CN103159914B - Cyclenes hydro carbons ring-opening copolymer - Google Patents

Cyclenes hydro carbons ring-opening copolymer Download PDF

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CN103159914B
CN103159914B CN201210509022.1A CN201210509022A CN103159914B CN 103159914 B CN103159914 B CN 103159914B CN 201210509022 A CN201210509022 A CN 201210509022A CN 103159914 B CN103159914 B CN 103159914B
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hydro carbons
ring
opening copolymer
cyclenes hydro
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CN103159914A (en
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神谷育代
庄田良平
凑裕二
多田罗了嗣
铃木理奈
茂木武志
丸山洋郎
丸山洋一郎
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use

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Abstract

There is provided a kind of and can realize high optical characteristics (high index of refraction, high Abbe number, low-birefringence) and excellent resin processability simultaneously, and there is the cycloolefin ring-opening copolymer of low oxygen permeability, high strength.A kind of cyclenes hydro carbons ring-opening copolymer, the repetitive represented by its contained (1) and formula (2).M is the integer of 1～3, and p, q are each independently the integer of 0～2, R1～R12Separately represent hydrogen atom, halogen atom, any one of the aliphatic alkyl that carbon number is 1～4 that also can be substituted with halogen atoms.

Description

Cyclenes hydro carbons ring-opening copolymer
Technical field
The present invention relates to one and there is high index of refraction, high Abbe number and low birefringence, and resin processing Property excellent, and there is the cyclenes hydro carbons ring-opening copolymer of low oxygen permeability, high strength.
Background technology
Cyclenes hydrocarbon monomer is carried out ring opening metathesis polymerization (Ring-Opening Metathesis Polymerization, hereinafter referred to as ROMP), thereafter double bond contained in this copolymer is hydrogenated (with It is also known as down ROMP-hydrogenation) and the cyclenes hydro carbons ring-opening copolymer of gained is to have high transmission rate and high folding Penetrate the thermoplastic transparent resin of the feature such as rate and high-fire resistance.
In the optical lens or the optical material such as optical fiber, optical thin film field of required above-mentioned functions, this heat The application of plastic transparent resin constantly expands.Particularly in optical lens purposes, along with carrying optical lens The miniaturization of the goods of mirror, it is desirable to further high index of refraction (nD≥1.525).And, simultaneously Produce following problem: in order to realize the raising of image boldness, it has to reach high Abbe number (>=53), low-birefringence (CR(stress-optical coefficient)≤1300 × 10-12Pa-1)。
Above-mentioned thermoplastic resin is good forming ability owing to the mobility when transparency is high, melted is high, and resistance to Dissolved or good chemical resistance, be the most also applicable to prefilled syringe, vial, transfusion use In the various container for medical use such as bag etc..In this purposes, from the viewpoint of the quality of medicine keeps, Seek low oxygen permeability.And, it is desirable to it is resistant to the high strength of practicality.
As the high index of refraction (n realizing transparent resinD>=1.525) and high Abbe number (>=53) Method, reports the technology (patent documentation making the cyclenes hydro carbons monomer copolymerization represented by following formula (12) 1)。
[changing 1]
In formula (12), m is the integer of 1～3, R13For the fat that hydrogen atom, carbon number are 1～10 Race's alkyl, alicyclic alkyl or aromatic hydrocarbyl.
It addition, in the chemical formula of this specification, omit institute on the looped carbon atom of structure and this carbon atom The hydrogen atom of bond and record.
To the particularly R in the cyclenes hydrocarbon monomer represented by above-mentioned formula (12)13Monomer for hydrogen atom Individually carry out ROMP-hydrogenation and the n of the polymer of gainedDBe 1.541, Abbe number be 56, CRValue is 1100×10-12Pa-1, meet required above-mentioned optical characteristics.
But, as the polymer that this optical characteristics is excellent, vitrification point (hereinafter referred to as Tg) shows It it is 193 DEG C.Cyclenes hydro carbons ring-opening polymerization polymer is made molded body through forming steps such as ejection formations and is used, If but forming temperature is too high, then produces polymer variable color in the fabrication process, add the phenomenon of heat deterioration.For Corresponding with practical forming temperature, it is necessary to the Tg making cyclenes hydro carbons ring-opening polymerization polymer is 120 DEG C～180 DEG C Region.
Before, as the technology in order to make the Tg of cycloolefin class ring-opening polymerization polymer reduce, it is known to make double Ring [2.2.1] hept-2-ene" (norborene) or three ring [4.3.0.12,5] decyl-3,7-diene (bicyclopentadiene) etc. The method (patent documentation 1) of copolymerization.
But, if making those compound copolymerization, then increase along with copolymerization ratios and cause Tg to reduce, but produce Raw CRValue is more than 1300 × 10-12Pa-1Problem.As mentioned above, it is difficult to obtain and can make CRValue reduces, That is under the state maintaining low birefringence, make Tg reduce and improve the cyclenes hydro carbons ring opening copolymer of processability Thing.
Monomer component as cyclenes hydro carbons ring-opening copolymer, it is known to there is the fall ice of benzyl ring at side chain Sheet alkene (patent documentation 2, patent documentation 3).
But, about the most unknown with the copolymer of the cyclenes hydrocarbon monomer represented by above-mentioned formula (12), Further with regards to the synthesis of cyclenes hydro carbons ring-opening copolymer that those compounds are hydrogenated, Yi Jiqi Physical property is the most unknown.
Prior art literature
Patent documentation
Patent documentation 1 Japanese Patent Laid-Open 2011-26587 publication
Patent documentation 2 Japanese Patent Laid-Open No. Sho 51-11900 publication
Patent documentation 3 Japanese Patent Laid-Open 10-120768 publication
Summary of the invention
The present invention forms to tackle above-mentioned problem, its object is to offer and can realize high light simultaneously Learn characteristic (high index of refraction, high Abbe number, low-birefringence) and excellent resin processability, and have suitable Low oxygen permeability, the cycloolefin ring-opening copolymer of high strength in medical container purposes.
The MOLECULE DESIGN of the cycloolefin ring-opening copolymer with following character is studied: maintain display For refractive index nDBe more than 1.525, Abbe number be more than 53, CRValue is 1300 × 10-12Pa-1Following Excellent optical characteristics, can make Tg to improve resin processability is 120 DEG C～180 DEG C.
The optics that can be obtained excellence by the homopolymer of the cyclenes hydrocarbon monomer represented by above-mentioned formula (12) is special Property.This homopolymer is shown as nDBe 1.541, Abbe number be 56, CRValue is 1100 × 10-12Pa-1.So And, the Tg of this homopolymer is 193 DEG C, resin poor in processability.
If making the cyclenes hydrocarbon monomer represented by above-mentioned formula (12) and norborene or bicyclopentadiene copolymerization, Or with there is the monomer copolymerization of aliphatic lateral chain, then can reduce Tg.It will be appreciated, however, that those copolymers are led Cause the particularly C in optical characteristicsRThe rising of value.
Understand by the ring carbon atom making 5 or No. 6 positions at dicyclo [2.2.1] hept-2-ene" (norborene) On be imported with the monomer copolymerization of alicyclic alkyl, C can be manufacturedRValue is 1300 × 10-12Pa-1Below and Tg It it is the cycloolefin ring-opening copolymer of less than 180 DEG C.
Think that the main chain of cycloolefin ring-opening copolymer is given just by it by importing clicyclic hydrocarbon base side chain Property, and by the ring carbon atom of 5 or No. 6 positions of above-mentioned norborene and constituting clicyclic hydrocarbon with singly-bound Ring carbon atom carry out bond, this alicyclic alkyl becomes to be carried out as central shaft by bond axle certain Rotation.Its result, maintains excellent optical characteristics, and Tg can be made to reduce.The present invention is based on this kind Knowledge opinion.
The cyclenes hydro carbons ring-opening copolymer of the present invention is characterised by comprising following formula (1) and formula (2) institute The repetitive represented.
[changing 2]
In formula (1), m is the integer of 1～3, and in formula (2), p, q are each independently 0～2 Integer, R1～R12Separately represent any one of following (i)～(iii):
(i) hydrogen atom,
(ii) halogen atom,
(iii) carbon number also can being substituted with halogen atoms is the aliphatic alkyl of 1～4.
The cyclenes hydro carbons ring-opening copolymer of the present invention is characterised by: comprise 30 matter in all construction units Amount %～the repetitive represented by above-mentioned formula (1), 10 mass %～70 mass % upper of 90 mass % State the repetitive represented by formula (2).
And, it is characterised in that: in all construction units, comprise the following of below 10 mass % further Repetitive represented by formula (3).
[changing 3]
In formula (3), n is the integer of 0～3, B1～B4Separately represent following (i)～(v) Any one:
(i) hydrogen atom,
(ii) halogen atom,
(iii) group that free alkoxyl, hydroxyl, ester group, cyano group, amino and mercapto constituted is selected Polar group,
(iv) also can be by halogen atom or aliphatic that described polar group (iii) substituted carbon number is 1～10 Alkyl,
(v)B1With B3、B1With B4、B2With B3, or B2With B4Mutually bond and with bond respectively Carbon atom together forms circulus, and is not involved in the B of above-mentioned bond1～B4Represent above-mentioned independently of each other Any one of (i)～(iv).
The cyclenes hydro carbons ring-opening copolymer of the present invention is characterised by: utilize chromatograph of gel permeation to measure The weight average molecular weight of polystyrene conversion be 20,000～150,000.
Other cyclenes hydro carbons ring-opening copolymers of the present invention are characterised by: comprise following formula (1a) institute table The repetitive shown with selected from the repetition represented by least 1 formula of following formula (4) and following formula (5) Unit.
[changing 4]
M, p, q, R in formula (1a), formula (4) and formula (5)1～R12With formula (1) and formula (2) In m, p, q, R1～R12Identical.
And, it is characterised in that: comprise the repetitive represented by following formula (3a) further.
[changing 5]
N, B in formula (3a)1～B4With n, the B in formula (3)1～B4Identical.
The cyclenes hydro carbons ring-opening copolymer of the present invention comprises the repetition represented by above-mentioned formula (1) and formula (2) Unit, therefore obtains and realizes high index of refraction and high Abbe number and low-birefringence, and it is excellent to have mouldability The optical material of the Tg with practicality.And, it is thus achieved that there is the doctor of low oxygen permeability, high strength Treat appliance material.
Detailed description of the invention
The cyclenes hydro carbons ring-opening copolymer of the present invention comprises the repetition represented by above-mentioned formula (1) and formula (2) Unit.
Preferably in formula (1) and formula (2), m is 1, and p, q are respectively 0, R1～R12For hydrogen atom.
And, the cyclenes hydro carbons ring-opening copolymer of the present invention can not make CRValue enters one in the range of deteriorating Step has the repetitive represented by above-mentioned formula (3).
In the cyclenes hydro carbons ring-opening copolymer of the present invention, the content ratio of each repetitive there is no limit especially Fixed, all repetitives comprise preferably 30 mass %～90 mass %, more preferably 40 mass The repetitive (1) of about %～85 mass %, even more preferably comprises 60 mass %～80 mass % The repetitive (1) of left and right, and, all repetitives comprise preferably 10 mass %～70 About quality %, more preferably 15 mass %～60 mass %, be even more preferably 20 mass %～40 Repetitive (2) about quality %.
In the case of cyclenes hydro carbons ring-opening copolymer comprises repetitive (3) further, in all repetitions Ratio contained in unit preferably becomes below 10 mass %.
Comprise the cyclenes hydro carbons ring-opening copolymer of repetitive represented by above-mentioned formula (1) and formula (2) Molecular weight can suitably adjust according to purposes etc. and manufacture, and is not particularly limited, but utilizes gel infiltration color Spectrometer (Gel Permeation Chromatography, GPC) and the weight of polystyrene conversion that measures Mean molecule quantity (Mw) is preferably 20,000～150,000.In the case of mean molecule quantity is too small, There is the phenomenon of the intensity step-down of products formed.On the other hand, in the case of mean molecule quantity is excessive, molten Fluid viscosity excessively uprises, and there is productivity or the mouldability of the cyclenes hydro carbons ring-opening copolymer of the present invention, adds The phenomenon that work deteriorates.
And, the molecular weight distribution (Mw/Mn) of the cyclenes hydro carbons ring-opening copolymer of the present invention there is no especially Limit, such as in the case of the middle uses such as thin film application, it is generally desirable to be usually 1.5～10, be preferably 2～8, more preferably 2.2～5.
Cyclenes hydro carbons ring opening copolymer as the repetitive comprised represented by above-mentioned formula (1) and formula (2) The optical characteristic value of thing, refractive index nDBeing more than 1.525, be preferably more than 1.530, Abbe number is 53 Above, it is preferably more than 55, CRValue is 1300 × 10-12Pa-1Below, 1250 × 10 it are preferably-12Pa-1 Below.
Herein, refractive index nD is to use prism coupler, utilizes 408nm, 633nm and 830nm LASER Light Source, measure film sample any 5 at refractive index, with Cauchy Formula, the value of gained is entered Row regression Calculation, calculates the refractive index of 589nm (25 DEG C) and the value obtained.
Abbe number represents and utilizes v=(nD-1)/(nF-nC) formula and the value (v) that calculates.So-called herein ND、nF、nC589.2nm, 486.1nm, the 656.3nm being to utilize above-mentioned regression Calculation and obtain Refractive index.
CRValue is (stress-optical coefficient) value, is the amount of the size representing photoelasticity effect.It is to confession When sample of having a try applies external force and is deformed, as the birefringent mark produced due to optical anisotropy 2 accurate refractive indexs n1、n2Poor Δ n (=n1-n2) divided by the value of the stress σ corresponding with this deformation, That is Δ n/ σ is CRValue.
Cyclenes hydro carbons ring-opening copolymer is made the extruded thin plate that thickness is 1mm, measures oneself and become The Δ n value (delay under 550nm when the parallel direction of type pellicular front applies the external force of 5kg～15kg weight Value/thin film is thick).
Comprise the cyclenes hydro carbons ring-opening copolymer of repetitive represented by above-mentioned formula (1) and formula (2) Tg is preferably 120 DEG C～180 DEG C, more preferably 125 DEG C～170 DEG C.If Tg becomes less than 120 DEG C , then there is the situation that the final goodss such as optical lens become and are weak to practicality in value.On the other hand, if Tg More than 180 DEG C, then ejection formation temperature must be set to the high temperature of more than 300 DEG C, there is generation resin and The situation of color.
Cyclenes hydro carbons ring opening copolymer at the repetitive that will comprise represented by above-mentioned formula (1) and formula (2) In the case of in thing medical container purposes in medical apparatus Material Field, from the quality of keeping medicine From the viewpoint of holding, it is desirable to oxygen permeability is low.As oxygen permeability, (unit is oxygen transmission rate cm3·mm/m2/ day/atm) the lowest more good, the preferably oxygen transmission rate less than 70, more preferably less than 50 Oxygen transmission rate.
And, in the case of using in medical container purposes, consider from viewpoint in practical use, it is desirable to high Mechanical strength.Bending strength shown in ASTM D790 can be made by the mechanical strength of above-mentioned copolymer It it is an index.Bending strength (unit is MPa) is the highest more good, the bending strength of preferably more than 70, The bending strength of more preferably more than 73, is even more preferably the bending strength of more than 80.
In medical apparatus Material Field, preferably oxygen permeability and mechanical strength is excellent, and oxygen transmission rate is less than 70 (cm3·mm/m2/ day/atm) and bending strength be more than 70MPa, be preferably more than 73MPa, more It is preferably more than 80MPa.
The cyclenes hydro carbons ring-opening copolymer comprising the repetitive represented by above-mentioned formula (1) and formula (2) can Obtain by the cyclenes hydro carbons ring-opening copolymer becoming intermediate is hydrogenated.
As becoming the cyclenes hydro carbons ring-opening copolymer of intermediate, can enumerate and comprise above-mentioned formula (1a) institute table The repetitive that shows and selected from above-mentioned formula (4) and the weight represented by least 1 formula of above-mentioned formula (5) The copolymer of multiple unit.Preferably enumerate the repetitive represented by contained (1a) and formula (4) is represented The copolymer (first) of repetitive or contained (1a) represented by repetitive and formula (5) The copolymer (second) of represented repetitive, more preferably becomes the copolymer (second) easily hydrogenated.
Become and the cyclenes hydro carbons ring-opening copolymer of intermediate can further include represented by above-mentioned formula (3a) Repetitive.
The repetitive represented by formula (1a) of the cyclenes hydro carbons ring-opening copolymer becoming intermediate can Obtain by the cyclenes hydrocarbon monomer represented by following formula (1m) is carried out ROMP.
[changing 6]
In formula (1m), m is the integer of 1～3.
The preferred five rings of the concrete example [6.5.1.0 of the cyclenes hydrocarbon monomer represented by formula (1m)2,7.13,6.09,13] ten Five carbon-4,10-diene (the most also known as " three cyclopentadiene ") (m=1), seven rings [8.7.0.12,9.03,8.14,7.111,17.012,16] 20 carbon-5,13-diene (the most also known as " tetracyclopentadiene ") (m =2) and nine ring [10.9.1.02,11.13,10.04,9.15,8.013,21.114,20.015,19] 25 carbon-6,16-diene (with The most also known as " five cyclopentadiene ") (m=3), in those compounds, particularly preferably use is readily synthesized and obtains Three cyclopentadiene obtained.
Repetitive represented by above-mentioned formula (4) can be by the cycloolefin represented by following formula (4m) Class monomer carries out ROMP and obtains.
[changing 7]
In formula (4m), p, q are each independently the integer of 0～2, R1～R12Separately represent The i fat that carbon number is 1～4 that () hydrogen atom, (ii) halogen atom, (iii) also can be substituted with halogen atoms Race's alkyl.
Herein, halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms.
Carbon number be 1～4 aliphatic alkyl include, for example the alkyl such as methyl, ethyl, propyl group, vinyl, The thiazolinyl such as pi-allyl, acrylic.
The concrete example of the monomer represented by formula (4m) is preferably 5-phenyl-dicyclo [2.2.1] hept-2-ene", 5-first Base-5-phenyl-dicyclo [2.2.1] hept-2-ene", 6-methyl-5-phenyl-dicyclo [2.2.1] hept-2-ene", 5-fluoro-5-phenyl -dicyclo [2.2.1] hept-2-ene", 5-2 '-naphthyl-dicyclo [2.2.1] hept-2-ene", 5-trifluoromethyl-5-phenyl-dicyclo [2.2.1] hept-2-ene", particularly preferably uses the 5-phenyl-dicyclo being readily synthesized and obtaining in those compounds [2.2.1] hept-2-ene".
Repetitive represented by above-mentioned formula (5) can be by the cycloolefin represented by following formula (5m) Class monomer carries out ROMP and obtains.
[changing 8]
In formula (5m), R1～R3、R5、R6、R8、R10、R11With the R in above-mentioned formula (4m)1 Etc. identical.
The concrete example of the monomer represented by formula (5m) is preferably 5-(3-cyclohexene-1-base) dicyclo [2.2.1] hept-2- Alkene, 5-methyl-5-(3-cyclohexene-1-base) dicyclo [2.2.1] hept-2-ene", 5-methyl-5-(4-methyl-3-cyclohexene-1- Base) dicyclo [2.2.1] hept-2-ene", 6-methyl-5-(3-cyclohexene-1-base) dicyclo [2.2.1] hept-2-ene", 5-fluoro-5-(3- Cyclohexene-1-base) dicyclo [2.2.1] hept-2-ene", 5-trifluoromethyl-5-(3-cyclohexene-1-base) dicyclo [2.2.1] heptan -2-alkene, particularly preferably uses 5-(3-cyclohexene-1-base) dicyclo being readily synthesized and obtaining in those compounds [2.2.1] hept-2-ene".
Become the repetition represented by formula (3a) that can contain in the cyclenes hydro carbons ring-opening copolymer of intermediate Unit can obtain by the cyclenes hydrocarbon monomer represented by following formula (3m) is carried out ROMP.
[changing 9]
In formula (3m), n and B1～B4With n and B in above-mentioned formula (3a)1～B4Identical.
At B1～B4In, polar group can enumerate alkoxyl, hydroxyl, ester group, cyano group, amino and mercapto. Alkoxyl include, for example methoxyl group, ethyoxyl etc., and preferably carbon number is the alkoxyl of 1～10.Ester It is 1～10 that base include, for example the alkoxy carbonyl such as methoxycarbonyl, ethoxy carbonyl, preferably carbon number Alkoxy carbonyl.Amino preferably enumerates the primary amino radical that primary amino radical, preferably carbon number are 1～10.
The concrete example of the monomer represented by formula (3m) can enumerate dicyclo [2.2.1] hept-2-ene" (norborene), 5-methyl-bicyclo [2.2.1] hept-2-ene", 5-ethyl-dicyclo [2.2.1] hept-2-ene", 5-propyl group-dicyclo [2.2.1] hept-2- Alkene, 5-butyl-dicyclo [2.2.1] hept-2-ene", 5-hexyl-dicyclo [2.2.1] hept-2-ene", 5-heptyl-dicyclo [2.2.1] Hept-2-ene", 5-octyl group-dicyclo [2.2.1] hept-2-ene", three ring [4.3.0.12,5] decyl-3,7-diene (bicyclopentadiene), Three ring [4.3.0.12,5] decyl-3-alkene, three ring [4.4.0.12,5] 11 carbon-3-alkene, 7-methyl-three ring [4.3.0.12,5] last of the ten Heavenly stems -3-alkene, 7-ethyl-three ring [4.3.0.12,5] decyl-3-alkene, 7,8-dimethyl-three ring [4.3.0.12,5] decyl-3-alkene, 7,8,9- Trimethyl-three ring [4.3.0.12,5] decyl-3-alkene, 8-methyl-three ring [4.4.0.12,5] 11 carbon-3-alkene, 5-methoxyl group Carbonyl-dicyclo [2.2.1] hept-2-ene", 5-trifluoromethyl-5-methoxycarbonyl-dicyclo [2.2.1] hept-2-ene", 5-first Base-5-methoxycarbonyl-dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-dicyclo [2.2.1] hept-2-ene", 5-ethoxy- Dicyclo [2.2.1] hept-2-ene", 5-cyano group-dicyclo [2.2.1] hept-2-ene", 5-amino-bicyclic [2.2.1] hept-2-ene", 8-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-methyl-8-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-trifluoromethyl-8-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 Carbon-3-alkene, 8-hydroxyl-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-ethoxy-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-methyl-8-ethoxy-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-cyano group-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 8-amino-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene etc..
Comprise the repetitive represented by above-mentioned formula (1a) and selected from above-mentioned formula (4) and above-mentioned formula (5) The copolymer of the repetitive represented by least 1 formula can be by above-mentioned cyclenes hydrocarbon monomer be carried out ROMP and obtain.
The polymerization that can use in the ring opening copolymer of cyclenes hydrocarbon monomer can be used in ring opening copolymer step to urge Agent.Polymerization catalyst can there is no particular restriction ground use choosing free ruthenium compound, molybdenum compound, tungsten At least one compound of the group that compound, rhenium compound, vfanadium compound and titanium compound are constituted.
Ruthenium compound can use with first generation Ge Labu catalyst (double (tricyclohexyl phosphine) dichloride of benzylidene Ruthenium), second filial generation Ge Labu catalyst (benzylidene (1,3-double (2,4,6-trimethylphenyl)-2-imidazoline subunits) Dichloro (tricyclohexyl phosphine) ruthenium) etc. headed by ruthenium carbene complex.
Molybdenum compound can use with 2,6-diisopropyl phenyl imide tert-butylphenylene molybdenum (VI) double (six Fluorine tert butoxide) molybdenum carbene complex headed by (executing Roc (Schrock) catalyst) etc..
Tungsten compound or other metallic compounds can be set forth in olefin metathesis reaction and metathesis polymerization (Olefin Metathesis and Metathesis Polymerization) (K.J. Ai Wen (IVIN), J.C. More (MOL), academic press of the U.S. (Academic Press) 1997) in described compound, example Such as WCl6、WOCl4、W(CO)6、MoCl5、MoO3、Mo(CO)6、ReCl5、Re2O7、ReOCl3、 VCl4、VOCl3、V2O5、TiCl4Deng compound (a).Those compounds can be used alone one, also Can be used in combination of two or more.
Above-claimed cpd (a) is preferably applied in combination with organo-aluminum compound (b).
Organo-aluminum compound (b) can enumerate the compound represented by following formula (6).
[changing 10]
Al Rn X3-n (6)
R represents straight chained alkyl or branched alkyl groups, and X represents halogen atom.
And, organo-aluminum compound also can use aluminum oxide.
It addition, organo-aluminum compound (b) also can be used to react with compounds such as methanol, ethanol, phenol And the organic alkoxy compound of gained.
Specifically, include, for example (C2H5)3Al、(iBu)3Al、(C2H5)2AlCl、(C2H5)1.5AlCl1.5、 (C2H5)AlCl2, MAO, (C2H5)2Al(OCH3)、(iBu)2Al(OCH3) etc..
Those organo-aluminum compounds (b) can be used alone one, also can be used in combination of two or more.
The use ratio of the organo-aluminum compound (b) modulated as polymerization catalyst/compound (a) is also Being not particularly limited, for catalyst activity aspect, metallic atom (mole) ratio of (b)/(a) is excellent Elect the scope of satisfied 0.1/1～50/1 as, more preferably meet the scope of 0.3/1～10/1.
For compound (a), in order to improve the stability of its catalyst activity kind, can add further with Under compound (c).
(c) select the group that free nitrile, ketone, ether and ester constituted at least one compound,
Compound (c) can use with no particular limitation choosing freely contain the compound of itrile group, ketonic compound, At least one compound of the group that compound containing ether and ester group compound are constituted.Preferably Compound containing itrile group can enumerate the compound represented by following formula (7), and preferred ketone can be enumerated following Compound represented by formula (8), the preferably compound containing ether can enumerate following formula (9) institute table The compound shown, the preferably compound containing ester group can enumerate the compound represented by following formula (10).
[changing 11]
In formula (7)～formula (10), R ', R " and R ' " represent straight-chain or the branch that carbon number is 1～20 Shape alkyl, carbon number be 5～20 alicyclic alkyl, carbon number be 2～20 straight-chain or branch-like thiazolinyl, Carbon number is the aryl of 6～20.Z represents the alkylene that methylene, carbon number are 2～4, r represent 0～3 whole Number.Wherein, R ' " any hydrogen atom also can be optionally substituted by a hydroxyl group.
The compound of formula (7) can enumerate acetonitrile, benzonitrile etc..
The compound of formula (8) include, for example acetone, butanone, methyl iso-butyl ketone (MIBK), 1-Phenylethanone., hexichol Ketone etc..
The compound of formula (9) include, for example dimethyl ether, diethyl ether, butyl oxide, methyl ethyl ether, second Glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol two Ether, diethylene glycol ethylmethyl ether, dibutyl ethylene glycol ether, dimethyl ether, triethylene glycol diformazan Ether etc..
The compound of formula (10) can enumerate methyl acetate, ethyl acetate, butyl acetate, acetate, Ethyl lactate, butyl lactate, essence of Niobe, ethyl benzoate, 5-methyl-5-methoxycarbonyl-dicyclo [2.2.1] hept-2-ene", 2-methyl-2-methoxycarbonyl-dicyclo [2.2.1] heptane, 8-methyl-8-methoxycarbonyl- Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene, 2-methyl-2-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 Alkane etc..
In the case of use compound (c), it is preferably used and contacts in advance with compound (a) Mixture (A) and carry out ring opening copolymer.This operation can be under the inert gas environment such as nitrogen or argon, from room Temperature is implemented in the range of 100 DEG C aptly.Mixing ratio is not particularly limited, in catalyst activity aspect For, to be preferably the scope of 1/1～100/1 for the molar ratio computing of (c)/(a).Made during mixing Solvent can use the hydrocarbon system solvent such as toluene, hexamethylene.This mixed liquor can be immediately available for gathering after manufacturing In conjunction.
As catalyst component relative to the usage amount of cyclenes hydrocarbon monomer, " single with the mol ratio of monomer total amount Body total amount/catalyst component " be preferably greater than 500/1 scope, more preferably higher than 1, the scope of 000/1. The scope that if this ratio is little, catalytic amount is many, then the catalyst quantitative change remained in the copolymer of gained Many, there is the tone to polymer, deterioration, resistance to dissolved cause the situation of large effect.
Polymer solvent can use the solvent of dissolving or central dispersion olefin monomer and catalyst component.It is polymerized molten The concrete example of agent can enumerate the alkanes such as pentane, hexane, heptane, octane, nonane, decane, hexamethylene, The naphthenic such as cycloheptane, cyclooctane, decahydronaphthalene, norbornane, benzene,toluene,xylene, ethylo benzene, The aromatic hydrocarbons such as isopropylbenzene, chlorobutane, bromohexane, dichloromethane, dichloroethanes, 1,6-dibromo-hexane, The halogenation alkane such as chlorobenzene, chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, isobutyl acetate, The saturated carboxylic acid esters such as methyl propionate, the ethers such as butyl oxide, oxolane, dimethoxy-ethane.As Polymer solvent used in the present invention, preferably comprise in those solvents to the list represented by formula (1m) Monomer represented by body and formula (4m) or the monomer represented by formula (1m) and formula (5m) are represented The fragrance such as clicyclic hydrocarbon and toluene such as the hexamethylene of favorable solubility of copolymer of monomer copolymerization Race's hydrocarbon.And, those polymer solvents can be used alone or be used in combination of two or more.
In the manufacture of cyclenes hydro carbons ring-opening copolymer, the cycloolefin analog copolymer of gained can according to purposes with Become the mode of desired molecular weight and adjust suitable ring opening copolymer reaction condition, anti-at ring opening copolymer Also molecular weight regulator can be used in Ying.
The concrete example of the molecular weight regulator that can suitably use can enumerate ethylene, propylene, 1-butylene, 1-amylene, Alpha-olefines and the styrene etc. such as 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, special in those Not preferably 1-butylene, 1-hexene.Those compounds can be individually or by two or more combinations as molecule Amount regulator.
The usage amount of molecular weight regulator is not particularly limited, it is generally desirable to anti-relative to being supplied to ring opening copolymer Be preferably for the cyclenes hydrocarbon monomer answered 1 mole 0.005 mole～0.6 mole, more preferably 0.02～ The scope of 0.5 mole.
Response time when carrying out ring opening copolymer reaction is not particularly limited, it is generally desirable to for producing above It is 0.1 hour～10 hours, is preferably 0.1 hour～5 hours, more preferably 0.1 hour～3 hours. And, reaction temperature is preferably 50 DEG C～the scope of 180 DEG C.
As it has been described above, only cyclenes hydrocarbon monomer to be carried out the cyclenes hydro carbons ring opening copolymer of ring opening copolymer Thing also can be used directly, but owing to there is alkene unsaturated bond in intramolecular, the thermostability according to purposes And insufficient, the most preferably further carry out hydrogenating (hydrogenation).
Applicable known method in step of hydrogenation in the present invention.Such as, can be special by applicable Japan Profit JP 63-218726 publication, Japanese Patent Laid-Open 1-132626 publication, Japan Patent are special Open flat 1-240517 publication, Japanese Patent Laid-Open 2-10221 publication, Japanese Patent Laid-Open 2005-162617 publication, Japanese Patent Laid-Open 2005-162618 publication, Japanese Patent Laid-Open 2005-213370 publication, Japanese Patent Laid-Open 2007-1967 publication, Japanese Patent Laid-Open 2007-106932 Catalyst described in publication etc. or solvent and temperature conditions etc. and implement step of hydrogenation.
It addition, in the case of the copolymer of the monomer represented by the formula of use (5m), hydrogenation solvent Aromatic hydrocarbon can be used；In the case of the copolymer of the monomer represented by the formula of use (4m), in order to accord with Closing the hydrogenation of aromatic rings, hydrogenation solvent is preferably used the clicyclic hydrocarbons such as hexamethylene.
Hydrogenation ratio as the alkene unsaturated bond of cyclenes hydro carbons ring-opening copolymer, it is generally desirable to usually More than 80mol%, it is preferably more than 90mol%, more preferably more than 95mol%, even more preferably For more than 99mol%.
Carry out as described above, cyclenes hydrocarbon monomer is carried out ring opening copolymer, optionally carry out hydrogenating and institute Cyclenes hydro carbons ring-opening copolymer also can optionally utilize known method and be purified, denitrating catalyst, Desolventizings etc. use after processing.
The cyclenes hydro carbons ring-opening copolymer of the present invention can be directly used for molding, but resistance to adds heat deterioration to improve Property or light resistance and the additives such as known antioxidant or UV absorbent can be added and use.As Additive, such as, can use as the additive in resin known phenolic compound, thio-alcohol Compound, thio-ether type compounds, disulfide compound, phosphorus species etc., by relative to the present invention Cyclenes hydro carbons ring-opening copolymer 100 mass parts and add 0.01 mass parts～10 mass parts those at least 1 kind of compound, can make the characteristics such as resistance to heating deterioration or light resistance improve.
And, in the cyclenes hydro carbons ring-opening copolymer of the present invention, also can be according to the spy of the molded body of target Property etc. add other additives and use.Such as, in order to obtain the thin film of coloring, also can add dyestuff, The coloring agent such as pigment, can also make the flatness of the thin film of gained rise to feature and add levelling agent.All Agent include, for example fluorine class nonionic surfactant, special crylic acid resin levelling agent, silicone Levelling agent etc..
The cyclenes hydro carbons ring-opening copolymer of the present invention, cyclenes hydro carbons ring opening copolymer especially as hydride Thing such as can be shaped to lenticular, film like, the desired shape such as lamellar by known method And use, may be suitably used in the purposes such as various optical elements such as optical thin film.
[example]
Hereinafter, Case-based Reasoning is to present invention more specific description in addition, but the present invention is not limited to those Example.In Examples below and comparative example, implement polyreaction, catalyst modulation in a nitrogen environment Etc. each step.
And, may utilize following methods and carry out each mensuration and evaluation.
Vitrification point (Tg):
Use differential scanning calorimeter (manufacture of Seiko electronics (Seiko Instruments) company, trade name: DSC6200), vitrification initial temperature of extrapolating according to Japanese Industrial Standards K7121 is as vitrification temperature Degree (Tg).
Weight average molecular weight and molecular weight distribution:
Use chromatograph of gel permeation (GPC, TOSOH Co., Ltd's manufacture, trade name HLC-8020), Use oxolane (THF) as solvent, measure the weight average molecular weight (Mw) of polystyrene conversion And molecular weight distribution (Mw/Mn).
The conversion ratio of monomer:
Use gas chromatograph (Gas chromatograph) (Shimadzu Corporation's manufacture, commodity Entitled GC-2014) amount of residual monomers contained in analytical reactions solution and calculate.
It addition, utilize aforesaid method and measure refractive index nD, Abbe number and CRValue.
Oxygen transmission rate:
The polymer of gained is added the film sample that hot extrusion molding making thickness is 100 μm.Separately Outward, Mold Temperatures set is 280 DEG C.Utilize adding pressure type air penetrability determinator (Gasperm-100, Japan Light splitting manufactures) and measure the oxygen transmission rate of the thin film of gained.
Bending strength:
The polymer of gained is carried out ejection formation, makes the plate of wide 10mm × long 80mm × thickness 4mm. The bending strength (MPa) of the plate of gained is measured according to ISO178.
Example 1
Using as cyclenes hydrocarbon monomer 5-phenyl-dicyclo [2.2.1] hept-2-ene" (" phenyl norbornene " ( Table 1 represents with Ph-NB)) (13.5g, 132mmol), five rings [6.5.1.02,7.13,6.09,13] 15 Carbon-4,10-diene (" three cyclopentadiene " (representing with TCP in Table 1)) (46.5g, 391mmol), 1-butylene (0.37g, 6.59mmol) as molecular weight regulator makes an addition to hexamethylene (107g), first In butylcyclohexane (19g), it is heated to 100 DEG C and is stirred.Prepare following formula (11) institute separately The ruthenium carbene complex catalyst (0.684mg, 1.046 μm ol) represented adds to toluene (0.55g) In and the solution of gained.For aforesaid monomer solution, add this ruthenium carbene complex catalyst solution and Start polyreaction.After polymerization 1 hour, add the ethyl vinyl ether (0.0735 as reaction stopping agent G, 1.046 μm ol) toluene (0.55g) solution, it is thus achieved that ring-opening copolymer solution.Measure turning of monomer Rate, result is 99 mass %.By making one part precipitate in substantial amounts of methanol, drying under reduced pressure and Obtain ring-opening copolymer.Weight average molecular weight (Mw) and the molecular weight distribution of GPC method will be utilized (Mw/Mn) measurement result is shown in Table 1.
[changing 12]
The solution of the above-mentioned ring-opening copolymer of gained is transferred in hydrogenation container, adds hexamethylene (43.4g), decahydronaphthalenes (154g) be stirred and make uniform solution, add as hydrogenation (cobalt naphthenate/Mineral spirits=48/52 mass %) (0.502g, 0.524mmol), triethyl group of catalyst Toluene (3.6g) solution of aluminum (299mg, 2.618mmol).At room temperature hydrogen is directed into 8MPa After, temperature rises to 160 DEG C～165 DEG C the most at last so that it is react 3 hours.Make the product of gained greatly The methanol of amount precipitates, carries out drying under reduced pressure, obtain intramolecular alkene unsaturated bond and virtue therefrom The ring-opening copolymer (representing with hydrogenated copolymer in Table 1) that fragrant both rings are hydrogenated.According to1The analysis of H-NMR, the hydrogenation ratio of aromatic rings and alkene unsaturated bond entirety is 99.6mol%.
By the weight average molecular weight (Mw) of the hydrogenated copolymer of gained, molecular weight distribution (Mw/Mn), Tg、nD, Abbe number and CR(×10-12Pa-1) value be shown in Table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) be shown in Table 1.
Example 2
Using as cyclenes hydrocarbon monomer phenyl norbornene (representing with Ph-NB in Table 1) (18g, 176mmol), three cyclopentadiene (tricyclopentadiene, TCP) (42g, 353mmol), conduct The 1-butylene (0.37g, 6.67mmol) of molecular weight regulator adds to hexamethylene (107g), methyl ring In hexane (19g), it is heated to 100 DEG C and is stirred.Prepare above-mentioned formula (11) represented separately Ruthenium carbene complex (0.416mg, 0.635 μm ol) add in toluene (0.55g) molten Liquid.For aforesaid monomer solution, add this ruthenium carbene complex catalyst solution and start polyreaction. After polymerization 1 hour, add the ethyl vinyl ether (0.046mg, 0.635 μm ol) as reaction stopping agent Toluene (0.55g) solution, it is thus achieved that ring-opening copolymer solution.Measuring the conversion ratio of monomer, result is 99 mass %.By making one part precipitate in substantial amounts of methanol, drying under reduced pressure and obtain ring opening copolymer Thing.The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) that utilize GPC method are measured Result is shown in Table 1.
The solution of the above-mentioned ring-opening copolymer of gained is transferred in hydrogenation container, adds hexamethylene (617g), decahydronaphthalenes (123g) be stirred and make uniform solution, add urge as hydrogenation (cobalt naphthenate/Mineral spirits=48/52 mass %) (1.930g, 1.984mmol), triethyl aluminum of agent Toluene (15.0g) solution of (1.245g, 10.91mmol).At room temperature hydrogen is directed into 8MPa After, temperature rises to 160 DEG C～165 DEG C the most at last so that it is react 3 hours.Make the product of gained greatly The methanol of amount precipitates, carries out drying under reduced pressure, obtain hydrogenated copolymer therefrom.According to1H-NMR's Analyzing, hydrogenation ratio is 99.9mol%.
By the weight average molecular weight (Mw) of the hydrogenated copolymer of gained, molecular weight distribution (Mw/Mn), Tg、nD, Abbe number and CR(×10-12Pa-1) value be shown in Table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) be shown in Table 1.
Example 3
Using as three cyclopentadiene (TCP) (64.5g, 0.325mol) of cyclenes hydrocarbon monomer, 5-(3- Cyclohexene-1-base) dicyclo [2.2.1] hept-2-ene" (representing with CHXe-NB in Table 1) (29.0g, 0.166 Mol), 8-methyl-8-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene are (in Table 1 with DNM And represent) (6.5g, 0.028mol), 1-hexene (0.65g, 5.2mmol) as molecular weight regulator Add to toluene (150g), be heated to 100 DEG C and be stirred.Prepare triisobutyl aluminium separately (83 μm ol) adds the solution to methanol (12 μm ol).For aforesaid monomer solution, add After adding this organo-aluminium solution, add the WCl of 100 μm ol6And start polyreaction.Polymerization 1 hour After, add the LiOH (600 μm ol) as reaction stopping agent, it is thus achieved that ring-opening copolymer solution.Measure The conversion ratio of monomer, result is 99 mass %.By making one part precipitate in substantial amounts of methanol, subtract Press dry dry and obtain ring-opening copolymer.Weight average molecular weight (Mw) and the molecule of GPC method will be utilized Amount distribution (Mw/Mn) measurement result is shown in Table 1.
The solution of the above-mentioned ring-opening copolymer of gained is put into autoclave, adds 150g's further Toluene.Secondly, add 100 μm ol as hydrogenation catalyst Ru[4-CH3(CH2)4C6H4CO2]H(CO)[P(C6H5)3], after being heated to 90 DEG C, hydrogen is put into instead Answering in device, making pressure is 10MPa.Thereafter, when pressure is remained 10MPa, finally Temperature is risen to 160 DEG C～165 DEG C so that it is react 3 hours.Make the product of gained at substantial amounts of methanol Middle precipitation, carries out drying under reduced pressure, obtains hydrogenated copolymer therefrom.According to1The analysis of H-NMR, hydrogen Rate is 99.8mol%.
By the weight average molecular weight (Mw) of the hydrogenated copolymer of gained, molecular weight distribution (Mw/Mn), Tg、nD, Abbe number and CR(×10-12Pa-1) value be shown in Table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) be shown in Table 1.
Example 4
In example 3, monomer is replaced with three cyclopentadiene (TCP) (68.0g, 0.343mol), 5-(3- Cyclohexene-1-base) dicyclo [2.2.1] hept-2-ene" (CHXe-NB) (29.0g, 0.166mol), 8-methyl-8- Methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] 12 carbon-3-alkene (DNM) (3.0g, 0.013mol), remove This with external with example 3 identical under conditions of carry out ROMP-hydrogenation, it is thus achieved that hydrogenated copolymer.According to1The analysis of H-NMR, hydrogenation ratio is 99.8mol%.
ROMP will be utilized and the weight average molecular weight (Mw) of ring opening copolymer of gained, molecular weight distribution And utilize hydrogenation subsequently and the weight average molecular weight of the hydrogenated copolymer of gained (Mw/Mn) (Mw), molecular weight distribution (Mw/Mn), Tg, nD, Abbe number and CR(×10-12Pa-1) value show In table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) It is shown in Table 1.
Comparative example 1
In example 3, monomer is replaced with three cyclopentadiene (TCP) (85.0g, 0.429mol), double Ring [2.2.1] hept-2-ene" (norborene represents with NB in Table 1) (15.0g, 0.159mol), ROMP-hydrogenation is carried out in addition, it is thus achieved that hydrogenated copolymer under conditions of identical with example 3.According to1The analysis of H-NMR, hydrogenation ratio is 99.8mol%.
By the weight average molecular weight (Mw) of the hydrogenated copolymer of gained, molecular weight distribution (Mw/Mn), Tg、nD, Abbe number and CR(×10-12Pa-1) value in table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) be shown in Table 1.
Although the hydrogenated copolymer n of gained in comparative example 1DBe 1.540, Abbe number be 56, but CRFor height Reach 1630 × 10-12Pa-1Value.And, although oxygen transmission rate is 41 (cm3·mm/m2/ day/atm), but curved Qu Qiangdu is but the value of as little as 65 (MPa).
Comparative example 2
In example 3, monomer is replaced with three cyclopentadiene (TCP) (70.0g, 0.353mol), three Ring [4.3.0.12,5] decyl-3,7-diene (bicyclopentadiene represents with DCP in Table 1) (15.0g, 0.113 Mol), dicyclo [2.2.1] hept-2-ene" (norborene represents with NB in Table 1) (15.0g, 0.159 Mol), under conditions of identical with example 3, ROMP-hydrogenation is carried out in addition, it is thus achieved that hydrogenated copolymer. According to1The analysis of H-NMR, hydrogenation ratio is 99.7mol%.
By the weight average molecular weight (Mw) of the hydrogenated copolymer of gained, molecular weight distribution (Mw/Mn), Tg、nD, Abbe number and CR(×10-12Pa-1) value be shown in Table 1.And, by oxygen transmission rate (cm3·mm/m2/ day/atm) and the value of bending strength (MPa) be shown in Table 1.
Although the hydrogenated copolymer n of gained in comparative example 2DBe 1.539, Abbe number be 56, but CRFor height Reach 2010 × 10-12Pa-1Value.
Comparative example 3
In example 3, monomer is replaced with three cyclopentadiene (TCP) (55.0g, 0.277mol), double Ring [2.2.1] hept-2-ene" (norborene, represent with NB in Table 1) (15.0g, 0.159mol), 8-methyl-8-methoxycarbonyl-Fourth Ring [4.4.0.12,5.17,10] the 12 carbon-3-alkene (tables with DNM in Table 1 Show) (30.0g, 0.129mol), under conditions of identical with example 3, carry out ROMP-hydrogen in addition Change, it is thus achieved that hydrogenated copolymer.According to1The analysis of H-NMR, hydrogenation ratio is 99.8mol%.
ROMP will be utilized and the weight average molecular weight (Mw) of ring opening copolymer of gained, molecular weight distribution And utilize hydrogenation subsequently and the weight average molecular weight of the hydrogenated copolymer of gained (Mw/Mn) (Mw), molecular weight distribution (Mw/Mn), Tg, oxygen transmission rate (cm3·mm/m2/ day/atm) and bending The value of intensity (MPa) is shown in Table 1.
Although the hydrogenated copolymer bending strength of gained is 87 (MPa) in comparative example 3, but oxygen transmission rate is high Reach 70 (cm3·mm/m2/ day/atm) value.
[table 1]
The evaluation towards optical applications of each example can realize high refractive index and low CR value simultaneously.Separately On the one hand, the evaluation towards medical application can realize high bending strength and low oxygen permeability simultaneously.
The cyclenes hydro carbons ring-opening copolymer of the present invention realizes high index of refraction and high Abbe number and low-birefringence, And there is low oxygen permeability, high strength, and there is the Tg with practicality that mouldability is excellent, because of This can be used as optical material, insulant, medical device material.

Claims (8)

1. a cyclenes hydro carbons ring-opening copolymer, it is characterised in that:
Comprise the repetitive represented by following formula (1) and formula (2),
[changing 13]
In formula (1), m is the integer of 1～3, and in formula (2), p, q are each independently 0～2 Integer, R1～R12Separately represent any one of following (i)～(iii):
(i) hydrogen atom,
(ii) halogen atom,
(iii) carbon number also can being substituted with halogen atoms is the aliphatic alkyl of 1～4.
Cyclenes hydro carbons ring-opening copolymer the most according to claim 1, it is characterised in that:
The weight represented by described formula (1) of 40 mass %～85 mass % is comprised in all construction units Multiple unit, 60 mass %～the repetitive represented by described formula (2) of 15 mass %.
Cyclenes hydro carbons ring-opening copolymer the most according to claim 1 and 2, it is characterised in that:
The weight represented by following formula (3) of below 10 mass % is comprised further in all construction units Multiple unit,
[changing 14]
In formula (3), n is the integer of 0～3, B1～B4Separately represent following (i)～(v) Any one:
(i) hydrogen atom,
(ii) halogen atom,
(iii) group that free alkoxyl, hydroxyl, ester group, cyano group, amino and mercapto constituted is selected Polar group,
(iv) also can be by halogen atom or aliphatic that described polar group (iii) substituted carbon number is 1～10 Alkyl,
(v)B1With B3、B1With B4、B2With B3, or B2With B4Mutually bond and with bond respectively Carbon atom together forms circulus, and is not involved in the B of described bond1～B4Represent described independently of each other Any one of (i)～(iv).
Cyclenes hydro carbons ring-opening copolymer the most according to claim 1 and 2, it is characterised in that:
The weight average molecular weight of the polystyrene conversion utilizing chromatograph of gel permeation and measure is 20,000～150,000.
5. a cyclenes hydro carbons ring-opening copolymer, it is characterised in that:
Comprise the repetitive represented by following formula (1a) and selected from following formula (4) and following formula (5) The repetitive represented by least 1 formula,
[changing 15]
In formula (1a), m is the integer of 1～3, and in formula (4), p, q are each independently 0～2 Integer, in formula (4) and formula (5), R1～R12Separately represent following (i)～(iii) Any one:
(i) hydrogen atom,
(ii) halogen atom,
(iii) carbon number also can being substituted with halogen atoms is the aliphatic alkyl of 1～4.
Cyclenes hydro carbons ring-opening copolymer the most according to claim 5, it is characterised in that:
Comprise the repetitive represented by following formula (3a) further,
[changing 16]
In formula (3a), n is the integer of 0～3, B1～B4Separately represent following (i)～(v) Any one:
(i) hydrogen atom,
(ii) halogen atom,
(iii) group that free alkoxyl, hydroxyl, ester group, cyano group, amino and mercapto constituted is selected Polar group,
(iv) also can be by halogen atom or aliphatic that described polar group (iii) substituted carbon number is 1～10 Alkyl,
(v)B1With B3、B1With B4、B2With B3, or B2With B4Mutually bond and with bond respectively Carbon atom together forms circulus, and is not involved in the B of described bond1～B4Represent described independently of each other Any one of (i)～(iv).
7. a cyclenes hydro carbons ring-opening copolymer, it is the optical material used in optical material field By cyclenes hydro carbons ring-opening copolymer,
Described cyclenes hydro carbons ring-opening copolymer is that cyclenes hydro carbons open loop according to claim 1 and 2 is total to Polymers.
8. a cyclenes hydro carbons ring-opening copolymer, it is the medical treatment used in medical apparatus Material Field Appliance material cyclenes hydro carbons ring-opening copolymer,
Described cyclenes hydro carbons ring-opening copolymer is that cyclenes hydro carbons open loop according to claim 1 and 2 is total to Polymers.
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