WO2012077546A1 - 環状オレフィン開環重合体、その水素化体および該水素化体組成物、ならびにトリシクロペンタジエン - Google Patents

環状オレフィン開環重合体、その水素化体および該水素化体組成物、ならびにトリシクロペンタジエン Download PDF

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WO2012077546A1
WO2012077546A1 PCT/JP2011/077634 JP2011077634W WO2012077546A1 WO 2012077546 A1 WO2012077546 A1 WO 2012077546A1 JP 2011077634 W JP2011077634 W JP 2011077634W WO 2012077546 A1 WO2012077546 A1 WO 2012077546A1
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cyclic olefin
compound
group
represented
ring
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PCT/JP2011/077634
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English (en)
French (fr)
Japanese (ja)
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多田羅　了嗣
優 木村
健 糸見
育代 神谷
充孝 海津
丸山　洋一郎
鈴木　義信
中村　和洋
拓 柴田
泰三 金山
哲徳 菅原
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Jsr株式会社
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Priority to CN201180052900.5A priority Critical patent/CN103201307B/zh
Priority to JP2012547799A priority patent/JP5742853B2/ja
Priority to KR1020137015342A priority patent/KR101850169B1/ko
Publication of WO2012077546A1 publication Critical patent/WO2012077546A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present invention relates to a cyclic olefin ring-opening polymer having a high refractive index and a high abebe number useful for optical materials, a hydrogenated product thereof, a composition of the cyclic olefin ring-opening polymerized hydrogenated product, and tricyclopentadiene.
  • Cyclic olefin ring-opening polymers particularly hydrogenated cyclic olefin ring-opening polymers (hereinafter referred to as cyclic olefin ring-opening polymers, hydrogenated cyclic olefin ring-opening polymers, including copolymers, (Also referred to as a ring polymer) has attracted attention as a thermoplastic transparent resin excellent in light transmittance and heat resistance.
  • This polymer is widely used in the field of optical materials such as optical lenses, optical fibers, and optical films.
  • mobile devices such as mobile phones in which these optical lenses are incorporated are being developed in the direction of further miniaturization and higher performance. For this reason, the component devices are required to be further reduced in size, weight, and functionality.
  • the lens resin is required to have a higher refractive index and a higher abe number so that it can function even if it is small and thin.
  • the design needs to be realized.
  • Patent Document 1 In order to increase the solubility of the cyclic olefin ring-opening polymer, it is known that it is effective to introduce a functional group such as an ester group into the side chain (Patent Document 1). On the other hand, the presence of a functional group hinders an increase in refractive index. Accordingly, the present inventors have conducted a preliminary study of a polymer that can achieve both solubility and high refractive index by copolymerizing with a monomer having no functional group. However, typical tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (dicyclopentadiene) or tetracyclo [4.4.0.1 2 ] as a monomer having no functional group. , 5 . 1 7,10] dodeca-3-ene (DMON), etc., the effect of improving the refractive index is small, previously only possible values of the refractive index inferior to existing resin (n D ⁇ 1.525).
  • DMON dodeca-3-ene
  • Patent Document 2 As another technique for achieving both a high refractive index of a cyclic olefin ring-opening polymer and solubility in a solvent, there is a technique of blending a polymer having a functional group introduced with polystyrene (Patent Document 2). With this technique, the refractive index can be increased in proportion to the increase in the amount of polystyrene blended, but on the other hand, the abbe number decreases and the chromatic aberration of the lens increases.
  • the present inventors searched for a monomer to be copolymerized in order to realize a high refractive index and a high abebe number.
  • pentacyclo [6.5.1.0 2,7 . 1 3,6 . 0 9,13] pentadeca-4,10-diene by copolymerization 3-5 mer (tricyclopentadiene) cyclopentadiene such as a high refractive index and high abbe number over the prior monomer Realized.
  • the solubility to a solvent was securable by making it a copolymer of a suitable composition with the monomer which has a functional group.
  • pentacyclo [6.5.1.0 2,7 . 1 3,6 . 0 9,13] pentadeca-4,10-diene ratio of geometric isomers in 3-5 mer (tricyclopentadiene) cyclopentadiene and the like, that affect the refractive index of the resulting polymer
  • pentacyclo 6.5.1.0 2,7 . 1 3,6 . 0 9,13
  • the present inventors have polymerized a cyclopentadiene polymer as a constituent monomer of a cyclic olefin, and then hydrogenated the polymer to exhibit very excellent characteristics for optical applications. I found it.
  • the reaction rate polymerization yield
  • the amount of outgas is large at the time of molding, which causes defects and cannot be used for optical materials and medical materials.
  • Patent Document 3 is known as a method for producing tricyclopentadiene, which is a trimer of cyclopentadiene.
  • tricyclopentadiene obtained by this method is 1,4,4a, 4b, 5,8,8a, 9a-octahydro-1,4; 5,8-dimethano-1H represented by the following formula (6): -Fluorene and isomers of 3a, 4,4a, 5,8,8a, 9,9a-octahydro-4,9; 5,8-dimethano-1H-benzo [f] indene represented by formula (5) 1,4,4a, 4b, 5,8,8a, 9a-octahydro-1,4; 5,8-dimethano-1H-fluorene represented by the formula (6) is as described above.
  • a crosslinking reaction occurs during the polymerization reaction, the resulting polymer has a high molecular weight, causing problems such as a decrease in solubility in a solvent
  • JP-A-1-240517 Japanese Unexamined Patent Publication No. 1-158029 Japanese Patent Laid-Open No. 2001-10983
  • the present invention relates to a cyclic olefin ring-opening copolymer having a high refractive index and abbe number, having solubility in a solvent, and useful for optical materials, a hydrogenated product thereof, and a cyclic olefin ring-opening polymerization hydrogenated composition. And tricyclopentadiene.
  • the cyclic olefin ring-opening polymer of the present invention is obtained by polymerizing cyclic olefin monomers containing the compound (1) represented by the following formula (1).
  • n is 1, 2 or 3
  • an enantiomer when present, it is a compound containing it.
  • the cyclic olefin monomers preferably further include a compound (3) represented by the following formula (3).
  • m is an integer of 0 to 3
  • a 1 to A 4 each independently represents any of the following (i) to (iv), and at least one of them represents (iii ).
  • a hydrogen atom (I) a hydrogen atom, (Ii) a halogen atom, (Iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group, (Iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii).
  • the cyclic olefin monomers preferably further include a compound (4) represented by the following formula (4).
  • B 1 to B 4 each independently represent any of the following (i) to (iii), or (iv) or (v).
  • the cyclic olefin ring-opening polymerized hydrogenated product of the present invention is preferably obtained by hydrogenating any of the above cyclic olefin ring-opened polymers. Further, in the cyclic olefin ring-opening polymerization hydrogenated composition of the present invention, the cyclic olefin ring-opening polymerization hydrogenated product is 90 to 99.99% by mass and the compounding agent incompatible with the hydrogenated product is 10 to 0.00. 01% by mass is contained. This compounding agent component is dispersed as microdomains in the hydride.
  • the tricyclopentadiene of the present invention is represented by the following formula (5).
  • the tricyclopentadiene has at least one characteristic represented by the following (a), (b) and (c).
  • (A) 1,4,4a, 4b, 5,8,8a, 9a-octahydro-1,4; 5,8-dimethano-1H-fluorene represented by the following formula (6) is 1% by mass or less
  • (B) Tricyclopentadiene represented by the following formula (5) is 3a, 4,4a, 5,8,8a, 9,9a-octahydro-4,9 represented by the following formula (2-1);
  • the endo form of 5,8-dimethano-1H-benzo [f] indene is represented by 3a, 4,4a, 5,8,8a, 9,9a-octahydro represented by the endo form and the following formula (2-1a) -4,9; 5,8-dimethano-1H-benzo [f] indene is contained in an amount
  • a cyclic olefin ring-opening polymer that has a high refractive index and abbe number and is useful for optical material applications.
  • tricyclopentadiene having at least one characteristic represented by the above (a), (b) and (c) is excellent in polymerization conversion rate as a monomer for producing a cyclic olefin polymer.
  • the resulting polymer has a high refractive index and abbe number, resulting in an excellent optical material.
  • Cyclic olefin ring-opening polymer The cyclic olefin ring-opening polymer of the present invention is produced by ring-opening polymerization of a cyclic olefin monomer containing a cyclic olefin compound.
  • the cyclic olefin monomer used in the present invention is composed of a mixture containing at least one compound (1) represented by the following formula (1) (hereinafter also referred to as “cyclic olefin compound (1)”), and the above cyclic olefin monomer.
  • n 1 to 3.
  • the amount of the cyclic olefin compound (1) contained in the cyclic olefin monomer is not particularly limited.
  • the content of the cyclic olefin compound (1) is preferably 10 to 90 mol%, preferably 30 to 80 mol% in the cyclic olefin monomer.
  • the cyclic olefin monomer (1) is contained in an amount of 10 mol% or more in the cyclic olefin monomer, the resulting ring-opening copolymer has a high refractive index, which is preferable.
  • the geometric isomer (2) contained in the cyclic olefin compound (1) is 55 mol% or more, preferably 60 mol% or more, and more preferably 80 mol% or more.
  • the tricyclopentadiene (hereinafter referred to as TCP) of the present invention is obtained by performing a Diels-Alder reaction type thermal addition reaction of dicyclopentadiene (hereinafter referred to as DCP) or DCP and cyclopentadiene (hereinafter referred to as CPD). It is synthesized by Diels-Alder reaction, and the desired monomer is obtained by distillation purification.
  • This TCP can be used as a monomer for producing a cyclic olefin ring-opening polymer.
  • TCP includes isomers represented by formula (5) and formula (6) (hereinafter, TCP represented by formula (5) is 6,6,5-TCP, and TCP represented by formula (6) is 6,5,6-TCP), and isomers having a configuration represented by endo (hereinafter referred to as endo) and exo (hereinafter referred to as exo) exist.
  • the compound represented by the above formula (2-1) is an endo isomer of 6,6,5-TCP
  • the compound represented by the above formula (2-1a) is an exo isomer of 6,6,5-TCP. is there.
  • the compounds represented by the formulas (2-1) and (2-1a) include enantiomers.
  • DCP includes endo-DCP as stereoisomerism and exo-DCP produced by the transfer of this endo-DCP with heat during the reaction.
  • TCP is generated by adding CPD to endo
  • exo-DCP there are two types of cases where CPD adds endo (FIG. 1 ( ⁇ )) and exo adds (FIG. 1 ( ⁇ )).
  • CPD adds endo
  • exo adds FIG. 1 ( ⁇ )
  • the TCP of the present invention has at least one characteristic represented by the following (a), (b) and (c).
  • (A) 6,5,6-TCP represented by the above formula (6) is 1% by mass or less, preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3%. It is below mass%. If the amount of 6,5,6-TCP exceeds 1% by mass, gelation may occur during polymerization using this monomer, and the resulting polymer may have a wide molecular weight distribution.
  • (B) The 6,6,5-TCP represented by the above formula (2-1) is 50 mol% or more, preferably 55 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol%. % Or more.
  • the term “endo body of 50 mol% or more” means that the ratio is 50/50 or more in the endo / exo ratio.
  • the content of the oxide contained in the total amount of the monomers represented by the above formula (5) and the above formula (6) is 100 ppm or less. If it exceeds 100 ppm, the polymerization activity is significantly reduced. Therefore, the TCP of the present invention is preferably stored in a nitrogen atmosphere with an antioxidant added in an amount of about 10 ppm to 500 ppm. Note that the oxide is considered to be an oxide of the TCP.
  • the TCP of the present invention preferably has all the characteristics shown in the above (a), (b) and (c).
  • Such TCP can be manufactured by the following method.
  • the purity of DCP and / or CPD as a raw material is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 98% by mass or more.
  • impurities of DCP there are mainly adducts of C 5 to C 9 chain or cyclic diene compounds and dicyclopentadiene in addition to tetrahydromethylindene, and these amounts increase, and the purity of the raw material DCP is high. When it is less than 90% by mass, heavy by-products increase in the production process.
  • the endo / exo ratio in the DCP as a raw material is preferably 80/20 or more, more preferably 90/10 or more, and further preferably 95/5 or more. If the endo / exo ratio is less than 80/20, the endo / exo ratio in TCP produced after the Diels-Alder reaction is lowered, so that the endo ratio in 6,6,5-TCP after distillation is also lowered.
  • the Diels-Alder reaction conditions are such that the reaction temperature is preferably 120 ° C. to 250 ° C., more preferably 130 ° C. to 230 ° C., still more preferably 150 ° C. to 210 ° C., and the reaction time is preferably 0.1 to 50 hours. More preferably, it is 0.5 to 10 hours.
  • the conversion rate of DCP is preferably about 30% to 50%. When the DCP conversion rate exceeds 50%, a large amount of deuterated components of CPD tetramer or more is produced, so that the selectivity of TCP is lowered, and when deuterated components are concentrated during distillation, they are precipitated. There is a risk of solidification and line blockage. When the DCP conversion rate is less than 30%, the yield of TCP is lowered and the production efficiency is lowered.
  • 6,5,6-TCP 4 to 6% by mass
  • the crude TCP is purified by a distillation purification process.
  • the distillation method is not particularly limited, but it is preferable to carry out distillation purification in two stages using a crude distillation column and a precision distillation column.
  • the unreacted DCP is removed, and then the heavy boiling point of the CPD tetramer or higher is preferably removed.
  • the distillation kettle temperature during rectification can be lowered and the reaction can be suppressed.
  • DCP is 0 to 5% by mass
  • 6,5,6-TCP 10 to 20% by mass
  • a TCP before precision distillation having a boiling point of about 90% by mass and a CPD tetramer or more of about 0-5% by mass is obtained.
  • the DCP recovered in the crude distillation process can be reused as a raw material for the Diels-Alder reaction process.
  • precision distillation is performed to remove 6,5,6-TCP represented by the formula (6) from the TCP-containing material after the crude distillation. Since 6,5,6-TCP represented by the formula (6) and 6,6,5-TCP represented by the formula (5) have very close boiling points and small relative volatility, In order to separate, it is preferable to carry out under a high vacuum in a distillation column having a high theoretical plate number.
  • the number of theoretical plates is preferably 20 or more, more preferably 25 or more.
  • the pressure at the top of the column is 0.01 kPa to 10 kPa, preferably 0.1 kPa to 5 kPa.
  • the distillation kettle temperature during rectification is preferably 200 ° C. or lower, more preferably 180 ° C.
  • the purified 6,6,5-TCP is easily oxidized, and when the amount of oxide exceeds 100 ppm, the polymerization activity is significantly reduced. For this reason, it is preferable to store an antioxidant in an amount of 100 ppm or less in a nitrogen atmosphere by adding about 10 ppm to 1000 ppm of an antioxidant.
  • an antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, dibutylhydroxytoluene and the like can be used.
  • the purified 6,6,5-TCP can be used as a monomer for producing a cyclic olefin polymer.
  • 6,6,5-TCP can be used alone or as a component of a copolymer.
  • DCP can also be used as a monomer.
  • the cyclic olefin monomer used in the present invention preferably further includes at least one cyclic olefin compound represented by the following formula (3) (hereinafter also referred to as “cyclic olefin compound (3)”).
  • cyclic olefin compound (3) represents at least one cyclic olefin compound represented by the following formula (3).
  • m is an integer of 0 to 3
  • a 1 to A 4 each independently represents any of the following (i) to (iv), and at least one of them represents (iii ).
  • Iv an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, which may be substituted with a halogen atom or the polar group (iii).
  • the cyclic olefin monomer used in the present invention may further contain at least one cyclic olefin compound represented by the following formula (4) (hereinafter also referred to as “cyclic olefin compound (4)”).
  • cyclic olefin compound (4) represents at least one cyclic olefin compound represented by the following formula (4).
  • B 1 to B 4 each independently represent any of the following (i) to (iii), or (iv) or (v).
  • (Iv) B 1 and B 2 , or B 3 and B 4 are bonded to each other to form an alkylidene group, and B 1 to B 4 not participating in the bond are independently selected from the above (i) to (iii )
  • a fluorine atom, a chlorine atom, and a bromine atom are mentioned as a halogen atom.
  • examples of the polar group include an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amino group, and a thiol group.
  • examples of the alkoxy group include a methoxy group and an ethoxy group, and an alkoxy group having 1 to 10 carbon atoms is preferable.
  • ester group examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aryloxycarbonyl groups such as phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, and biphenylyloxycarbonyl group. Those having 1 to 10 carbon atoms are preferred.
  • the amino group is preferably a primary amino group.
  • examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group, vinyl group, allyl group, and propenyl. And alkenyl groups such as groups.
  • the alicyclic hydrocarbon group is preferably one having 5 to 10 carbon atoms, and examples thereof include cycloalkyl groups such as cyclopentyl group and cyclohexyl group. This alicyclic hydrocarbon group does not have a double bond in the ring.
  • the aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, an indenyl group, a fluorenyl group, and an anthracenyl group.
  • cyclic olefin compound (3) include the following compounds. 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene, 5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene, 5-trifluoromethyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene, 5-hydroxy-bicyclo [2.2.1
  • cyclic olefin compound (3) 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene is preferably used.
  • the amount of the cyclic olefin compound (3) contained in the cyclic olefin monomer is not particularly limited.
  • the content of the cyclic olefin compound (3) in the cyclic olefin monomer is 4 to 45 mol%.
  • the content ratio of the cyclic olefin compound (3) in the cyclic olefin monomer is preferably 4 mol% or more because the obtained ring-opening copolymer tends to show solubility in a solvent such as toluene, It is preferable for the amount to be 45 mol% or less because a decrease in the refractive index of the resulting ring-opening copolymer can be suppressed.
  • cyclic olefin compound (4) include the following compounds.
  • the cyclic olefin polymer of the present invention obtained by ring-opening copolymerization of the cyclic olefin monomer, and a hydride thereof.
  • the glass transition temperature (Tg) can be easily adjusted. For example, it is possible to achieve a desired Tg temperature in the range of 110 ° C. to 180 ° C., which is desirable for use as a molded body.
  • the cyclic olefin monomer contains the cyclic olefin compound (4)
  • the higher the content of the cyclic olefin compound (4) the more the obtained open olefin compound.
  • the Tg of the ring copolymer tends to decrease, the Tg of the ring-opening copolymer becomes a desired temperature depending on the balance with the required amount of the compound (1) and the compound (4) in the monomer.
  • the amount can be selected as appropriate, whereby the Tg can be adjusted.
  • the cyclic olefin monomer according to the present invention may contain a copolymerizable monomer other than the above-mentioned cyclic olefin compounds (1), (3) and (4), but the content thereof is 20 mol%. Hereinafter, it is preferably 10 mol% or less.
  • the cyclic olefin ring-opening polymer of the present invention is produced by ring-opening copolymerization of cyclic olefin monomers containing a cyclic olefin compound.
  • a catalyst that can be used for ring-opening copolymerization of a cyclic olefin compound can be used without limitation.
  • a preferred catalyst is a catalyst using the following catalyst components (a), (b) and (c).
  • C At least one compound selected from the group consisting of tungsten compounds, molybdenum compounds, rhenium compounds, vanadium compounds, and titanium compounds.
  • organoaluminum compound which is a catalyst component (a) what is represented by following formula (7) is preferable.
  • R represents a linear alkyl group or a branched alkyl group
  • X represents a halogen atom.
  • an aluminum oxy compound can also be used as the organoaluminum compound (a).
  • organoaluminum compound (a) examples include (C 2 H 5 ) 3 Al, (i-Bu) 3 Al, (C 2 H 5 ) 2 AlCl, and (C 2 H 5 ) 1.5 AlCl 1.5. , (C 2 H 5 ) AlCl 2 , methylalumoxane and the like. These organoaluminum compounds (a) can be used singly or in combination of two or more.
  • At least one compound selected from the group consisting of nitrile group-containing compounds, ketone compounds, ether group-containing compounds, alcohol compounds and ester compounds can be used without particular limitation.
  • Examples of the nitrile group-containing compound include acetonitrile and benzonitrile.
  • Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and the like.
  • Examples of the ether group-containing compound include dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether. , Dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like.
  • Examples of the alcohol compound include methanol, ethanol, normal propanol, isopropanol, and isobutanol.
  • Examples of the ester compound include acetic acid methyl ester, acetic acid ethyl ester, acetic acid butyl ester, acetic acid phenyl ester, lactic acid ethyl ester, lactic acid butyl ester, benzoic acid methyl ester, benzoic acid ethyl ester, 5-methyl-5-methoxycarbonyl-bicyclo [ 2.2.1] hept-2-ene, 2-methyl-2-methoxycarbonyl-bicyclo [2.2.1] heptane, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2 , 5 .
  • catalyst components (b) can be used singly or in combination of two or more.
  • the catalyst component (c) at least one compound selected from the group consisting of tungsten compounds, molybdenum compounds, rhenium compounds, vanadium compounds, and titanium compounds can be used without particular limitation.
  • the compound suitably used as the catalyst component (c) include compounds described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997), for example, WCl 6 , WOCl 4 , W (CO) 6 , MoCl 5 , MoCl 5 , MoO 3 , Mo (CO) 6 , ReCl 5 , Re 2 O 7 , ReOCl 3 , VCl 4 , VOCl 3 , V 2 O 5 , TiCl 4 and the like. These can be used singly or in combination of two or more.
  • the catalyst components (a), (b) and (c) described above are used together as a ring-opening copolymerization catalyst. More preferably, a mixture (A) obtained by previously contacting the catalyst components (a) and (b) and a mixture (B) obtained by previously contacting the catalyst components (b) and (c) are used. .
  • the operation of preparing the mixture (A) by bringing the catalyst components (a) and (b) into contact with each other can be carried out in the range of room temperature to 100 ° C. under an inert gas atmosphere such as nitrogen or argon.
  • the mixing ratio is not particularly limited, but in order to improve the catalyst activity, the molar ratio (b) / (a) is preferably in the range of 0.01 / 1 to 10/1.
  • a hydrocarbon solvent such as toluene or cyclohexane can be used. This mixed solution can be used for polymerization immediately after preparation.
  • the operation of preparing the mixture (B) by bringing the catalyst components (b) and (c) into contact with each other can also be carried out in the range of room temperature to 100 ° C. in an inert gas atmosphere such as nitrogen or argon.
  • the mixing ratio is not particularly limited, but in order to improve the catalyst activity, the molar ratio (b) / (c) is preferably in the range of 1/1 to 100/1.
  • the solvent used at the time of mixing can be a hydrocarbon solvent such as toluene or cyclohexane.
  • This mixed solution can also be used for polymerization immediately after production, but it may be altered over time depending on the type of catalyst component (b) to be added, so it is desirable to use it within 1 hour after production. More preferably, it is used within 30 minutes.
  • the use ratio of the mixture (A) ((a) + (b) component) and the mixture (B) ((b) + (c) component) added to the polymerization system is not particularly limited, but the catalytic activity is improved.
  • the metal atom (mole) ratio of (a) / (c) is preferably in a range satisfying 0.5 / 1 to 50/1, and more preferably 1.5 / 1 to 30/1. The range to satisfy is more preferable.
  • the amount of the catalyst component (c) used relative to the cyclic olefin monomer is preferably such that the molar ratio with respect to the total amount of monomers and the “total amount of monomer / catalyst component (c)” is greater than 500/1. More preferred is a range larger than 1,000,000. If this ratio is small and the amount of catalyst is large, the amount of catalyst remaining in the resulting copolymer increases, which may have a great influence on the hue and deterioration of the polymer.
  • the polymerization solvent a solvent capable of dissolving or dispersing the cyclic olefin monomer and the catalyst components (a) to (c) can be used.
  • the polymerization solvent include alkanes such as pentane, hexane, heptane, octane, nonane, decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, benzene, toluene, xylene, ethylbenzene, cumene.
  • Aromatic hydrocarbons such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, etc.
  • saturated ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane.
  • the ring-opening copolymerization reaction conditions can be appropriately adjusted so that the obtained cyclic olefin copolymer has a desired molecular weight depending on the application.
  • a molecular weight regulator can also be used.
  • molecular weight regulators that can be suitably used include ⁇ - such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like.
  • ⁇ - such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like.
  • examples include olefins and styrene. Of these, 1-butene and 1-hexene are particularly preferred. These compounds can be used as molecular weight regulators alone or in combination of two or more.
  • the amount of the molecular weight regulator used is not particularly limited, but is preferably 0.005 to 0.6 moles per mole of the cyclic olefin monomer subjected to the ring-opening copolymerization reaction. The range of 0.02 to 0.5 mol is desirable.
  • the reaction time for carrying out the ring-opening copolymerization reaction is not particularly limited, but in order to improve productivity, it is 0.1 to 10 hours, preferably 0.1 to 5 hours, and more preferably 0.1 to 3 hours. It is desirable to be time.
  • the reaction temperature is desirably in the range of about 50 to 180 ° C., preferably about 70 to 160 ° C.
  • a cyclic olefin ring-opened polymer obtained by ring-opening polymerization of a cyclic olefin monomer can be used as it is, but has an olefinically unsaturated bond in the molecule. For this reason, since heat resistance is not enough depending on the use, it is preferable to further carry out hydrogenation (hydrogenation reaction) to obtain a cyclic olefin ring-opening polymerization hydrogenated product.
  • a known method can be applied to the hydrogenation step in the present invention.
  • Japanese Patent Application Laid-Open Nos. 63-218726, 1-132626, 1-224017, 2-102221, 2005-162617, 2005-162618 The hydrogenation step can be performed by applying the catalyst, solvent, temperature conditions, and the like described in Kaikai 2005-213370, JP2007-1967, and JP2007-106932A.
  • the hydrogenation rate of the olefinically unsaturated bond of the cyclic olefin ring-opening polymer is usually 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more.
  • the hydrogenation in the present invention refers to olefinic unsaturated bonds in the molecule.
  • the aromatic group has optical characteristics such as refractive index and Since it may act advantageously in heat resistance, it does not necessarily have to be hydrogenated.
  • a cyclic olefin ring-opening polymer and a cyclic olefin ring-opening polymerization hydrogenated product obtained by ring-opening polymerization of a cyclic olefin monomer and hydrogenating as necessary are known as described above.
  • the method may be used after treatment such as purification, decatalysis, and desolvation.
  • the molecular weights of the cyclic olefin ring-opened polymer and hydrogenated product of the present invention can be appropriately adjusted and produced according to the use and the like, and are not particularly limited. However, by gel permeation chromatography (GPC)
  • the polystyrene-equivalent weight average molecular weight (Mw) to be measured is preferably 20,000 to 150,000. If the molecular weight is less than 20,000, the strength of the molded product may be reduced.
  • the molecular weight distribution (Mw / Mn) of the cyclic olefin polymer and the hydride according to the present invention is not particularly limited. Preferably, it is usually 10 or less, preferably 7 or less, more preferably 4 or less. When the molecular weight distribution is wide and many low molecular weight components are mixed, the strength of the molded product may be lowered.
  • the cyclic olefin ring-opening polymerization hydrogenated product of the present invention has a high refractive index by using the cyclic olefin monomer (1) containing 55 mol%, preferably 60 mol% or more of the specific geometric isomer (2). And a high abbe number. That is, the cyclic olefin ring-opening polymerization hydrogenated product of the present invention preferably has a refractive index n D of 1.531 or more.
  • the refractive index n D is a refractive index measured at arbitrary five locations of a film sample with a laser light source of 408 nm, 633 nm, and 830 nm using a prism coupler, and the obtained value is expressed as a Cauchy equation. And the refractive index at 589 nm at 25 ° C. was calculated.
  • the cyclic olefin ring-opening polymerization hydrogenated product of the present invention preferably has an abbe number of 53 or more, more preferably 55 or more.
  • n D , n F , and n C are refractive indexes at 589.2 nm, 486.1 nm, and 656.3 nm obtained by the above regression calculation.
  • the Tg of the cyclic olefin ring-opening polymerization hydrogenated product of the present invention is preferably 125 ° C. to 200 ° C., more preferably 130 to 190 ° C. If the Tg is lower than 125 ° C., the final product such as an optical lens cannot be put into practical use. On the other hand, if the Tg exceeds 200 ° C., the injection molding temperature must be set to a high temperature of 300 ° C. or more, and the deterioration coloring of the resin becomes remarkable.
  • Such a cyclic olefin ring-opening polymerization hydrogenated product of the present invention can be suitably produced by the above-described production method of the cyclic olefin ring-opening polymer.
  • the cyclic olefin ring-opened polymer of the present invention may be used for molding as it is, but it is used by adding additives such as known antioxidants and ultraviolet absorbers for improving heat resistance and light resistance. Can do.
  • additives for example, known phenol compounds, thiol compounds, sulfide compounds, disulfide compounds, phosphorus compounds, etc. can be used as additives to the resin.
  • additives may be added to the cyclic olefin ring-opening polymer of the present invention depending on the properties of the target molded article.
  • colorants such as dyes and pigments may be added, and a leveling agent may be added to improve the smoothness of the resulting film.
  • the leveling agent include a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, and a silicone leveling agent.
  • a compounding agent may be added to the cyclic olefin ring-opening polymerization hydrogenated product.
  • a rubbery polymer is preferable. Examples of the rubbery polymer are incompatible with the copolymer of an aromatic vinyl monomer and a conjugated diene monomer, a hydrogenated product thereof, and the cyclic olefin ring-opening polymerization hydrogenated product of the present invention. Examples include norbornene rubbery polymers.
  • the copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. From the viewpoint of weather resistance, hydrogenated olefinic double bond moieties other than aromatic rings are more preferred.
  • styrene / butadiene block copolymer styrene / butadiene / styrene / block copolymer, styrene / ethylene butylene / styrene / block copolymer, styrene / isoprene / block copolymer, styrene / isoprene / styrene.
  • -Block copolymers, and hydrogenated products thereof styrene / butadiene / random copolymers and the like.
  • the compounding agent when the composition of the present invention is molded into a container, it is necessary to have transparency enough to confirm the amount and state of the contents.
  • the compounding agent preferably has a small difference in refractive index from the cyclic olefin ring-opening polymerization hydrogenated product to which the compounding agent is added.
  • the content becomes so opaque that the amount of contents cannot be seen when added in a large amount.
  • the amount is too small, turbidity prevention in the steam sterilization treatment becomes insufficient.
  • the cyclic olefin ring-opening polymerization hydrogenated product is 90 to 99.99% by mass, preferably 95 to 99.98% by mass, more preferably 99 to 99.95% by mass, and particularly preferably 99.5%. 10 to 0.01% by weight, preferably 5 to 0.02% by weight, more preferably 1 to 0.05% by weight, and particularly preferably 0.5 to 0.1% by weight.
  • Add and disperse in the cyclic olefin ring-opening polymerization hydride If the amount added is too large, the transparency, glass transition temperature, and heat resistance of the resin will decrease. If there is too little addition amount, the effect which mix
  • the method to be added is not particularly limited as long as the compounding agent is sufficiently dispersed as a microdomain in the cyclic olefin ring-opening polymerization hydrogenated product.
  • a rubber polymer is used as a compounding agent, a method of kneading the resin temperature in a molten state with a mixer, a twin-screw kneader or the like, a solidifying method, a casting method, There is a method of removing the solvent by a direct drying method.
  • the microdomain When the rubbery polymer is used as a compounding agent, the microdomain is almost spherical and the variation in particle size among particles is small. Usually, the diameter is 0.3 ⁇ m0.3 or less, preferably 0.2 ⁇ m or less. If it is this particle size, the fall of the transparency of the cyclic olefin ring-opening polymerization hydrogenated composition by addition of a rubber-like polymer is small, and does not become a problem.
  • the microdomains are preferably substantially spherical, preferably have no variation in particle size among particles, and preferably have a diameter of 0.3 ⁇ m or less, particularly 0.2 ⁇ m or less. Even when the microdomain does not have a spherical shape, the diameter of the smallest sphere that can confine the microdomain is preferably 0.3 ⁇ m or less, particularly preferably 0.2 ⁇ m or less.
  • the cyclic olefin ring-opening polymer according to the present invention in particular, the cyclic olefin ring-opening polymerization hydrogenated product, which is a hydride, is molded into a desired shape such as a lens shape, a film shape, or a sheet shape by a known method. It can be suitably used for various optical components such as optical lenses and medical containers such as prefilled syringes.
  • Glass transition temperature (Tg) Using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.), an extrapolated glass transition start temperature (hereinafter simply referred to as glass transition temperature (Tg)) was determined according to Japanese Industrial Standard K7121.
  • Weight average molecular weight and molecular weight distribution Using gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), tetrahydrofuran (THF) as a solvent, weight average molecular weight (Mw) and molecular weight in terms of polystyrene Distribution (Mw / Mn) was measured.
  • GPC gel permeation chromatography
  • HLC-8020 tetrahydrofuran
  • Mw weight average molecular weight
  • Mn molecular weight in terms of polystyrene Distribution
  • Geometric isomer (2) in cyclic olefin compound (1) Geometric isomer contained in cyclic olefin compound (1) using gas chromatography (manufactured by Shimadzu Corporation, trade name: GC-2014) The ratio of the geometric isomer (2) to the whole was calculated.
  • the refractive index was measured at any five locations on the film sample, and the average value of three points excluding the maximum and minimum values was adopted.
  • the laser light source of 408 nm, 633 nm, and 830 nm was used as the light source, and the refractive index at 589 nm (25 ° C.) was calculated from the obtained refractive index by regression calculation using the Cauchy equation.
  • the polymer was kneaded with a twin-screw kneader (TEM-37BS manufactured by Toshiba Machine, temperature 280 ° C., screw rotation speed 100 rpm, feeder rotation speed 10 rpm, discharge rate 18 Kg / hour) and extruded to give pellets 1.
  • Example 1 As a cyclic olefin monomer, TCP containing 82% of a compound represented by the formula (2-1) (including enantiomers, hereinafter also referred to as compound (2-1)) in the geometric isomer ( 71.9 g, 363 mmol, the content of geometric isomers other than compound (2-1) is 18%.), 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2,5 . 1 7,10] dodeca-3-ene (37.5 g, 161 mmol. Hereinafter, referred to as DNM.), Bicyclo [2.2.1] hept-2-ene (22.1 g, 235 mmol.
  • NB 1-butene (1.69 g, 30.1 mmol) as a molecular weight regulator was added to toluene (275 g), and the mixture was heated to 105 ° C. with stirring. Separately, a toluene solution (0.28 mL) obtained by mixing i-Bu 3 Al (75 ⁇ mol) and methanol (11 ⁇ mol) at room temperature and a toluene solution (0.75 mL) of WCl 6 (38 ⁇ mol) were prepared.
  • the monomer-derived composition in the polymer was 48.1 mol% derived from tricyclopentadiene, and 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 2, 5 . It was 21.4 mol% derived from 1 7,10 ] dodec-3-ene and 30.5 mol% derived from bicyclo [2.2.1] hept-2-ene.
  • the toluene solution (353 g) of the ring-opening copolymer [1] obtained as described above was transferred to a hydrogenation reaction vessel, and toluene (236 g) was added and stirred to obtain a homogeneous solution.
  • Certain Ru [4-CH 3 (CH 2 ) 4 C 6 H 4 CO 2 ] H (CO) [P (C 6 H 5 ) 3 ] (49.3 mg, 582 ⁇ mol) was added.
  • hydrogen was introduced to 7 MPa, and finally the temperature was raised to 160 to 165 ° C., and the reaction was carried out for 3 hours with the introduced hydrogen gas pressure being 9 to 10 MPa.
  • Example 4 Hydrogenated ring-opening copolymer obtained in Example 1 [1] 99.6 parts by mass of rubber polymer (JSR Dynalon 8903P: styrene / ethylene butylene / styrene / block copolymer) 0.4 parts by mass, Anti-aging agent (BASF Irganox 1010) 0.03 part by mass was added, twin screw kneader (Toshiba Machine TEM-37BS, temperature 280 ° C., screw rotation speed 100 rpm, feeder rotation speed 10 rpm, discharge rate 18 kg / hour. ) And extruded to obtain pellets 1.
  • Rubber polymer JSR Dynalon 8903P: styrene / ethylene butylene / styrene / block copolymer
  • Anti-aging agent BASF Irganox 1010
  • twin screw kneader Toshiba Machine TEM-37BS, temperature 280 ° C., screw rotation speed 100
  • the pellet 1 was used for injection molding (S2000i100B manufactured by FANUC, clamping pressure 100 tons, resin temperature 280 ° C., mold temperature 120 ° C.) to prepare a test plate of 60 mm ⁇ 80 mm ⁇ 1.0 mm. This plate was sliced to a thickness of about 0.1 ⁇ m, the polystyrene part was stained with ruthenium tetroxide, and observed with a transmission electron microscope. The rubbery polymer was found to have a diameter of about 0.2 ⁇ m in a hydride matrix. The structure was almost spherical microdomain.
  • test plate was hung on a dedicated metal basket, set in an autoclave (HV-240MIV manufactured by Hirayama Seisakusho), and treated at 123 ° C. for 70 minutes. After 70 minutes, after cooling to 60 degrees, the apparatus was opened and the metal basket was taken out and aged in the atmosphere for 30 minutes. The appearance of the test plate after aging was good, and no white turbidity, cracking, deformation due to heat, or cracking was observed with a microscope.
  • HV-240MIV manufactured by Hirayama Seisakusho
  • Example 2 0.03 parts by mass of an antioxidant (BASF Irganox 1010) was added to 100 parts by mass of the hydrogenated ring-opening copolymer [1] obtained in Example 1, and a twin-screw kneader (TEM-37BS manufactured by Toshiba Machine). And the same conditions as in Example 4) and extruded to obtain pellets 2. Using this pellet 2, injection molding (S2000i100S manufactured by FANUC, the same conditions as in Example 4) was performed to prepare a test plate of 60 mm ⁇ 80 mm ⁇ 1.0 mm.
  • BASF Irganox 1010 antioxidant
  • TEM-37BS manufactured by Toshiba Machine
  • test plate When the test plate was autoclaved in the same manner as in Example 4 and observed, it was visually opaque and opaque, and cracking was also confirmed by microscope observation.
  • TCP TCP
  • the molecular weight and Tg were measured by the methods described above, and the other evaluation items, namely intrinsic viscosity, gel evaluation and the proportion of structural units in the polymer, were measured or evaluated by the following methods.
  • Intrinsic viscosity [ ⁇ inh ] Using an Ubbelohde viscometer, the intrinsic viscosity was measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in chlorobenzene.
  • the criterion was that the smaller the number of gels, the better the gel generation suppression performance.
  • the number of gels was 0-2, “ ⁇ ”, 3-9 “ ⁇ ”, and 10 or more “x”. When the number of gels is 10 or more, defects at the time of commercialization are remarkably confirmed, which is an unacceptable level.
  • (3) Composition of each component in TCP containing material It measured by gas chromatography (GC). As the capillary column, TC-WAX manufactured by GL Sciences Inc. was used.
  • TCP-containing material (I) was simply distilled to obtain a TCP-containing material (II) from which light-boiling components such as unreacted DCP and heavy-boiling material higher than the CPD tetramer were removed.
  • TCP-containing material (II) was subjected to rectification in a distillation column (packing: Helipak) at a column top pressure of 0.5 kPa and a reflux ratio of 30, and expressed in Formula (5) in the distillate.
  • mass ratio of the compound / the compound represented by the formula (6) reached 99.0 / 1.0
  • recovery of the TCP-containing material (III) was started.
  • 200 ppm of an antioxidant was added to the recovered TCP-containing material (III) to obtain TCP (A).
  • a gas chromatography chart is shown in FIG.
  • TCP (J) was obtained from TCP (B) in the same manner as in Example 1 except that the conditions described in Table 1 were changed.
  • Table 2 shows the characteristics of TCP (B) to TCP (J).
  • Polymer Example 1 100 parts by mass of TCP (A) obtained in Monomer Example 1 and 9 parts by mass of 1-hexene as a molecular weight regulator were added to 280 parts by mass of cyclohexane, and the mixture was heated and stirred at 105 ° C. Separately, 0.005 part by mass of triisobutylaluminum and 0.003 part by mass of methanol were added, and further 0.005 part by mass of WCl 6 was added and reacted for 1 hour to obtain a polymer. The polymer yield was as good as 99% by mass. The obtained polymer solution was put into an autoclave, and 200 parts by mass of cyclohexane was further added.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Tg glass transition temperature
  • the obtained cyclic olefin polymerized hydrogen adduct solution was solidified using a large amount of methanol and dried to obtain a cyclic olefin polymerized hydrogen adduct.
  • the number of gels was 1, and it was determined as “ ⁇ ”.
  • the overall evaluation of each example and each comparative example is a case where the polymerization conversion rate is 92% or more, the molecular weight distribution (Mw / Mn) is 2.9 or less, and the gel evaluation satisfies all the characteristics of ⁇ or more. “O”, and “x” when not satisfied.
  • the results are shown in Table 3.
  • the cyclic olefin ring-opening polymer according to the present invention can be suitably used as an optical component as a thermoplastic transparent resin excellent in light transmittance and heat resistance.
  • optical components include optical lenses, films, and sheets. Specific examples thereof include imaging lenses, light guide plates, retardation films, protective films, adhesive films, touch panels, transparent electrode substrates, TFT substrates, and colors. Examples thereof include medical containers such as filter substrates and prefilled syringes.
  • the cyclic olefin ring-opening polymer according to the present invention in particular the cyclic olefin ring-opening copolymer hydrogenated hydride, has a high refractive index and a high abebe number, and thus can be suitably used for various molded article production applications.
  • it can be suitably used for the production of molded articles used for various optical applications such as lenses and films, and can be suitably used for optical lens applications.

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EP3162350A4 (en) * 2014-06-30 2018-04-04 Taisei Kako Co., Ltd. Pharmaceutical product container and pharmaceutical preparation
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