CN117510797A - Cycloolefin polymer optical resin and preparation method and application thereof - Google Patents
Cycloolefin polymer optical resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN117510797A CN117510797A CN202311556446.8A CN202311556446A CN117510797A CN 117510797 A CN117510797 A CN 117510797A CN 202311556446 A CN202311556446 A CN 202311556446A CN 117510797 A CN117510797 A CN 117510797A
- Authority
- CN
- China
- Prior art keywords
- ring
- cycloolefin
- dicyclopentadiene
- polymer
- optical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 230000003287 optical effect Effects 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000011347 resin Substances 0.000 title claims abstract description 57
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 72
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 50
- 150000001925 cycloalkenes Chemical group 0.000 claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 12
- 150000002848 norbornenes Chemical class 0.000 claims abstract description 7
- -1 norbornene compound Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000004210 ether based solvent Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000008378 aryl ethers Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012788 optical film Substances 0.000 claims description 4
- 230000003712 anti-aging effect Effects 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- GCYUJISWSVALJD-UHFFFAOYSA-N 1,1-diethylcyclohexane Chemical compound CCC1(CC)CCCCC1 GCYUJISWSVALJD-UHFFFAOYSA-N 0.000 description 1
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- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- RYCPAQDFTLUNRR-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)anthracene Chemical compound C1=CC=C2C=C3C(C4CC5CC4C=C5)=CC=CC3=CC2=C1 RYCPAQDFTLUNRR-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- CGEDFMIHOGFQGN-UHFFFAOYSA-N 2,3,3a,4,5,6-hexahydro-1H-indene cyclohexane Chemical compound C1CCCCC1.C1CCC=C2CCCC21 CGEDFMIHOGFQGN-UHFFFAOYSA-N 0.000 description 1
- UCWRHXBFPRXNKA-UHFFFAOYSA-N 2,3-di(ethylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=CC UCWRHXBFPRXNKA-UHFFFAOYSA-N 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- KHXRZKUYYFOLAR-UHFFFAOYSA-N 2,3-diphenylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C=1C=CC=CC=1)C2C1=CC=CC=C1 KHXRZKUYYFOLAR-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- DRWYRROCDFQZQF-UHFFFAOYSA-N 2-methylpenta-1,4-diene Chemical compound CC(=C)CC=C DRWYRROCDFQZQF-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- PTLFPVGFZJKZSP-UHFFFAOYSA-N 5-(2-ethylphenyl)bicyclo[2.2.1]hept-2-ene Chemical compound CCC1=CC=CC=C1C1C(C=C2)CC2C1 PTLFPVGFZJKZSP-UHFFFAOYSA-N 0.000 description 1
- KEUSWSGBDGZTQU-UHFFFAOYSA-N 5-(2-methylphenyl)bicyclo[2.2.1]hept-2-ene Chemical compound CC1=CC=CC=C1C1C(C=C2)CC2C1 KEUSWSGBDGZTQU-UHFFFAOYSA-N 0.000 description 1
- CCOOUGMPJLNWQN-UHFFFAOYSA-N 5-(2-propan-2-ylphenyl)bicyclo[2.2.1]hept-2-ene Chemical compound CC(C)C1=CC=CC=C1C1C(C=C2)CC2C1 CCOOUGMPJLNWQN-UHFFFAOYSA-N 0.000 description 1
- UVFFMASFIIKUOD-UHFFFAOYSA-N 5-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCl)CC1C=C2 UVFFMASFIIKUOD-UHFFFAOYSA-N 0.000 description 1
- JGLIHSMBVDZMSA-UHFFFAOYSA-N 5-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CCCCC1 JGLIHSMBVDZMSA-UHFFFAOYSA-N 0.000 description 1
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- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- LFBHYIUTPVORTR-UHFFFAOYSA-N 5-fluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)CC1C=C2 LFBHYIUTPVORTR-UHFFFAOYSA-N 0.000 description 1
- SLLQHXBUQMCLGK-UHFFFAOYSA-N 5-methyl-5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1(C)C1=CC=CC=C1 SLLQHXBUQMCLGK-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- UAKPCRIFCXQISY-UHFFFAOYSA-N 5-prop-2-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC=C)CC1C=C2 UAKPCRIFCXQISY-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- AKHDGSRSWWFVIZ-UHFFFAOYSA-N 5-propylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCC)CC1C=C2 AKHDGSRSWWFVIZ-UHFFFAOYSA-N 0.000 description 1
- WKWWISMSTOFOGJ-UHFFFAOYSA-N 5-propylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CCC)CC1C=C2 WKWWISMSTOFOGJ-UHFFFAOYSA-N 0.000 description 1
- AVFRNNALLLVPGJ-UHFFFAOYSA-N 7-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1C2C AVFRNNALLLVPGJ-UHFFFAOYSA-N 0.000 description 1
- RNWXYWOPADFOAS-UHFFFAOYSA-N 9,10-diphenyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2C(C=2C=CC=CC=2)C1C1=CC=CC=C1 RNWXYWOPADFOAS-UHFFFAOYSA-N 0.000 description 1
- XPBJOKKVDANCLK-UHFFFAOYSA-N 9-(5-bicyclo[2.2.1]hept-2-enyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1CC2CC1C=C2 XPBJOKKVDANCLK-UHFFFAOYSA-N 0.000 description 1
- ZTSMCYDMAXKWGR-UHFFFAOYSA-N 9-anthracen-1-yltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1=CC=C2C=C3C(C4CC5CC4C4C6C=CC(C54)C6)=CC=CC3=CC2=C1 ZTSMCYDMAXKWGR-UHFFFAOYSA-N 0.000 description 1
- DWAVOXKPWJGLAQ-UHFFFAOYSA-N 9-methyl-9-phenyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C2C3CC(C=C3)C22)CC2C1(C)C1=CC=CC=C1 DWAVOXKPWJGLAQ-UHFFFAOYSA-N 0.000 description 1
- LUZRCAIWLRPMQK-UHFFFAOYSA-N 9-phenyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C1=CC=CC=C1 LUZRCAIWLRPMQK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
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- HFNNQOKJIQHMAT-UHFFFAOYSA-N CC1(CC=CC(CC23C=CC(CC2)C3)=C1)C(=O)O Chemical compound CC1(CC=CC(CC23C=CC(CC2)C3)=C1)C(=O)O HFNNQOKJIQHMAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
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- 239000005909 Kieselgur Substances 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical compound C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 238000005187 foaming Methods 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- GUVXZFRDPCKWEM-UHFFFAOYSA-N pentalene Chemical compound C1=CC2=CC=CC2=C1 GUVXZFRDPCKWEM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical group 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- 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
-
- 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
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
- C08G2261/724—Hydrogenation
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a cycloolefin polymer optical resin and a preparation method and application thereof. The cycloolefin polymer optical resin provided by the invention is prepared by hydrogenation and molding of cycloolefin ring-opening polymer; the cycloolefin ring-opening polymer is prepared by ring-opening metathesis polymerization of dicyclopentadiene and norbornene compounds; the turbidity value of the dicyclopentadiene when the dicyclopentadiene is prepared into a 50wt% toluene solution is 2NTU or less. The present invention has surprisingly found that the turbidity of dicyclopentadiene used in preparing a cycloolefin ring-opening polymer affects the quality of an optical resin prepared from the cycloolefin ring-opening polymer, and is particularly closely related to indexes such as a birefringence of the product. Accordingly, the present invention obtains a cycloolefin polymer optical resin material having excellent optical properties by controlling the haze of dicyclopentadiene.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a cycloolefin polymer optical resin and a preparation method and application thereof.
Background
Most of optical materials commonly used for preparing transparent resins are polyacrylate and polycarbonate, and the materials have good transparency, but the transparent materials prepared from inorganic glass cannot be replaced by the methods of heat resistance, moisture absorption resistance, adhesion, breaking strength and the like. In order to meet the above performance requirements, a cycloolefin polymer optical material (COC/COP) is brought into the field of view by using a resin material instead of an inorganic glass.
However, as a cycloolefin copolymer used as an optical material (such as an optical part, a lens, an image pickup module, an optical film, a display panel, a light guide plate, and an electronic device), on the one hand, it is prepared by a reaction of a high activity such as ROMP, which causes a problem that it is liable to be accompanied with a severe heat release of the reaction and a gel formation; on the other hand, the melt viscosity of the cycloolefin polymer is higher, and the problems of large surface stress, high photoelastic coefficient and the like easily occur in the molding process of three stages of filling, pressure maintaining and cooling, so that the birefringence of the optical material is larger, and the optical performance of the optical material is influenced.
Currently, in the field of cycloolefin optical resins, there are few patents and literature concerning dicyclopentadiene raw materials. On the one hand, the research on influencing factors of the quality of the optical lens is focused on the composition and the components, for example, the Chinese patent CN106687500 improves the melt index of an optical component by increasing the content of tetracyclododecene, so that the formability of the optical component is improved, but the optical component is influenced by the steric effect of the polycyclic structure of tetracyclododecene, the adjustable range of the melt index is narrow, and the optical component is further improved for electronic and optical materials; the U.S. patent No. 20230287169A1 improves the visible light transmittance of an optical lens and the like by controlling the sequence distribution and the relative content of a double-ring structure and an aliphatic chain segment in a molecular structure, but the problems of gel formation, influence on the yield of polymerization reaction or the performance of a product and the like are solved in the polymerization process, and the mass production is difficult; on the other hand, many researches on factors affecting the quality of an optical lens are focused on the deashing treatment of a reaction solution of a cyclic olefin ring-opening polymer, for example, chinese patent CN114345300B uses a chelating resin adsorbent to remove metal ions in the cyclic olefin ring-opening polymer, thereby improving optical properties such as transparency of an optical material, and japanese patent JP2002128820a discloses a method of removing impurity metals in a polymerization solution by contacting with a solid adsorbent (such as alumina, silica gel solid) in order to improve white spot problem in molding of an optical lens, but these post-treatment methods inevitably introduce a solvent, and the number of treatments is large, resulting in problems of solvent recovery and process complexity.
Disclosure of Invention
In view of the above, the present invention is directed to a cycloolefin polymer optical resin having excellent optical properties (i.e., low birefringence) and a method for preparing the same and applications thereof.
The invention provides a cycloolefin polymer optical resin, which is prepared by hydrogenation and molding of cycloolefin ring-opening polymer;
the cycloolefin ring-opening polymer is prepared by ring-opening metathesis polymerization of dicyclopentadiene and norbornene compounds;
the turbidity value of the dicyclopentadiene when the dicyclopentadiene is prepared into a 50wt% toluene solution is 2NTU or less.
Preferably, the dicyclopentadiene has a turbidity value of 1NTU or less when it is prepared into a 50wt% toluene solution.
Preferably, the turbidity of the cycloolefin ring-opening polymer is 12NTU or less when the cycloolefin ring-opening polymer is prepared into a 20wt% toluene solution after being stored in a glass bottle at 25 ℃ for 30 days under the environment that the water content is less than or equal to 1ppm and the oxygen content is less than or equal to 1 ppm.
Preferably, the turbidity of the cycloolefin ring-opening polymer is 10NTU or less when the cycloolefin ring-opening polymer is prepared into a 20wt% toluene solution after being stored in a glass bottle at 25 ℃ for 30 days under the environment that the water content is less than or equal to 1ppm and the oxygen content is less than or equal to 1 ppm.
Preferably, the cycloolefin ring-opening polymer comprises a structural unit of the formula (1) and a structural unit of the formula (2):
wherein a is an integer between 1 and 100; b is an integer between 1 and 100; n, m and s are independently 0,1, 2 or 3; r is R 1 ～R 10 Independently a hydrogen atom, a halogen atom other than a fluorine atom or a hydrocarbon group having 1to 10 carbon atoms substituted with a halogen atom other than a fluorine atom; r is R 3 、R 4 、R 9 And R is 10 Is an independent substituent, or R 3 、R 4 、R 9 And R is 10 At least one pair of substituents being bonded to form a ring; r is R 5 、R 6 、R 7 And R is 8 Is an independent substituent, or R 5 、R 6 、R 7 And R is 8 At least one pair of substituents being bonded to form a ring.
Preferably, R 3 Or R is 4 And R is R 9 Or R is 10 、R 3 And R is R 4 、R 9 And R is R 10 Can be bonded to each other to form a single ring or multiple rings, and R is when n=1 5 And R is R 6 、R 6 And R is R 7 、R 7 And R is R 8 Can be bonded to each other to form a single ring or multiple rings, and R is represented by n=2 or 3 5 And R is R 5 、R 5 And R is R 6 、R 6 And R is R 7 、R 7 And R is R 8 、R 8 And R is R 8 Can be bonded to each other to form a single ring or multiple rings, which may have a double bond, and which may be aromatic rings.
Preferably, the cycloolefin ring-opening polymer is a non-aromatic norbornene-based polymer, in which case the structural unit of formula (2) satisfies the following condition:
n must be 0, and when m+.0, R 1 ～R 4 、R 9 ～R 10 Wherein R is not an aromatic ring 3 Or R is 4 And R is R 9 Or R is 10 、R 3 And R is R 4 、R 9 And R is R 10 May be bonded to each other to form a single ring or multiple rings, which may also have a double bond, but which may not contain an aromatic ring.
Preferably, the cycloolefin ring-opening polymer is an aromatic norbornene-based polymer, in which case the structural unit of formula (2) satisfies the following condition:
a) When m and n are 0 at the same time, R 1 ～R 2 Each independently is a hydrogen atom, a halogen atom other than fluorine atom or a hydrocarbon group of 1to 10 carbon atoms substituted with a halogen atom other than fluorine atom, and R 1 ～R 2 An aromatic ring must be included;
b) When n=0, R 1 ～R 10 Each independently is a hydrogen atom, a halogen atom other than fluorine atom or a hydrocarbon group of 1to 10 carbon atoms substituted with a halogen atom other than fluorine atom, and R 1 ～R 4 And R is 9 ～R 10 Wherein the aromatic ring must be contained, or R 3 Or R is 4 And R is R 9 Or R is 10 The rings bonded to each other to form a single ring or multiple rings must contain aromatic rings;
c) When n=1, R 1 ～R 10 Each independently represents a hydrogen atom, a halogen atom other than fluorine atom or a hydrocarbon group having 1to 10 carbon atoms substituted by a halogen atom other than fluorine atom, R 5 And R is R 6 、R 6 And R is R 7 、R 7 And R is R 8 Can be bonded to each other to form a single ring or multiple rings, and R is represented by n=2 or 3 5 And R is R 5 、R 5 And R is R 6 、R 6 And R is R 7 、R 7 And R is R 8 、R 8 And R is R 8 Can be bonded to each other to form a single ring or multiple rings, which may have a double bond, and which may be aromatic rings.
Preferably, the cycloolefin polymer optical resin further comprises one or more of an antioxidant, a plasticizer, a heat stabilizer and an anti-aging agent.
The invention also provides a preparation method of the cycloolefin polymer optical resin, which comprises the following steps:
providing dicyclopentadiene having a turbidity value of 2NTU or less when the dicyclopentadiene is prepared into a 50wt% toluene solution;
performing ring-opening metathesis polymerization on the dicyclopentadiene and a norbornene compound to obtain a cycloolefin ring-opening polymer;
and (3) hydrogenating and molding the cycloolefin ring-opening polymer to obtain the cycloolefin polymer optical resin.
Preferably, the ring-opening metathesis polymerization reaction is carried out in the presence of a ring-opening metathesis catalyst.
Preferably, the temperature of the ring-opening metathesis polymerization reaction is 30-90 ℃, the pressure is 0-2 MPa, and the time is 0.5-10 h.
Preferably, the ring-opening metathesis polymerization reaction is carried out in an inert solvent; the inert solvent is one or more of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents and aromatic ether solvents.
The invention also provides an optical product which is made of the cycloolefin polymer optical resin disclosed in the technical scheme or the cycloolefin polymer optical resin manufactured by the manufacturing method disclosed in the technical scheme.
Preferably, the optical product is an optical lens, an optical film, an optical disk, a light guide plate or a display panel.
Preferably, the optical lens is a spectacle lens, a camera lens, a sensor lens, an illumination lens or an imaging lens.
Preferably, the optical article has stress birefringence (C R ) At-500×10 -12 ～1400×10 -12 Pa -1 Between them.
Compared with the prior art, the invention provides a cycloolefin polymer optical resin and a preparation method and application thereof. The cycloolefin polymer optical resin provided by the invention is prepared by hydrogenation and molding of cycloolefin ring-opening polymer; the cycloolefin ring-opening polymer is prepared by ring-opening metathesis polymerization of dicyclopentadiene and norbornene compounds; the turbidity value of the dicyclopentadiene when the dicyclopentadiene is prepared into a 50wt% toluene solution is 2NTU or less. The present invention has surprisingly found that the turbidity of dicyclopentadiene used in preparing a cycloolefin ring-opening polymer affects the quality of an optical resin prepared from the cycloolefin ring-opening polymer, and is particularly closely related to indexes such as a birefringence of the product. Accordingly, the present invention obtains a cycloolefin polymer optical resin material having excellent optical properties by controlling the haze of dicyclopentadiene.
More specifically, the technical scheme of the invention has at least the following beneficial effects:
(1) By rapidly and simply controlling the quality of the raw materials, the fine difference of the raw materials is found, the cycloolefin polymer resin optical product with excellent performance is prepared with lower cost and higher efficiency, and the obtained optical product has low birefringence;
(2) The turbidity of dicyclopentadiene is controlled, the phenomena of ripple, blushing, speckling or foaming and the like of an optical product can be effectively reduced, the appearance quality of the product is effectively improved, and the defective rate is remarkably reduced.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a cycloolefin polymer optical resin, which is prepared by hydrogenation and molding of cycloolefin ring-opening polymer; the cycloolefin ring-opening polymer is prepared from dicyclopentadiene and norbornene compounds through ring-opening metathesis polymerization.
In the cycloolefin polymer optical resin according to the present invention, the dicyclopentadiene is dicyclopentadiene having a low turbidity, and the turbidity value when a 50wt% toluene solution is produced is 2NTU or less, preferably 1NTU or less, more preferably 0.5NTU or less, and most preferably 0.1NTU or less. In the present invention, the purity of toluene in the above toluene solution is 99.5% or more, and the water content is 50ppm or less, preferably 20ppm or less.
In the cycloolefin polymer optical resin provided by the invention, the reason for selecting dicyclopentadiene with low turbidity is that, through research, the following is found: when the turbidity value of dicyclopentadiene in preparing 50wt% toluene solution is greater than 2NTU, the stability of the prepared cycloolefin ring-opening polymer is reduced, and cloudiness occurs in a short period (1-3 days); when the haze value is more than 5NTU, the incidence rate of optical deformation of the product is increased, so that the birefringence of the prepared cycloolefin polymer optical resin is obviously reduced, the quality of the product is reduced, and the product is difficult to effectively produce.
In the cycloolefin polymer optical resin provided by the invention, dicyclopentadiene is a dimer of cyclopentadiene, and two isomers of bridged ring type and hanging ring type are arranged on the space structure, and the bridged ring type dicyclopentadiene is used for synthesis. At present, the preparation methods of the bridged-ring dicyclopentadiene mainly comprise 2 methods, namely thermal dimerization-depolymerization-distillation and thermal dimerization-extractive distillation-rectification, and more particularly, the bridged-ring dicyclopentadiene can be prepared according to the following process route: taking C5 fraction of petroleum pyrolysis as a raw material, dimerization is carried out on the C5 fraction, light components are removed to obtain crude dicyclopentadiene, then acidic substances loaded by an inorganic carrier are taken as a catalyst, and catalytic depolymerization is carried out on the crude dicyclopentadiene at 100-200 ℃ to obtain high-purity cyclopentadiene; finally, the dicyclopentadiene is subjected to dimerization to remove light components, so that the dicyclopentadiene with high purity is obtained.
In the cycloolefin polymer optical resin provided by the present invention, in order to make the turbidity of dicyclopentadiene less than a certain value, the dicyclopentadiene raw material which does not satisfy the turbidity requirement can be further distilled and dehydrated and purified.
In the cycloolefin polymer optical resin according to the present invention, the norbornene compound contains all the compounds capable of obtaining the structural unit represented by the above formula (2), and specifically, a norbornene compound containing no aromatic ring can be used, and includes: bicyclic compounds such as norbornene, 1-methyl-2-norbornene, 5-methyl-2-norbornene, 7-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-phenyl-2-norbornene, 5, 6-dimethyl-2-norbornene, 5, 6-trimethyl-2-norbornene, 5-chloro-2-norbornene, 5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5, 6-trifluoro-6-trifluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5, 6-diethylidene-2-norbornene, 5-cyclohexenyl-2-norbornene, and 2, 5-norbornadiene; tricyclopentadiene (cyclopentadiene dimer), 1, 2-dihydro dicyclopentadiene, 5, 6-dihydro dicyclopentadiene and other tricyclic compounds; 1,4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene, 2-methyl-1, 4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene 2-ethyl-1, 4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene 2-ethyl-1, 4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene 2-fluoro-1, 4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene, 1, 5-dimethyl-1, 4,5, 8-two-bridge methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene 2-cyclohexyl-1, 4,5, 8-dimethanolidene-1, 2,3, 4a,5,8 a-octahydronaphthalene tetracyclic compounds such as 2, 3-dichloro-1, 4,5, 8-dimethanolidene-1, 2,3, 4a,5,8 a-octahydronaphthalene and 2-isobutyl-1, 4,5, 8-dimethanolidene-1, 2,3, 4a,5,8 a-octahydronaphthalene; pentalene trimer and other pentacyclic compounds; one or more than 2 kinds of heptacyclic compounds such as cyclopentadiene tetramer; norbornene compounds containing aromatic rings, such as: 5-phenyl-2-norbornene, 5-methyl-5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-benzyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene [ i.e., 5- (4-methylphenyl) -2-norbornene ], 5- (ethylphenyl) -bicyclo [2.2.1] hept-2-ene, 5- (isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 5-methyl-5-carboxybenzyl bicyclo [2.2.1] hept-2-ene, 8-phenyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8-methyl-8-phenyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8-benzyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene 8-tolyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (isopropylphenyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8, 9-diphenyl-tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (. Beta. -naphthyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (. Alpha. -naphthyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.12,5.17,10] -3-dodecene, 11-phenyl-hexamethylene [6.6.1.13,6.110,13.02,7.09,14] -4-heptadecene, 6- (. Alpha. -naphthyl) -bicyclo [2.2.1] -hept-2-ene, 5- (anthracenyl) -bicyclo [2.2.1] -hept-2-ene, 5- (biphenyl) -bicyclo [2.2.1] -hept-2-ene, 5- (. Beta. -naphthyl) -bicyclo [2.2.1] -hept-2-ene, 5, 6-diphenyl-bicyclo [2.2.1] -hept-2-ene, 9- (2-norbornene-5-yl) -carbazole 1, 4-methyl-1, 4a,4b,5, 8a,9 a-octahydrofluorene, 1, 4-methyl-1, 4a,9 a-tetrahydrofluorene, 1, 4-methyl-8-methyl-1, 4a,9 a-tetrahydrofluorene 1, 4-methyl-8-chloro-1, 4a,9 a-tetrahydrofluorene, 1, 4-methyl-8-bromo-1, 4a,9 a-tetrahydrofluorene 1, 4-methyl-8-chloro-1, 4a,9 a-tetrahydrofluorene 1, 4-methyl-8-bromo-1, 4a,9 a-tetrahydrofluorene, further, a cyclopentyldiene compound, 11, 12-benzo-pentacyclo [6.5.1.13,6.02,7.09,13] -4-pentadecene, 11, 12-benzo-pentacyclo [6.1]13,6.02,7.09,14] -4-hexadecene, 14, 15-benzo-heptacyclo [8.7.0.12,9.14,7.111,17.03,8.012,16] -5-eicosene, and the like are added to the cyclopentyldiene-acenaphthylene adduct. In the present invention, one norbornene compound may be used alone, or two or more norbornene compounds may be used in combination. In one embodiment of the present invention, the norbornene-based compound includes a norbornene-based compound containing no aromatic ring and a norbornene-based compound containing an aromatic ring, and the mass ratio of the norbornene-based compound containing no aromatic ring to the norbornene-based compound containing an aromatic ring is preferably (2 to 8): 1, more preferably (3 to 6): 1.
In the cycloolefin polymer optical resin according to the present invention, the mass ratio of the dicyclopentadiene to the norbornene-based compound is preferably (0.1 to 3): 1, more preferably (0.2 to 2.5): 1, and most preferably (0.3 to 2): 1. In the present invention, if the mass ratio of dicyclopentadiene to norbornene-based compound is less than 0.1:1 or more than 3:1, the remaining amount of unreacted raw materials becomes large, which is not economically preferable.
In the cycloolefin polymer optical resin according to the present invention, the turbidity of the cycloolefin ring-opening polymer is preferably 12NTU or less when the cycloolefin ring-opening polymer is prepared into a 20wt% toluene solution after being stored in a glass bottle at 25℃for 30 days in an environment having a water content of 1ppm or less and an oxygen content of 1ppm or less. In the present invention, the stability of the cycloolefin ring-opening polymer is evaluated using turbidity, and there is no problem as long as the turbidity value is 12NTU or less, preferably 10NTU or less. In the present invention, the longer the shelf life of the sample is, the better the turbidity value test is, but generally, the turbidity value after 3 days, preferably after 7 days, more preferably after 14 days, and most preferably after 30 days is 12NTU or less, and preferably 10NTU or less. A period of less than 3 days greater than 12NTU does not allow for low cost and efficient production. Specifically, when the turbidity is more than 12NTU, on one hand, the cyclic olefin ring-opening polymer may easily form gel during subsequent high-temperature hydrogenation, which affects the yield; on the other hand, internal stress is easy to form in the molding process, so that the optical performance (namely, the double refractive index) of the cycloolefin polymer optical resin is obviously reduced, and the product quality is influenced.
In the cycloolefin polymer optical resin provided by the invention, one or more of an antioxidant, a plasticizer, a heat stabilizer and an anti-aging agent is preferably further included in the cycloolefin polymer optical resin, wherein the antioxidant comprises one or more of a phenolic antioxidant, a phosphorus antioxidant and a sulfur antioxidant, and particularly beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate can be selected.
The invention also provides a preparation method of the cycloolefin polymer optical resin, which comprises the following steps:
providing dicyclopentadiene having a turbidity value of 2NTU or less when the dicyclopentadiene is prepared into a 50wt% toluene solution;
performing ring-opening metathesis polymerization on the dicyclopentadiene and a norbornene compound to obtain a cycloolefin ring-opening polymer;
and (3) hydrogenating and molding the cycloolefin ring-opening polymer to obtain the cycloolefin polymer optical resin.
In the preparation method provided by the invention, the specific information and the dosage proportion of the dicyclopentadiene and the norbornene compound are described in the foregoing, and are not repeated here.
In the production method provided by the present invention, the ring-opening metathesis polymerization reaction is preferably carried out in the presence of a ring-opening metathesis catalyst. Wherein the ring-opening metathesis catalyst may be a catalyst system comprising a halide, nitrate or acetylacetonate of a metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum and the like, and a reducing agent; catalyst systems composed of halides or acetylacetonates of metals selected from titanium, vanadium, zirconium, tungsten and molybdenum and organoaluminium compounds of cocatalysts may also be used; the active ring-opening metathesis catalysts disclosed in the prior patent or literature may be used alone or in combination of two or more kinds. In the present invention, the ring-opening metathesis catalyst is used in an amount of usually 1 (50 to 2000000), preferably 1 (200 to 1000000), more preferably 1 (500 to 500000), in terms of the mass ratio of the central metal of the catalyst to the total cyclic olefin monomers (dicyclopentadiene and norbornene-based compounds). In the present invention, the subsequent removal becomes difficult when the amount of the ring-opening metathesis catalyst is too large, and sufficient catalytic activity cannot be obtained when too small.
In the production method provided by the present invention, in order to adjust the molecular weight of the produced cycloolefin ring-opening polymer, it is preferable to add an appropriate amount of a molecular weight adjusting agent such as a vinyl compound or a diene compound to the polymerization reaction system during the reaction. In the present invention, the vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group, and examples thereof include: alpha-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyl toluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide, and the like. In the present invention, examples of the diene compound used for molecular weight control include: non-conjugated dienes such as 1, 4-pentadiene, 1, 4-hexadiene, 1, 5-hexadiene, 1, 6-heptadiene, 2-methyl-1, 4-pentadiene, 2, 5-dimethyl-1, 5-hexadiene and the like; conjugated dienes such as 1, 3-butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene and 1, 3-hexadiene. In the present invention, the molecular weight modifier is added in an amount sufficient to obtain a cycloolefin ring-opened polymer having a desired molecular weight, and the mass ratio of the molecular weight modifier to the total monomer of the cyclic olefin is usually 1 (20 to 1000000), preferably 1 (20 to 3000), more preferably 1 (20 to 1000).
In the preparation method provided by the invention, a solvent is generally required for the ring-opening metathesis polymerization reaction. In the present invention, the solvent to be used is not particularly limited as long as it is an organic solvent that does not affect the polymerization reaction and dissolves or disperses the obtained polymer under predetermined conditions, and examples thereof include: aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decalin, bicycloheptane, tricyclodecane, hexahydroindene cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogen aliphatic hydrocarbons such as methylene chloride, chloroform, and 1, 2-dichloroethane; halogen aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; and aromatic ether solvents such as anisole and phenetole. In the present invention, the solvent is preferably one or more of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, an ether solvent and an aromatic ether solvent which are industrially used, and more preferably one or more of toluene, cyclohexane and tetrahydrofuran.
In the production method provided by the present invention, the temperature at which the ring-opening metathesis polymerization reaction is carried out needs to be strictly controlled, usually at-20 to 100 ℃, preferably at 20 to 95 ℃, more preferably at 30 to 90 ℃, and most preferably at 60 ℃. In the present invention, if the reaction temperature is too low, the rate should be lowered; if the reaction temperature is too high, side reactions may occur, widening the molecular weight distribution, and requiring staged temperature control.
In the production method of the present invention, the polymerization pressure at the time of carrying out the ring-opening metathesis polymerization reaction is not particularly limited, and is usually 2MPa or less, preferably 1MPa or less, and more preferably 0.1 to 0.3MPa.
In the production method provided by the present invention, the time for carrying out the ring-opening metathesis polymerization reaction is generally not particularly limited; in general, the polymerization time is from 1min to 100h, preferably from 0.5 to 10h.
In the production method provided by the present invention, the ring-opening metathesis polymerization reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon to prevent deterioration and coloration of the resulting polymer due to oxidation.
In the preparation method provided by the invention, the polymerization monomer and the solvent are subjected to strict water removal treatment, and the water content is required to be lower than 50ppm.
In the preparation method provided by the invention, the hydrogenation of the cycloolefin ring-opening polymer is a reaction of completely hydrogenating all carbon-carbon double bonds and unsaturated bonds such as benzene rings and the like existing on the main chain or/and side chains of the cycloolefin ring-opening polymer; the hydrogenation reaction is carried out by adding a hydrogenation catalyst to a cycloolefin ring-opened polymer in an inert solvent and supplying hydrogen to the reaction system.
In the preparation method provided by the invention, in the process of carrying out the hydrogenation reaction, the hydrogenation catalyst used can be: hydrogenation catalysts comprising dicyclopentyl titanium halide, organic nickel carboxylate, organic cobalt carboxylate, etc., and organometallic compounds of main groups I to III of the periodic table; nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts, cobalt, nickel, rhodium, ruthenium complexes, and the like supported on carbon, silica, diatomaceous earth, and the like; high power lithium aluminum, hydrogenated compounds such as p-toluenesulfonyl hydrazide, and the like; wherein the hydrogenation catalyst is preferably a ruthenium compound, specifically RuHCl (CO) (PPh) 3 ) 3 、RuHCl(CO)[P(p-Me-Ph) 3 ] 3 、RuHCl(CO)(PCy 3 ) 2 、RuHCl(CO)[P(n-Bu) 3 ] 3 、RuHCl(CO)[P(i-Pr) 3 ] 2 、RuH 2 (CO)(PPh 3 ) 3 、RuH 2 (CO)[P(p-Me-Ph) 3 ] 3 、RuH 2 (CO)(PCy 3 ) 3 、RuH 2 (CO)[P(n-Bu) 3 ] 3 、RuH(OCOCH 3 )(CO)(PPh 3 ) 2 、RuH(OCOPh)(CO)(PPh 3 ) 2 、RuH(OCOPh-CH 3 )(CO)(PPh 3 ) 2 、RuH(OCOPh-OCH 3 )(CO)(PPh 3 ) 2 And RuH (OCOPh) (CO) (PCy) 3 ) 2 One or more of the following. In the present invention, the mass ratio of the hydrogenation catalyst to the double bond in the cycloolefin ring-opening polymer is usually 1 (5 to 100000), preferably 1 (5 to 10000).
In the preparation method provided by the invention, the inert solvent used in the hydrogenation reaction comprises, but is not limited to, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halogenated aromatic hydrocarbon, nitrogen-containing hydrocarbon, ether and the like, and specifically cyclohexane can be selected.
In the production method provided by the present invention, the hydrogenation temperature varies depending on the hydrogenation catalyst used during the hydrogenation reaction, but the hydrogenation temperature is usually-20 to 300 ℃, preferably 0 to 250 ℃, more preferably 100 to 200 ℃, and most preferably 140 to 170 ℃. In the present invention, if the hydrogenation temperature is too low, the reaction rate may be slow; if the hydrogenation temperature is too high, side reactions may occur.
In the production process of the present invention, the hydrogen pressure during the hydrogenation is generally 0.01 to 20MPa, preferably 0.1 to 10MPa, more preferably 1to 5MPa, and most preferably 2.5 to 4.5MPa. In the invention, the hydrogen pressure is too low, so that the hydrogenation reaction rate is slow; too high a hydrogen pressure would require a reactor that is resistant to high pressures.
In the production method of the present invention, the hydrogenation rate of the unsaturated bond in the obtained cyclic olefin ring-opening hydrogenated copolymer after completion of the hydrogenation reaction is preferably 90% or more, more preferably 95% or more, still more preferably 99% or more, and particularly preferably 99.5% or more. In the present invention, if the hydrogenation ratio of the hydrogenated copolymer is within the above range, coloration of the optical resin due to resin firing can be suppressed.
In the production method of the present invention, after the completion of the hydrogenation reaction, the obtained cyclic olefin ring-opening hydrogenated copolymer may be recovered by a conventional method, and the catalyst residue may be removed by filtration or the like at the time of recovering the hydrogenated copolymer.
In the preparation method provided by the invention, other high molecular materials and/or additives can be added in the process of preparing the cycloolefin polymer optical resin, and the preparation method is not particularly limited. The types of the polymer material and the additive are not particularly limited as long as the polymer material and the additive can be sufficiently dispersed in such a cyclic olefin ring-opening hydrogenated copolymer, and the polymer material and the additive may be mixed with the cyclic olefin ring-opening hydrogenated copolymer by any method. Specifically, the polymer material and the additive may be added during any process in the preparation of the cyclic olefin ring-opening hydrogenated copolymer, or may be kneaded with the cyclic olefin ring-opening hydrogenated copolymer using a kneader, or may be mixed with the cyclic olefin ring-opening hydrogenated copolymer in a molding apparatus.
The invention also provides an optical product which is made of the cycloolefin polymer optical resin disclosed in the technical scheme or the cycloolefin polymer optical resin manufactured by the manufacturing method disclosed in the technical scheme.
In the optical article provided by the present invention, the optical article is preferably an optical lens, an optical film, an optical disc, a light guide plate, or a display panel; wherein the optical lens is preferably a spectacle lens, a camera lens, a sensor lens, an illumination lens or an imaging lens.
In the optical article provided by the present invention, the stress birefringence (C R ) At-500×10 -12 ～1400×10 -12 Pa -1 Between them.
For the sake of clarity, the following examples and comparative examples are described in detail. The raw materials used in the examples below are all commercially available products, except for the specific descriptions, and the various proportions are all weight proportions.
In the following examples and comparative examples of the present invention, the evaluation methods were performed as follows.
Turbidity: the measurement range can be automatically selected by adopting a HACH2100N turbidimeter, the measurement range is 0-10000 NTU, the graduation value is 0.01NTU, the scattering mode comprises 90-degree scattering, forward scattering, backward scattering and transmission, and the tungsten lamp light source adopts 400-600 nm light.
Turbidity of dicyclopentadiene: a50 wt% toluene solution was prepared and turbidity was measured.
Turbidity of cycloolefin ring-opening polymer: preparing a toluene solution with 20wt% and measuring turbidity; the turbidity of 2NTU or less was ∈, the turbidity of 2 to 12NTU was Δ, the turbidity of more than 12NTU was x, and the turbidity of Δ or more was a usable grade.
Stress birefringence C of Polymer R Is determined by the following steps: shaping the polymer into a sheet shape with a length of 35mm, a width of 10mm and a thickness of 1mm to obtain a sample sheet; after fixing the two ends of the sample piece by using a clamp, fixing a weight of 55g on one clamp; next, after the temperature is set to the glass transition temperature (T g ) In an oven at +15℃, the sample piece was lifted for 1 hour from a jig without a fixed weight, and subjected to stretching treatment. Then slowly cooling the sample piece, and recovering to room temperature to obtain a measurement sample; a birefringent (WPA-100 manufactured by Photonic Crystal, inc.) was used for the measurement sample to measure the in-plane retardation (Re [ nm ] of the wavelength 543nm for the center portion of the measurement sample]) Measuring; further, the thickness (d [ mm]) Measuring; using these measured values Re and d, the measurement value was obtained by the following formula (S 1 ) Calculating the optical path difference delta of unit thickness n Value:
δ n ＝Re×(1/d)×10 -6 (S 1 )；
using the δn value and the stress (F) applied to the sample, the sample was obtained by the following formula (S 2 ) Calculation of stress birefringence (C) R )：
C R ＝δ n /F[Pa -1 ](S 2 )；
δ n The closer the value is to 0, the smaller the birefringence; in addition, the slow axis is a positive value when the slow axis is in the stretching direction, and the slow axis and the stretching direction are the sameThe extension direction is orthogonal and is represented as a negative value.
Yield is as follows: in this example, 100 tablets were visually observed under a high-pressure mercury lamp, and it was confirmed that products having a phenomenon that the local refractive index was different from the surrounding normal refractive index due to the difference in composition such as streaks and bubbles were judged to be defective, and the yield was calculated after statistics.
Example 1
Into a flask in which nitrogen substitution was performed, 30 parts of dicyclopentadiene having a turbidity of 0.05NTU as a 50wt% toluene solution of a cyclic olefin monomer, 10 parts of norbornene compound 1, 4-methyl-1, 4a,9 a-tetrahydrofluorene having an aromatic ring and 60 parts of 1,4,5, 8-bridged methylene-1, 2,3, 4a,5,8 a-octahydronaphthalene having no aromatic ring were sequentially added, 400 parts of toluene, 0.1 part of diethylaluminum, 0.15 part of isopropyl alcohol and 1.2 parts of 1-hexene as a chain transfer agent; 100.5 parts of toluene solution of 0.48wt% tungsten hexachloride catalyst was added thereto, and the reaction solution was stirred at 60℃and 0.2MPa for 2 hours or more to carry out ring-opening metathesis polymerization; after the polymerization was completed, the polymerization conversion of the monomer as determined by gas chromatography was 100% at the end of the polymerization; after the quenching reaction of the added ethanol, removing the solvent by high-temperature vacuum drying for 24 hours after ethanol chromatography, and obtaining the cycloolefin ring-opening polymer after cooling; the obtained cycloolefin ring-opened polymer was prepared into a 20wt% toluene solution, and the resultant solution was stored in a glass bottle (250 mL of a colorless and transparent wide-mouth flask made of PYREX (registered trademark), the same applies hereinafter) at 25℃under an environment having a water content of 1ppm or less and an oxygen content of 1ppm or less, and turbidity after 0, 3, 7, 14 and 30 days was measured, and the results are shown in Table 1.
Transferring the obtained cycloolefin ring-opened polymer into a pressure-resistant hydrogenation reactor, adding 0.5 part of palladium supported on alumina (manufactured by Adamas corporation, wet base 55%, palladium load 10% by weight) as a catalyst, adding cyclohexane as a solvent to prepare a solution with a polymer concentration of 20% by weight, and carrying out hydrogenation reaction at a temperature of 160 ℃ under a hydrogen pressure of 4.5MPa for 6 hours, wherein the catalyst is prepared by 1 The hydrogenation rate of the obtained hydride was 99.9% by H NMR measurement; after the hydrogenation reaction was completed, 0.1 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant was added thereto, and the mixture was dried in a vacuum oven (180 ℃ C., C.1 Torr) for 10 hours to obtain a cycloolefin polymer optical resin. The resultant cycloolefin polymer optical resin was tested for stress birefringence, and the results are shown in Table 1.
Examples 2 to 4
A cycloolefin ring-opening polymer was produced in the same manner as in example 1 using dicyclopentadiene having turbidity shown in table 1; the results of measuring turbidity after 0, 3, 7, 14 and 30 days in a glass bottle at 25℃under the conditions of water content of 1ppm or less and oxygen content of 1ppm or less in the same manner as in example 1 are shown in Table 1; a cycloolefin polymer optical resin was prepared in the same manner as in example 1, and the resultant cycloolefin polymer optical resin was tested for stress birefringence, and the results are shown in table 1.
Comparative examples 1to 3
Using dicyclopentadiene having turbidity shown in table 1, a cycloolefin ring-opened polymer was obtained in the same manner as in example 1; the results of measuring turbidity after 0, 3, 7, 14 and 30 days in a glass bottle at 25℃under the conditions of water content of 1ppm or less and oxygen content of 1ppm or less in the same manner as in example 1 are shown in Table 1; a cycloolefin polymer optical resin was prepared in the same manner as in example 1, and the resultant cycloolefin polymer optical resin was tested for stress birefringence, and the results are shown in table 1.
TABLE 1 raw material index and physical Property values of cycloolefin optical resin
From the comparison results of the above examples and comparative examples, it is understood that the turbidity index present in the dicyclopentadiene raw material has an important influence on the occurrence rate of optical deformation, and that the product quality can be effectively ensured when the turbidity of the dicyclopentadiene raw material is controlled to be 2NTU or less. In particular, when the turbidity of the dicyclopentadiene material is 1NTU or less, the obtained optical resin has better physical properties and higher yield. With the increase of turbidity content in dicyclopentadiene compound, the opaqueness of cycloolefin ring-opening polymer becomes more obvious, and various indexes of optical products become worse gradually, so that the quality of the products is reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An optical resin of cycloolefin polymer is characterized in that the optical resin is prepared by hydrogenation and molding of cycloolefin ring-opening polymer;
the cycloolefin ring-opening polymer is prepared by ring-opening metathesis polymerization of dicyclopentadiene and norbornene compounds;
the turbidity value of the dicyclopentadiene when the dicyclopentadiene is prepared into a 50wt% toluene solution is 2NTU or less.
2. The cycloolefin polymer optical resin according to claim 1, characterized in that the turbidity value of the dicyclopentadiene when it is made into a 50wt% toluene solution is 1NTU or less.
3. The cycloolefin polymer optical resin according to claim 1, characterized in that the cycloolefin ring-opening polymer contains a structural unit of the formula (1) and a structural unit of the formula (2):
wherein a is an integer between 1 and 100; b is an integer between 1 and 100; n, m and s are independently 0,1, 2 or 3; r is R 1 ～R 10 Independently a hydrogen atom, a halogen atom other than a fluorine atom or a hydrocarbon group having 1to 10 carbon atoms substituted with a halogen atom other than a fluorine atom; r is R 3 、R 4 、R 9 And R is 10 Is an independent substituent, or R 3 、R 4 、R 9 And R is 10 At least one pair of substituents being bonded to form a ring; r is R 5 、R 6 、R 7 And R is 8 Is an independent substituent, or R 5 、R 6 、R 7 And R is 8 At least one pair of substituents being bonded to form a ring.
4. The cycloolefin polymer optical resin according to claim 1, further comprising one or more of an antioxidant, a plasticizer, a heat stabilizer and an anti-aging agent.
5. A method for preparing a cycloolefin polymer optical resin, comprising the steps of:
providing dicyclopentadiene having a turbidity value of 2NTU or less when the dicyclopentadiene is prepared into a 50wt% toluene solution;
performing ring-opening metathesis polymerization on the dicyclopentadiene and a norbornene compound to obtain a cycloolefin ring-opening polymer;
and (3) hydrogenating and molding the cycloolefin ring-opening polymer to obtain the cycloolefin polymer optical resin.
6. The process according to claim 5, wherein the ring-opening metathesis polymerization is carried out at a temperature of 30 to 90℃and a pressure of 0 to 2MPa for a period of 0.5 to 10 hours.
7. The method according to claim 5, wherein the ring-opening metathesis polymerization reaction is carried out in an inert solvent; the inert solvent is one or more of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents and aromatic ether solvents.
8. An optical article, characterized in that the optical article is made of the cycloolefin polymer optical resin according to any one of claims 1to 4 or the cycloolefin polymer optical resin produced by the production method according to any one of claims 5 to 7.
9. The optical article of claim 8, wherein the optical article is an optical lens, an optical film, an optical disc, a light guide plate, or a display panel.
10. The optical article of claim 9, wherein the optical lens is a spectacle lens, a camera lens, a sensor lens, an illumination lens, or an imaging lens.
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