0 to 3.
• R a9, and R a10 are each independently, may be the same or different, a hydrogen atom, an organic substituent contain a heteroatom have carbon atoms which may 1 to 20, or inorganic It is a substituent.
• the two groups R a9 and R a10 may be bonded to each other to form a ring.
• the present invention even if a norbornene monomer and a monomer containing ethylene are polymerized under a condition in which polyethylene-like impurities having a high ethylene charging pressure are likely to be generated, glass while suppressing the formation of polyethylene-like impurities. It is possible to provide a method for producing a cyclic olefin copolymer capable of efficiently producing a cyclic olefin copolymer having a low transition temperature (Tg) and excellent processability.
• Tg transition temperature
• a cyclic olefin copolymer containing a structural unit derived from norbornene monomer and a structural unit derived from ethylene is produced.
• the manufacturing method is At least, the norbornene monomer and ethylene are charged as monomers in the polymerization vessel. It comprises polymerizing the monomers in the polymerization vessel in the presence of a metallocene catalyst.
• 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 is also referred to as a polymerization step.
• the pressure for charging ethylene into the polymerization vessel is 0.5 MPa or more.
• the charging pressure is a gauge pressure.
• the monomer in the polymerization vessel is polymerized in the presence of a metallocene catalyst.
• the metallocene catalyst used for the polymerization has a structure in which a ligand containing a cyclopentadiene ring and a heteroatom of N, O, S, or P are bonded to a transition metal of Group IV of the periodic table and sp2 carbon. Has.
• a metallocene catalyst having the above-mentioned predetermined structure when polymerizing ethylene charged at high pressure in a reaction vessel and a norbornene monomer, a cyclic olefin is used while suppressing the formation of polyethylene-like impurities. It is easy to produce a copolymer in a good yield.
• ⁇ Preparation process> In the charging step, 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 structural units derived from the norbornene monomer and the ratio of the structural units derived from ethylene in the cyclic olefin copolymer is typically 80% by mass or more with respect to all the structural units. Preferably, 95% by mass or more is more preferable. 98% by mass or more is more preferable.
• the norbornene monomer and 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, but 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.
• Ethylene is charged into the polymerization vessel so that the ethylene charging pressure 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, and even 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.
• solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, and chloroform, methylene chloride.
• Dichloromethane, dichloroethane, and halogenated hydrocarbon solvents such as 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.
• the norbornene monomer will be described below.
• 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.
• substituted norbornene is not particularly limited, and examples of the substituent contained in this substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group.
• substituent contained in this substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group.
• Specific examples of the substituted norbornene include those represented by the following general formula (I).
• R 1 to R 12 may be the same or different 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 group, phenethyl group and other alkyl groups substituted with aryl groups and the like. Yes, they may 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 propylidene 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 . 1 7, 10
• Dodeca-3-ene, 8-ethyltetracyclo 4.4.0.1 2,5 . 1 7, 10
• Dodeca-3-ene, 8-ethylidenetetracyclo 4.4.0.1 2,5 .
• 4-ring cyclic olefins such as dodeca-3-ene; 8-Cyclopentyl-tetracyclo [4.4.0.1 2,5 . 17 and 10 ]
• Tetradeca-4,9,11,13-tetraene also called 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 . 0 9,13] -4-pentadecene
• alkyl-substituted norbornene for example, bicyclo [2.2.1] hepta-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornene for example, 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 monomer in the polymerization vessel is polymerized in the presence of a metallocene catalyst.
• 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.
• a catalyst having a ligand containing a cyclopentadiene ring and 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 is used.
• 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 substituent bonded to the heteroatom and sp2 carbon is not particularly limited as long as the object of the present invention is not impaired.
• Ti As the Group IV transition metal of the periodic table in the metallocene catalyst, Ti, Zr, or Hf is preferable, and Ti is more preferable.
• Suitable examples of the cyclopentadiene-containing ligand contained in the metallocene catalyst include cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, n-butylcyclopentadiene, Di-n-butylcyclopentadiene, tert-butylcyclopentadiene, di-tert-butylcyclopentadiene, adamantylcyclopentadiene, monomethylinden, dimethylinden, trimethylinden, tetramethylinden, 4,5,6,7-tetrahydroinden, Fluorene, 5,10-dihydroindeno [1,2-b] indole, N-methyl-5,10-dihydroindeno [1,2-b] indole, N-phenyl-5,10-dihydroinden
• a preferred example of such a metallocene catalyst is 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 a Group IV transition metal of the periodic table, preferably Ti, Zr, or Hf, and Ti is easy to obtain and produce a metallocene catalyst, and Ti is active in terms of catalyst activity. Is particularly preferable.
• 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 adjacent groups 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 R a8 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 a group, and n1 is an integer of 0 to 3.
• R a9, and R a10 are each independently, may be the same or different, a hydrogen atom, an organic substituent contain a heteroatom have carbon atoms which may 1 to 20, or inorganic It is a substituent.
• the two groups R a9 and R a10 may be bonded to each other to form a ring.
• R a1 to R a5 may be independently the same or different, and may contain a hydrogen atom and a hetero atom, which are organic substituents having 1 to 20 carbon atoms or inorganic substituents. It is the basis. Regarding an 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 production reaction of the metallocene compound represented by the above formula (a1).
• 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 production reaction of the metallocene compound represented by the above formula (a1).
• Specific examples of the inorganic group 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.
• a preferred example of an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom as X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom as Ra1 to Ra5 . This is similar to the example of 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 R a8 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 a group, and n1 is an integer of 0 to 3. n1 is an integer of 0 to 3, preferably 0 or 1, more preferably 0. Specific examples of the above-mentioned groups for R a6 to R a8 in the formula (a1a) are the same as specific examples of the above-mentioned 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.
• R a9, and R a10 are each independently, may be the same or different, a hydrogen atom, an organic substituent contain a heteroatom have carbon atoms which may 1 to 20, or inorganic It is a substituent.
• the two groups R a9 and R a10 may be bonded to each other to form a ring.
• R a9, and as R a10 preferred examples of the organic substituents contain a heteroatom having 1 carbon atoms which may atom 20, R a1 as ⁇ R a5, carbon atoms which may contain a hetero atom This is the same as the example of the organic substituents of numbers 1 to 20.
• 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.
• Mono-substituted amino group as R a9, and R a10 in equation (a1b), or the disubstituted amino group preferred examples of the hydrocarbon group having 1 to 20 carbon atoms bonded to the nitrogen atom, R a1 ⁇ Preferred examples of organic substituents for R a5 include hydrocarbon groups.
• Preferred examples of the group represented by the formula (a1b) include the following groups.
• Preferred specific examples of the metallocene compound represented by the formula (a1) described above include the following metallocene compounds.
• M in the following formula is the same as M in 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 metallocene catalyst is preferably mixed with aluminoxane and / or an ionic compound to form a catalyst composition.
• the ionic compound is a compound that produces a cationic transition metal compound by reacting 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 0.000000001 to 20 mol / L.
• a quantity of solvent is used.
• the value of (M b1 + M b2) / M a is preferably 1 to 200000 and more preferably 100 to 100,000, as particularly preferably at from 1,000 to 80,000, the liquid is mixed containing raw materials of the catalyst composition It is preferable to be done.
• 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.
• aluminoxane As the alminoxane, various aluminoxanes conventionally used as cocatalysts 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.
• alkyl aluminoxane is preferably used as the aluminoxane.
• alkylaluminoxane examples 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 particularly A modified methylaluminoxane in which a part of the methyl group is replaced with an isobutyl group is more preferable.
• alkylaluminoxane examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxan and the like, and among them, methylaluminoxane and methylisobutylaluminoxane 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 alkylaluminoxane products include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), methylaminenoxane solution (manufactured by Albemarle Corporation), and the like. ..
• the ionic compound is a compound that produces a cationic transition metal compound by reacting with a metallocene catalyst.
• examples of such an ionic compound include an anion of tetrakis (pentafluorophenyl) borate, an amine cation having an active proton such as dimethylphenylammonium cation ((CH 3 ) 2 N (C 6 H 5 ) H + ), and (C 6 H). 5 )
• Ionic compounds containing ions such as trisubstituted carbonium cations such as 3 C + , carborane cations, metal carborane cations, and ferrosenium cations having a transition metal 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-methyldinormal decyl.
• Examples thereof include N-methyldialkylammonium tetrakis (pentafluorophenyl) borate such as ammonium tetrakis (pentafluorophenyl) borate.
• an aluminoxane, an alkylaluminum compound, or one or more thereof is added into the polymerization vessel before adding a metallocene catalyst or a catalyst composition containing a metallocene catalyst. It is preferable to have one or more selected from aromatic compounds having a phenolic hydroxyl group and one or more halogen atoms on an aromatic ring, and hindered phenol.
• the phenolic hydroxyl group and the halogen atom are bonded on the same aromatic ring which may be a monocyclic ring or a fused ring.
• Hindered phenols are phenols having a bulky substituent at at least one of the two adjacent positions of the phenolic hydroxyl group.
• Examples of 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
• BHT 2,6-di-tert-butyl-p-cresol
• Di-tert-butylphenol is preferred.
• Hindered phenol contributes to an increase in the yield of the cyclic olefin copolymer by reacting with the alkylaluminum compound in the polymerization system. For this reason, hindered phenol is preferably used with alkylaluminum.
• hindered phenol may be used by mixing with alkylaluminum in a polymerization machine. A mixture obtained by mixing alkylaluminum and hindered phenol before polymerization may be introduced into the polymerization machine.
• Alminoxane 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 alkylaluminum compound include compounds represented by the following general formula (II). (R 10 ) z AlX 3-z (II) (In formula (II), R 10 is an alkyl group having 1 to 15, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3.)
• alkyl group having 1 to 15 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-octyl group and the like.
• alkylaluminum compound examples include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum and trin-octylaluminum; dimethylaluminum chloride, Examples thereof include dialkylaluminum halides such as diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminummethoxyde.
• trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum and trin-octylaluminum
• the alkylaluminum compound acts as a chain transfer agent and promotes chain polymerization catalyzed by the catalyst composition described above.
• the chain transfer agent hydrogen is preferably used in addition to the alkylaluminum compound.
• the amount used is preferably 10 to 1,000,000 mol as the number of moles of aluminum in the aluminoxane with respect to 1 mol of the transition metal compound. , 100-100,000 mol is more preferred.
• the amount used is preferably 5 to 500,000 mol as the number of moles of aluminum per 1 mol of the transition metal compound. More preferably, 50,000 to 50,000 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 alkylaluminum.
• a metallocene catalyst an ionic compound and alkylaluminum
• 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 catalyst used is derived from the amount of transition metal compound used in its preparation.
• the amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, preferably 0.00000001 to 0.0005 mol, based on 1 mol of the norbornene monomer, as the mass of the transition metal compound used for the preparation thereof. More preferred.
• 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 to 120 hours, preferably 0.1 to 80 hours, and 0.2 to 80 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.
• the glass transition temperature is suppressed while suppressing the formation of polyethylene-like impurities.
• the glass transition temperature is not particularly limited, but is preferably 185 ° C. or lower, more preferably 160 ° C. or lower, further preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 100 ° C. or lower.
• the cyclic olefin copolymer produced by the above method is measured by a differential operating calorimeter (DSC) under a nitrogen atmosphere and a heating rate of 20 ° C./min according to the method described in JIS K7121. It is preferable that the obtained DSC curve does not have a peak of melting point (melting enthalpy) derived from polyethylene-like impurities. This means that the polyethylene-like impurities in the cyclic olefin copolymer are absent or extremely low. When the cyclic olefin copolymer contains polyethylene-like impurities, 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.
• 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-based copolymer produced by the above method is required to have a high degree of transparency in terms of optical function and aesthetics, such as an optical film or an optical sheet, a film for a packaging material, or a packaging material. It is particularly preferably used as a material for sheets.
• Example 1 to 14 and Comparative Examples 1 to 5 In producing the cyclic olefin resin composition, the following C1 or C2 was used as the metallocene catalyst in Examples and Comparative Examples 1 and 2.
• CC1 6.5% by mass (as Al atom content) MMAO-3A toluene solution ([ (CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO]
• n methylisobutylaluminoxane represented by n , manufactured by Tosoh Finechem Co., Ltd., and 6 mol% trimethylaluminum based on total Al.
• CC2 9.0% by mass (as Al atom content) TMAO-211 toluene solution (solution of methylaluminoxane, manufactured by Toso Finechem Co., Ltd., still containing 26 mol% of trimethylaluminum with respect to total Al)
• CC3 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.)
• CC4 Tetrakis (pentafluorophenyl) trityl borate (manufactured by Tokyo Chemical Industry Co., Ltd.)
• CC5 N-Methyldialkylammonium tetrakis (pentafluorophenyl) borate (alkyl: C14 to C18 (average: C17.5) (manufactured by Tosoh Finechem Co., Ltd.)
• CC6 Triisobutylaluminum (manufactured by Tosoh Finechem Co.,
• the polymerization solvent shown in Table 2 and 90 mmol of 2-norbornene were added to a well-dried 150 mL stainless steel autoclave containing a stir bar.
• the cocatalysts listed in Table 1 were then added as described below.
• CC1 or CC2 was added.
• CC1 or CC2 was added, and then CC3 was further added.
• CC4 or CC5 was added after the catalyst solution was added, as described later.
• the catalyst solution was prepared using the same solvent as the polymerization solvent shown in Table 2.
• Example 10 to 14 and Comparative Examples 1 and 2 CC6 or CC7 was added, and in Example 12, CC3 was further added thereafter.
• the autoclave was heated to the polymerization temperature shown in Table 2, and then the catalyst solution was added so that the amount of the catalyst was the amount shown in Table 1.
• the catalyst solution was added so that the amount of the catalyst was as shown in Table 1, and then the solution of CC4 or CC5 prepared by using the polymerization solvent shown in Table 2 was added.
• an ethylene pressure with a gauge pressure of 0.7 MPa was applied.
• the ethylene pressure was set to a gauge pressure of 0.4 MPa.
• the total volume of the monomer solution immediately before applying ethylene pressure was 80 mL.
• 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.
• the polymerization solution was added to 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 2 shows the copolymer yield (kg) per 1 g of the catalyst 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 2 indicates that a peak derived from polyethylene-like impurities is not detected on the DSC curve.
• the pressure for charging ethylene into the polymerization vessel is set to 0.5 MPa or more, and cyclo.

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