KR20230097467A - Polycarbonate copolymer having improved scratch resistance and high refractive index and method for preparing the same - Google Patents
Polycarbonate copolymer having improved scratch resistance and high refractive index and method for preparing the same Download PDFInfo
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- KR20230097467A KR20230097467A KR1020210186975A KR20210186975A KR20230097467A KR 20230097467 A KR20230097467 A KR 20230097467A KR 1020210186975 A KR1020210186975 A KR 1020210186975A KR 20210186975 A KR20210186975 A KR 20210186975A KR 20230097467 A KR20230097467 A KR 20230097467A
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- compound
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- formula
- carbon atoms
- polycarbonate
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 58
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 17
- -1 diallyl bisphenol Chemical compound 0.000 claims abstract description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- 150000002009 diols Chemical class 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 16
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 150000002220 fluorenes Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 125000003375 sulfoxide group Chemical group 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 28
- 229920001897 terpolymer Polymers 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical class C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 8
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- URFNSYWAGGETFK-UHFFFAOYSA-N 4,4'-Dihydroxybibenzyl Chemical compound C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 1
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- AYNPIRVEWMUJDE-UHFFFAOYSA-N 2,5-dichlorohydroquinone Chemical compound OC1=CC(Cl)=C(O)C=C1Cl AYNPIRVEWMUJDE-UHFFFAOYSA-N 0.000 description 1
- ZKZKMLKTQUCSNX-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfinylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)C1=CC(Br)=C(O)C(Br)=C1 ZKZKMLKTQUCSNX-UHFFFAOYSA-N 0.000 description 1
- TXYQFJWVHVYIHB-UHFFFAOYSA-N 2,6-dichloro-4-(3,5-dichloro-4-hydroxyphenoxy)phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1OC1=CC(Cl)=C(O)C(Cl)=C1 TXYQFJWVHVYIHB-UHFFFAOYSA-N 0.000 description 1
- WIFDRXSVRSCMMY-UHFFFAOYSA-N 2,6-dichloro-4-[(3,5-dichloro-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1CC1=CC(Cl)=C(O)C(Cl)=C1 WIFDRXSVRSCMMY-UHFFFAOYSA-N 0.000 description 1
- ANLICCDGDIUHJE-UHFFFAOYSA-N 2,6-dichloro-4-[1-(3,5-dichloro-4-hydroxyphenyl)cyclohexyl]phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1C1(C=2C=C(Cl)C(O)=C(Cl)C=2)CCCCC1 ANLICCDGDIUHJE-UHFFFAOYSA-N 0.000 description 1
- PWDGALQKQJSBKU-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Cl)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(Cl)=C1 PWDGALQKQJSBKU-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- KLPQUCKLVZXJEH-UHFFFAOYSA-N 2-fluoro-4-[2-(3-fluoro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(F)=CC=1C(C)(C)C1=CC=C(O)C(F)=C1 KLPQUCKLVZXJEH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- RKSBPFMNOJWYSB-UHFFFAOYSA-N 3,3-Bis(4-hydroxyphenyl)pentane Chemical compound C=1C=C(O)C=CC=1C(CC)(CC)C1=CC=C(O)C=C1 RKSBPFMNOJWYSB-UHFFFAOYSA-N 0.000 description 1
- ZGZVGZCIFZBNCN-UHFFFAOYSA-N 4,4'-(2-Methylpropylidene)bisphenol Chemical compound C=1C=C(O)C=CC=1C(C(C)C)C1=CC=C(O)C=C1 ZGZVGZCIFZBNCN-UHFFFAOYSA-N 0.000 description 1
- GXDIDDARPBFKNG-UHFFFAOYSA-N 4,4'-(Butane-1,1-diyl)diphenol Chemical compound C=1C=C(O)C=CC=1C(CCC)C1=CC=C(O)C=C1 GXDIDDARPBFKNG-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- MLDIQALUMKMHCC-UHFFFAOYSA-N 4,4-Bis(4-hydroxyphenyl)heptane Chemical compound C=1C=C(O)C=CC=1C(CCC)(CCC)C1=CC=C(O)C=C1 MLDIQALUMKMHCC-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- UHIIHYFGCONAHB-UHFFFAOYSA-N 4,6-dimethyl-1,3-dioxan-2-one Chemical compound CC1CC(C)OC(=O)O1 UHIIHYFGCONAHB-UHFFFAOYSA-N 0.000 description 1
- GDEHXPCZWFXRKC-UHFFFAOYSA-N 4-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC=C(O)C=C1 GDEHXPCZWFXRKC-UHFFFAOYSA-N 0.000 description 1
- KQSIVRHDEPHUII-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenoxy)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(OC=2C=C(C)C(O)=C(C)C=2)=C1 KQSIVRHDEPHUII-UHFFFAOYSA-N 0.000 description 1
- JPSMTGONABILTP-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfanyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(SC=2C=C(C)C(O)=C(C)C=2)=C1 JPSMTGONABILTP-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- HVXRCAWUNAOCTA-UHFFFAOYSA-N 4-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=C(O)C=C1 HVXRCAWUNAOCTA-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- QHSCVNPSSKNMQL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-naphthalen-1-ylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(O)C=C1 QHSCVNPSSKNMQL-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- FLCXQXDIBIICJR-UHFFFAOYSA-N 4-[1-(4-hydroxy-3,5-dimethylphenyl)cyclododecyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2(CCCCCCCCCCC2)C=2C=C(C)C(O)=C(C)C=2)=C1 FLCXQXDIBIICJR-UHFFFAOYSA-N 0.000 description 1
- BWCAVNWKMVHLFW-UHFFFAOYSA-N 4-[1-(4-hydroxy-3,5-dimethylphenyl)cyclohexyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2(CCCCC2)C=2C=C(C)C(O)=C(C)C=2)=C1 BWCAVNWKMVHLFW-UHFFFAOYSA-N 0.000 description 1
- ZRMMDTUHWYZHEW-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-1-naphthalen-1-ylethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C2=CC=CC=C2C=CC=1)(C)C1=CC=C(O)C=C1 ZRMMDTUHWYZHEW-UHFFFAOYSA-N 0.000 description 1
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- YTGYVXZVFCPXEP-UHFFFAOYSA-N 4-[10-(4-hydroxyphenyl)decyl]phenol Chemical compound C1=CC(O)=CC=C1CCCCCCCCCCC1=CC=C(O)C=C1 YTGYVXZVFCPXEP-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- ZQTPHEAGPRFALE-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)hexan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCC)C1=CC=C(O)C=C1 ZQTPHEAGPRFALE-UHFFFAOYSA-N 0.000 description 1
- KBWOAGGPYKQCAO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)nonan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCCC)C1=CC=C(O)C=C1 KBWOAGGPYKQCAO-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- NIRYBKWMEWFDPM-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-methylbutyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CCC1=CC=C(O)C=C1 NIRYBKWMEWFDPM-UHFFFAOYSA-N 0.000 description 1
- RHSDKKXLNNCMIC-UHFFFAOYSA-N 4-[4-(4-hydroxyphenyl)butyl]phenol Chemical compound C1=CC(O)=CC=C1CCCCC1=CC=C(O)C=C1 RHSDKKXLNNCMIC-UHFFFAOYSA-N 0.000 description 1
- OFOBGFGQFWCIBT-UHFFFAOYSA-N 4-ethyl-1,3-dioxan-2-one Chemical compound CCC1CCOC(=O)O1 OFOBGFGQFWCIBT-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- OVDQEUFSGODEBT-UHFFFAOYSA-N 4-methyl-1,3-dioxan-2-one Chemical compound CC1CCOC(=O)O1 OVDQEUFSGODEBT-UHFFFAOYSA-N 0.000 description 1
- JKNNDGRRIOGKKO-UHFFFAOYSA-N 4-methyl-1,3-dioxepan-2-one Chemical compound CC1CCCOC(=O)O1 JKNNDGRRIOGKKO-UHFFFAOYSA-N 0.000 description 1
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 description 1
- JRFXQKZEGILCCO-UHFFFAOYSA-N 5,5-dimethyl-1,3-dioxan-2-one Chemical compound CC1(C)COC(=O)OC1 JRFXQKZEGILCCO-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- QVJZYXSOHOBUFF-UHFFFAOYSA-N OC1=C(C=CC(=C1)O)C(C)(CC(C)C)C1=C(C=C(C=C1)O)O Chemical compound OC1=C(C=CC(=C1)O)C(C)(CC(C)C)C1=C(C=C(C=C1)O)O QVJZYXSOHOBUFF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- PDYNXWPJDVOHDW-UHFFFAOYSA-N bis(3-methylphenyl) carbonate Chemical compound CC1=CC=CC(OC(=O)OC=2C=C(C)C=CC=2)=C1 PDYNXWPJDVOHDW-UHFFFAOYSA-N 0.000 description 1
- JWAPUVVSOVJCJB-UHFFFAOYSA-N bis(4-hydroxy-3,5-dimethylphenyl)methanone Chemical compound CC1=C(O)C(C)=CC(C(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 JWAPUVVSOVJCJB-UHFFFAOYSA-N 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-M butyl carbonate Chemical compound CCCCOC([O-])=O DFFDSQBEGQFJJU-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RZTHZKJOZZSSOV-UHFFFAOYSA-N ethyl 2-methylpropyl carbonate Chemical compound CCOC(=O)OCC(C)C RZTHZKJOZZSSOV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/26—General preparatory processes using halocarbonates
- C08G64/28—General preparatory processes using halocarbonates and phenols
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
본 발명은 폴리카보네이트 공중합체 및 그 제조방법에 관한 것으로, 더욱 상세하게는, 디알릴 비스페놀계 화합물로부터 유래된 반복 단위; 플루오렌계 디올 화합물로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하며, 종래의 선형 폴리카보네이트 및 폴리카보네이트 공중합체 대비 내충격성 및 투명성을 우수하게 유지하면서도 향상된 내스크래치성 및 고굴절률을 나타내는 폴리카보네이트 공중합체 및 그 제조방법에 관한 것이다.The present invention relates to a polycarbonate copolymer and a method for producing the same, and more specifically, to a repeating unit derived from a diallyl bisphenol-based compound; repeating units derived from fluorene-based diol compounds; And a polycarbonate repeating unit; and a polycarbonate copolymer exhibiting improved scratch resistance and high refractive index while maintaining excellent impact resistance and transparency compared to conventional linear polycarbonate and polycarbonate copolymers, and a method for manufacturing the same. .
Description
본 발명은 폴리카보네이트 공중합체 및 그 제조방법에 관한 것으로, 더욱 상세하게는, 디알릴 비스페놀계 화합물로부터 유래된 반복 단위; 플루오렌계 디올 화합물로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하며, 종래의 선형 폴리카보네이트 및 폴리카보네이트 공중합체 대비 내충격성 및 투명성을 우수하게 유지하면서도 향상된 내스크래치성 및 고굴절률을 나타내는 폴리카보네이트 공중합체 및 그 제조방법에 관한 것이다.The present invention relates to a polycarbonate copolymer and a method for producing the same, and more specifically, to a repeating unit derived from a diallyl bisphenol-based compound; repeating units derived from fluorene-based diol compounds; And a polycarbonate repeating unit; and a polycarbonate copolymer exhibiting improved scratch resistance and high refractive index while maintaining excellent impact resistance and transparency compared to conventional linear polycarbonate and polycarbonate copolymers, and a method for manufacturing the same. .
폴리카보네이트는 인장 강도와 내충격성 등의 기계적 물성이 우수하고, 치수 안전성, 내열성 및 광학적 투명성 등이 우수하여 산업용으로 많이 사용되고 있다. 폴리카보네이트의 물성을 개선하기 위하여 다양한 공중합체에 대한 연구가 계속되고 있으며, 예컨대, 저온 내충격성의 개선을 위해 폴리실록산-폴리카보네이트 공중합체가 제안된 바 있다(미국공개특허 제2003-0105226호).Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and is widely used for industrial purposes because of its excellent dimensional stability, heat resistance, and optical transparency. In order to improve the physical properties of polycarbonate, research on various copolymers continues, and for example, a polysiloxane-polycarbonate copolymer has been proposed to improve low-temperature impact resistance (US Patent Publication No. 2003-0105226).
비스페놀 A 및 포스겐을 이용하여 제조된 폴리카보네이트의 화학적 구조는 기본적으로 말단기에 수산기를 지니고 있으며, 양 말단기의 수산기를 활성화하는 방법을 이용하여 새로운 형태의 고분자를 제조할 수 있다. 이 때, 중합은 수용성 용액 중에서, 계면에서, 또는 비수용성 용액 중에서 이루어질 수 있다. The chemical structure of polycarbonate prepared using bisphenol A and phosgene basically has a hydroxyl group at the end group, and a new type of polymer can be prepared using a method of activating the hydroxyl group at both terminal groups. At this time, polymerization may be performed in an aqueous solution, at an interface, or in a non-aqueous solution.
그러나, 특히 비스페놀 A로부터 제조된 폴리카보네이트는 제한된 내스크래치성을 가진다. 따라서 그 스크래치 손상을 막거나 또는 최소화하기 위해서는 표면 개질로서 하드 코트를 도포하여야 하는데, 이 하드 코트는 추가 공정과 비용이 수반되며, 내구성이 떨어지는 단점을 가진다. However, polycarbonates, especially made from bisphenol A, have limited scratch resistance. Therefore, in order to prevent or minimize the scratch damage, a hard coat must be applied as a surface modification, but this hard coat involves additional processes and costs, and has poor durability.
대한민국 등록특허 제10-1815930호는 내스크래치성 및 수증기 서림 방지 특성을 개선한 폴리카보네이트 공중합체를 개시하고 있으며, 여기에 개시된 폴리카보네이트 공중합체는 우수한 수증기 서림 방지 특성을 나타내지만, 내스크래치성 측면에서는 더욱 개선될 필요가 있다. Korean Patent Registration No. 10-1815930 discloses a polycarbonate copolymer with improved scratch resistance and anti-fogging properties, and the polycarbonate copolymer disclosed herein exhibits excellent anti-fogging properties, but also has anti-scratch properties. needs to be further improved.
따라서, 폴리카보네이트 고유의 물성인 투명성 및 충격강도를 우수하게 유지하면서 내스크래치성은 더욱 향상된 고굴절률의 폴리카보네이트 공중합체의 개발이 요구되고 있다.Therefore, there is a demand for the development of a polycarbonate copolymer having a high refractive index with improved scratch resistance while maintaining transparency and impact strength, which are inherent properties of polycarbonate.
본 발명은 상기와 같은 종래기술의 문제점을 해결하고자 한 것으로, 종래의 선형 폴리카보네이트 및 종래의 폴리카보네이트 공중합체 대비 내충격성 및 투명성을 우수하게 유지하면서도 향상된 내스크래치성 및 고굴절률을 나타내는 공중합체 및 그 제조방법을 제공하는 것을 기술적 과제로 한다.The present invention is to solve the problems of the prior art as described above, a copolymer showing improved scratch resistance and high refractive index while maintaining excellent impact resistance and transparency compared to conventional linear polycarbonate and conventional polycarbonate copolymer, and It is a technical task to provide a manufacturing method thereof.
상기한 기술적 과제를 해결하고자, 본 발명의 일 측면은, 치환되거나 비치환된 디알릴 비스페놀계 화합물로부터 유래된 반복 단위; 치환되거나 비치환된 플루오렌계 디올 화합물로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하는 폴리카보네이트 공중합체를 제공한다.In order to solve the above technical problem, one aspect of the present invention is a repeating unit derived from a substituted or unsubstituted diallyl bisphenol-based compound; repeating units derived from substituted or unsubstituted fluorene-based diol compounds; And polycarbonate repeating units; it provides a polycarbonate copolymer comprising a.
본 발명의 바람직한 일 구체예에 따르면, 본 발명은, 하기 화학식 1로 표시되는 화합물 유래 반복 단위; 하기 화학식 2로 표시되는 화합물 유래 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하는, 폴리카보네이트 공중합체를 제공한다:According to one preferred embodiment of the present invention, the present invention, a repeating unit derived from a compound represented by Formula 1; a repeating unit derived from a compound represented by Formula 2 below; And polycarbonate repeating units; provides a polycarbonate copolymer comprising:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 및 R2는 각각 독립적으로, 수소 원자, 탄소수 1 내지 30의 알킬기, 탄소수 3 내지 30의 사이클로알킬기, 또는 탄소수 6 내지 30의 아릴기를 나타내고,R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;
m 및 n은 각각 독립적으로, 0 내지 3의 정수를 나타내며;m and n each independently represents an integer of 0 to 3;
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
R3 및 R4는 각각 독립적으로, 수소 원자; 탄소수 1 내지 30의 알킬기; 탄소수 3 내지 30의 사이클로알킬기; 또는 탄소수 6 내지 30의 아릴기를 나타내고, R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,
q 및 r은 각각 독립적으로, 0 내지 4의 정수를 나타낸다.q and r each independently represent an integer of 0 to 4;
본 발명의 다른 측면은, 치환되거나 비치환된 디알릴 비스페놀계 화합물 및 치환되거나 비치환된 플루오렌계 디올 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하는, 폴리카보네이트 공중합체의 제조방법을 제공한다. Another aspect of the present invention is a diol component including a substituted or unsubstituted diallyl bisphenol-based compound and a substituted or unsubstituted fluorene-based diol compound; And a carbonic acid diester compound or a carbonate precursor; It provides a method for producing a polycarbonate copolymer comprising the step of copolymerizing.
본 발명의 바람직한 일 구체예에 따르면, 본 발명은, 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하는, 폴리카보네이트 공중합체의 제조방법을 제공한다.According to one preferred embodiment of the present invention, the present invention, a diol component including the compound represented by the formula (1) and the compound represented by the formula (2); And a carbonic acid diester compound or a carbonate precursor; It provides a method for producing a polycarbonate copolymer comprising the step of copolymerizing.
본 발명의 또 다른 측면은, 본 발명에 따른 폴리카보네이트 공중합체를 포함하는 성형품을 제공한다.Another aspect of the present invention provides a molded article comprising the polycarbonate copolymer according to the present invention.
본 발명에 따른 폴리카보네이트 공중합체는 내충격성 및 투명성을 우수하게 유지하면서도 향상된 내스크래치성 및 고굴절률을 나타내기 때문에, 이를 포함하는 성형품(예컨대, 필름, 시트, 렌즈, 커버글라스, 내외장재 등)은 다양한 산업에서 광학적 용도 및 자재 경량화 대체품의 용도에 매우 적합하게 사용될 수 있다.Since the polycarbonate copolymer according to the present invention exhibits improved scratch resistance and high refractive index while maintaining excellent impact resistance and transparency, molded articles including the same (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) It can be used very suitably for optical applications and materials lightweight alternatives in various industries.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 명세서에서 임의의 화합물, 기 또는 구조가 “치환된다”는 것은, 해당 화합물, 기 또는 구조가 할로겐 원자(예컨대, F, Cl 또는 Br), 히드록시기, 알킬기(예컨대, 탄소수 1 내지 10, 또는 탄소수 1 내지 6의 알킬기), 알콕시기(예컨대, 탄소수 1 내지 10, 또는 탄소수 1 내지 6의 알콕시기), 사이클로알킬기(예컨대, 탄소수 3 내지 10, 또는 탄소수 3 내지 6의 사이클로알킬기), 아릴기(예컨대, 탄소수 6 내지 12, 또는 탄소수 6의 아릴기) 또는 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상의 치환기에 의하여 치환됨을 의미한다.As used herein, any compound, group or structure “substituted” means that the compound, group or structure is a halogen atom (eg, F, Cl or Br), a hydroxy group, an alkyl group (eg, 1 to 10 carbon atoms or 1 to 10 carbon atoms). 1 to 6 alkyl group), an alkoxy group (eg, 1 to 10 carbon atoms or 1 to 6 carbon atoms alkoxy group), a cycloalkyl group (eg, 3 to 10 carbon atoms or 3 to 6 carbon atoms cycloalkyl group), an aryl group ( For example, an aryl group having 6 to 12 carbon atoms or 6 carbon atoms) or a combination thereof.
본 발명의 공중합체는, 치환되거나 비치환된 디알릴 비스페놀계 화합물로부터 유래된 반복 단위; 치환되거나 비치환된 플루오렌계 디올 화합물로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함한다.The copolymer of the present invention includes a repeating unit derived from a substituted or unsubstituted diallyl bisphenol-based compound; repeating units derived from substituted or unsubstituted fluorene-based diol compounds; and polycarbonate repeating units.
본 명세서에서, 디알릴 비스페놀계 화합물은 하나 이상의 “비스페놀” 구조를 함유하면서, 비스페놀 구조 중의 두 페놀 부위가 알릴기를 갖는 화합물을 의미하며, 상기 디알릴 비스페놀계 화합물은 치환되거나, 비치환된 것일 수 있다. In the present specification, a diallyl bisphenol-based compound refers to a compound containing at least one “bisphenol” structure and having allyl groups at two phenol sites in the bisphenol structure, and the diallyl bisphenol-based compound may be substituted or unsubstituted. there is.
일 구체예에서, 상기 디알릴 비스페놀계 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다:In one embodiment, the diallyl bisphenol-based compound may be a compound represented by Formula 1 below:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
R1 및 R2는 각각 독립적으로, 수소 원자, 탄소수 1 내지 30의 알킬기, 탄소수 3 내지 30의 사이클로알킬기, 또는 탄소수 6 내지 30의 아릴기를 나타내고,R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;
m 및 n은 각각 독립적으로, 0 내지 3의 정수를 나타낸다.m and n each independently represents an integer of 0 to 3;
보다 구체적으로, 상기 화학식 1에서, R1 및 R2는 각각 독립적으로, 수소 원자, 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 사이클로알킬기, 또는 탄소수 6 내지 20의 아릴기를 나타내고, 보다 더 구체적으로는, 수소 원자, 탄소수 1 내지 10의 알킬기, 탄소수 3 내지 10의 사이클로알킬기, 또는 탄소수 6 내지 12의 아릴기를 나타낸다.More specifically, in Formula 1, R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more specifically represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or an aryl group of 6 to 12 carbon atoms.
일 구체예에서, 상기 디알릴 비스페놀계 화합물은 치환되거나 비치환된 디알릴 비스페놀 A일 수 있고, 보다 구체적으로는, 하기 구조의 화합물일 수 있다:In one embodiment, the diallyl bisphenol-based compound may be substituted or unsubstituted diallyl bisphenol A, and more specifically, may be a compound having the following structure:
본 명세서에서, 플루오렌계 디올 화합물은 하나 이상의 “플루오렌” 구조를 함유하면서, 양 말단에 히드록시기를 갖는 화합물을 의미하며, 상기 플루오렌계 디올 화합물은 치환되거나, 비치환된 것일 수 있다. In the present specification, a fluorene-based diol compound refers to a compound having at least one “fluorene” structure and having hydroxyl groups at both ends, and the fluorene-based diol compound may be substituted or unsubstituted.
일 구체예에서, 상기 플루오렌계 디올 화합물은 하기 화학식 2로 표시되는 화합물일 수 있다:In one embodiment, the fluorene-based diol compound may be a compound represented by Formula 2 below:
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
R3 및 R4는 각각 독립적으로, 수소 원자; 탄소수 1 내지 30의 알킬기; 탄소수 3 내지 30의 사이클로알킬기; 또는 탄소수 6 내지 30의 아릴기를 나타내고, R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,
q 및 r은 각각 독립적으로, 0 내지 4의 정수를 나타낸다.q and r each independently represent an integer of 0 to 4;
보다 구체적으로, 상기 화학식 2에서, R3 및 R4는 각각 독립적으로, 수소 원자; 탄소수 1 내지 20의 알킬기; 탄소수 3 내지 20의 사이클로알킬기; 또는 탄소수 6 내지 20의 아릴기를 나타내고, 보다 구체적으로는, 수소 원자; 탄소수 1 내지 10의 알킬기; 탄소수 3 내지 10의 사이클로알킬기; 또는 탄소수 6 내지 12의 아릴기를 나타낸다.More specifically, in Formula 2, R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms, more specifically, a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; Or an aryl group having 6 to 12 carbon atoms.
바람직한 일 구체예에서, 본 발명의 공중합체는, 상기 화학식 1로 표시되는 화합물 유래 반복 단위; 상기 화학식 2로 표시되는 화합물 유래 반복 단위; 및 폴리카보네이트 반복 단위;를 포함한다.In a preferred embodiment, the copolymer of the present invention comprises a repeating unit derived from the compound represented by Formula 1; a repeating unit derived from the compound represented by Formula 2; and polycarbonate repeating units.
본 발명의 일 구체예에 따르면, 본 발명의 공중합체는, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 및 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 이외의 디올 화합물(이하, “추가의 디올 화합물”이라고도 한다)로부터 유래된 반복 단위를 더 포함할 수 있다.According to one embodiment of the present invention, the copolymer of the present invention is a substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 1) and a substituted or unsubstituted fluorene-based diol compound (more specifically, It may further include a repeating unit derived from a diol compound (hereinafter, also referred to as “an additional diol compound”) other than the compound of Formula 2).
일 구체예에서, 상기 추가의 디올 화합물은 2가 페놀류 화합물일 수 있다.In one embodiment, the additional diol compound may be a dihydric phenolic compound.
보다 구체적으로, 상기 2가 페놀류 화합물은 하기 화학식 3의 구조를 갖는 화합물일 수 있다:More specifically, the dihydric phenolic compound may be a compound having a structure represented by Formula 3 below:
[화학식 3][Formula 3]
상기 화학식 3에서,In Formula 3,
A는 작용기를 갖지 않는 직선형, 분지형 또는 환형 알킬렌기; 또는 설파이드기, 에테르기, 설폭사이드기, 설폰기, 케톤기, 페닐기, 이소부틸페닐기 또는 나프틸기로 이루어진 군으로부터 선택되는 하나 이상의 작용기를 포함하는 직선형, 분지형 또는 환형 알킬렌기(예컨대, 탄소수 1 내지 10의 직선형 알킬렌기, 탄소수 3 내지 10의 분지형 알킬렌기, 또는 탄소수 3 내지 10의 환형 알킬렌기)를 나타내고,A is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group (e.g., 1 carbon atom) containing at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a phenyl group, an isobutylphenyl group, or a naphthyl group. to 10 linear alkylene groups, C3 to 10 branched alkylene groups, or C3 to 10 cyclic alkylene groups),
R5및 R6은 각각 독립적으로, 할로겐 원자(예컨대, Cl 또는 Br 등); 또는 직선형, 분지형 또는 환형 알킬기(예컨대, 탄소수 1 내지 10의 직선형 알킬기, 탄소수 3 내지 10의 분지형 알킬기, 또는 탄소수 3 내지 10의 환형 알킬기)를 나타내며,R 5 and R 6 are each independently a halogen atom (eg, Cl or Br); Or a straight, branched or cyclic alkyl group (e.g., a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms),
o 및 p는 각각 독립적으로, 0 내지 4의 정수를 나타낸다.o and p each independently represents an integer of 0 to 4;
구체적으로, 상기 화학식 3의 화합물은, 예를 들어, 비스(4-히드록시페닐)메탄, 비스(4-히드록시페닐)페닐메탄, 비스(4-히드록시페닐)나프틸메탄, 비스(4-히드록시페닐)-(4-이소부틸페닐)메탄, 1,1-비스(4-히드록시페닐)에탄, 1-에틸-1,1-비스(4-히드록시페닐)프로판, 1-페닐-1,1-비스(4-히드록시페닐)에탄, 1-나프틸-1,1-비스(4-히드록시페닐)에탄, 1,2-비스(4-히드록시페닐)에탄, 1,10-비스(4-히드록시페닐)데칸, 2-메틸-1,1-비스(4-히드록시페닐)프로판, 2,2-비스(4-히드록시페닐)프로판, 2,2-비스(4-히드록시페닐)부탄, 2,2-비스(4-히드록시페닐)펜탄, 2,2-비스(4-히드록시페닐)헥산, 2,2-비스(4-히드록시페닐)노난, 2,2-비스(3-메틸-4-히드록시페닐)프로판, 2,2-비스(3-플루오로-4-히드록시페닐)프로판, 4-메틸-2,2-비스(4-히드록시페닐)펜탄, 4,4-비스(4-히드록시페닐)헵탄, 디페닐-비스(4-히드록시페닐)메탄, 레소시놀(Resorcinol), 하이드로퀴논(Hydroquinone), 4,4'-디히드록시페닐 에테르[비스(4-히드록시페닐)에테르], 4,4'-디히드록시-2,5-디히드록시디페닐 에테르, 4,4'-디히드록시-3,3'-디클로로디페닐에테르, 비스(3,5-디메틸-4-히드록시페닐)에테르, 비스(3,5-디클로로-4-히드록시페닐)에테르, 1,4-디히드록시-2,5-디클로로벤젠, 1,4-디히드록시-3-메틸벤젠, 4,4'-디히드록시디페놀[p,p'-디히드록시페닐], 3,3'-디클로로-4,4'-디히드록시페닐, 1,1-비스(4-히드록시페닐)사이클로헥산, 1,1-비스(3,5-디메틸-4-히드록시페닐)사이 클로헥산, 1,1-비스(3,5-디클로로-4-히드록시페닐)사이클로헥산, 1,1-비스(3,5-디메틸-4-히드록시페닐)사이클로도데칸, 1,1-비스(4-히드록시페닐)사이클로도데칸, 1,1-비스(4-히드록시페닐)부탄, 1,1-비스(4-히드록시페닐)데칸, 1,4-비스(4-히드록시페닐)프로판, 1,4-비스(4-히드록시페닐)부탄, 1,4-비스(4-히드록시페닐)이소부탄, 2,2-비스(4-히드록시페닐)부탄, 2,2-비스(3-클로로-4-히드록시페닐)프로판, 비스(3,5-디메틸-4-히드록시페닐)메탄, 비스(3,5-디클로로-4-히드록시페닐)메탄, 2,2-비스(3,5-디메틸-4-히드록시페닐)프로판, 2,2-비스(3,5-디브로모-4-히드록시페닐)프로판, 2,2-비스(3,5-디클로로-4-히드록시페닐)프로판, 2,4-비스(4-히드록시페닐)-2-메틸-부탄, 4,4'-티오디페놀[비스(4-히드록시페닐)설폰], 비스(3,5-디메틸-4-히드록시페닐)설폰, 비스(3-클로로-4-히드록시페닐)설폰, 비스(4-히드록시페닐)설파이드, 비스(4-히드록시페닐)설폭사이드, 비스(3-메틸-4-히드록시페닐)설파이드, 비스(3,5-디메틸-4-히드록시페닐)설파이드, 비스(3,5-디브로모-4-히드록시페닐)설폭사이드, 4,4'-디히드록시벤조페논, 3,3',5,5'-테트라메틸-4,4'-디히드록시벤조페논, 4,4'-디히드록시 디페닐, 메틸히드로퀴논, 1,5-디히드록시나프탈렌 또는 2,6-디히드록시나프탈렌 중에서 선택될 수 있으나, 반드시 이에 한정되는 것은 아니다. 대표적으로는 2,2-비스(4-히드록시페닐)프로판 (비스페놀 A)을 들 수 있다. 이외의 작용성 2가 페놀류들(dihydric phenol)은 미국특허 US 2,999,835호, US 3,028,365호, US 3,153,008호 및 US 3,334,154호 등을 참조할 수 있으며, 상기 2가 페놀류들은 단독으로 또는 2종 이상 조합되어 사용될 수 있다.Specifically, the compound of Formula 3, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) -Hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl -1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1, 10-bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxy hydroxyphenyl) pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'- Dihydroxyphenyl ether [bis(4-hydroxyphenyl)ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3' -Dichlorodiphenyl ether, bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5- Dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'- Dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3, 5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane , 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,4-bis (4 -hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxy Phenyl) propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2, 4-bis(4-hydroxyphenyl)-2-methyl-butane, 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl )sulfone, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl) Sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3, 3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-di It may be selected from hydroxynaphthalene, but is not necessarily limited thereto. Representatively, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is exemplified. Other functional dihydric phenols may be referred to US Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used alone or in combination of two or more. can be used
일 구체예에 따르면, 본 발명의 공중합체에 있어서, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위 1몰당 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 몰비는 0.5 초과, 0.51 이상, 0.6 이상, 0.7 이상, 0.8 이상, 0.9 이상 또는 1 이상일 수 있고, 또한 5 미만, 4.9 이하, 4.7 이하, 4.5 이하, 4.3 이하, 4.1 이하 또는 4 이하일 수 있다. 구체적으로는, 예컨대, 화학식 1의 화합물 유래 반복 단위 1몰당 화학식 2의 화합물 유래 반복 단위의 몰비는 0.5 초과 내지 5 미만일 수 있고, 보다 구체적으로는 0.51 내지 4.9, 0.7 내지 4.5, 0.5 내지 4 또는 1 내지 4일 수 있다.According to one embodiment, in the copolymer of the present invention, a substituted or unsubstituted fluorene-based diol compound per mole of a repeating unit derived from a substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 1) ( More specifically, the molar ratio of the repeating units derived from the compound of Formula 2) may be greater than 0.5, greater than 0.51, greater than 0.6, greater than 0.7, greater than 0.8, greater than 0.9, or greater than 1, and also less than 5, less than 4.9, less than 4.7, less than 4.5. , 4.3 or less, 4.1 or less, or 4 or less. Specifically, for example, the mole ratio of repeating units derived from the compound of Formula 2 per 1 mole of repeating units derived from the compound of Formula 1 may be greater than 0.5 and less than 5, and more specifically, 0.51 to 4.9, 0.7 to 4.5, 0.5 to 4, or 1 to 4 days.
본 발명의 공중합체에 있어서, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위 대비, 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 상대적 함량이 상기 수준보다 지나치게 적으면 공중합체의 내스크래치성이 열악해질 수 있고, 반대로 그 사용량이 상기 수준보다 지나치게 많으면 공중합체의 내충격성이 나빠질 수 있다.In the copolymer of the present invention, a substituted or unsubstituted fluorene-based diol compound (more specifically, Formula 2) compared to a repeating unit derived from a substituted or unsubstituted diallyl bisphenol-based compound (more specifically, a compound of Formula 1) If the relative content of the repeating unit derived from the compound of) is excessively less than the above level, scratch resistance of the copolymer may be deteriorated, and conversely, if the amount used is excessively greater than the above level, the impact resistance of the copolymer may be deteriorated.
일 구체예에 따르면, 본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 1몰당 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위와 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 합계 몰비는 0.2 초과, 0.21 이상, 0.23 이상, 0.25 이상, 0.27 이상, 0.29 이상 또는 0.3 이상일 수 있고, 또한 0.9 미만, 0.89 이하, 0.87 이하, 0.85 이하, 0.83 이하, 0.81 이하 또는 0.8 이하일 수 있다. 구체적으로, 전체 디올 성분 유래 반복 단위 1몰당, 예컨대, 화학식 1의 화합물 유래 반복 단위와 화학식 2의 화합물 유래 반복 단위의 합계 몰비는 0.2 초과 내지 0.9 미만일 수 있고, 보다 구체적으로는, 0.21 내지 0.89, 0.25 내지 0.65, 또는 0.3 내지 0.8일 수 있다. According to one embodiment, in the copolymer of the present invention, substituted or unsubstituted repeating units derived from diallyl bisphenol-based compounds (more specifically, the compound of Formula 1) and substituted or unsubstituted per 1 mole of repeating units derived from the total diol component The molar ratio of the total of the repeating units derived from the fluorene-based diol compound (more specifically, the compound of Formula 2) may be greater than 0.2, greater than 0.21, greater than 0.23, greater than 0.25, greater than 0.27, greater than 0.29, or greater than 0.3, and also less than 0.9; 0.89 or less, 0.87 or less, 0.85 or less, 0.83 or less, 0.81 or less, or 0.8 or less. Specifically, the total molar ratio of repeating units derived from the compound of Formula 1 and repeating units derived from the compound of Formula 2 per 1 mole of repeating units derived from all diol components may be greater than 0.2 and less than 0.9, more specifically, 0.21 to 0.89, 0.25 to 0.65, or 0.3 to 0.8.
본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 대비, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위와 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 합계의 상대적 함량이 상기 수준보다 지나치게 적으면 공중합체의 내스크래치성이 열악해질 수 있고, 반대로 상기 수준보다 지나치게 많으면 공중합체의 내충격성이 매우 나빠질 수 있다.In the copolymer of the present invention, substituted or unsubstituted repeating units derived from diallyl bisphenol-based compounds (more specifically, the compound of Formula 1) and substituted or unsubstituted fluorene-based diol compounds, compared to repeating units derived from all diol components If the relative content of the sum of repeating units derived from (more specifically, the compound of Formula 2) is too less than the above level, the copolymer may have poor scratch resistance. It can go bad.
본 발명의 공중합체에 포함되는 상기 폴리카보네이트 반복 단위는 탄산 디에스테르 화합물 또는 카보네이트 전구체로부터 유래될 수 있다.The polycarbonate repeating unit included in the copolymer of the present invention may be derived from a carbonic acid diester compound or a carbonate precursor.
일 구체예에서, 상기 탄산 디에스테르 화합물은 디알킬 카보네이트, 디아릴 카보네이트, 알킬렌 카보네이트 또는 이들의 조합으로부터 선택된 것일 수 있다. In one embodiment, the carbonic acid diester compound may be selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof.
일 구체예에서, 상기 디알킬 카보네이트의 예로는 디메틸 카보네이트, 디에틸 카보네이트, 디부틸 카보네이트, 디시클로헥실 카보네이트, 디이소부틸 카보네이트, 에틸노말부틸 카보네이트 및 에틸이소부틸 카보네이트 등을 들 수 있고, 상기 디아릴 카보네이트의 예로는 디페닐 카보네이트, 디톨릴 카보네이트, 비스(클로로페닐) 카보네이트 및 디(m-크레실) 카보네이트 등을 들 수 있으며, 상기 알킬렌 카보네이트의 예로는 에틸렌 카보네이트, 트리메틸렌 카보네이트, 테트라메틸렌 카보네이트, 1,2-프로필렌 카보네이트, 1,2-부틸렌 카보네이트, 1,3-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 1,3-펜틸렌 카보네이트, 1,4-펜틸렌 카보네이트, 1,5-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 2,4-펜틸렌 카보네이트 및 네오펜틸렌 카보네이트 등을 들 수 있다.In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl normal butyl carbonate, and ethyl isobutyl carbonate. Examples of the lyl carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di(m-cresyl) carbonate, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, and tetramethylene Carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1 ,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, neopentylene carbonate and the like.
일 구체예에서, 상기 탄산 디에스테르 화합물은 디메틸 카보네이트, 디에틸 카보네이트, 디페닐 카보네이트, 에틸렌 카보네이트 또는 이들의 조합으로부터 선택될 수 있으며, 보다 바람직하게는 디페닐 카보네이트일 수 있다.In one embodiment, the carbonic acid diester compound may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, more preferably diphenyl carbonate.
일 구체예에서, 상기 탄산 디에스테르 화합물은 하기 화학식 4로 표시되는 화합물로부터 선택된 것일 수 있다. In one embodiment, the carbonic acid diester compound may be selected from compounds represented by Formula 4 below.
[화학식 4][Formula 4]
상기 화학식 4에서, A 및 A'은 각각 독립적으로, 비치환되거나 할로겐-치환된, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기 또는 탄소수 7 내지 25의 아랄킬기로부터 선택되고, A 및 A'은 서로 동일하거나 상이할 수 있다. In Formula 4, A and A' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, and A and A' may be the same as or different from each other.
일 구체예에서, 상기 화학식 4로 표시되는 탄산 디에스테르 화합물로는 디페닐 카보네이트, 디톨릴카보네이트, 비스클로로페닐 카보네이트, 디메틸 카보네이트, 디에틸 카보네이트, 디-t-부틸 카보네이트 또는 이들의 혼합물로부터 선택되는 것을 사용할 수 있으나, 바람직하게는 디페닐 카보네이트 또는 디메틸 카보네이트를 사용할 수 있다.In one embodiment, the carbonic acid diester compound represented by Formula 4 is selected from diphenyl carbonate, ditolyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, or mixtures thereof may be used, but diphenyl carbonate or dimethyl carbonate may be preferably used.
일 구체예에서, 상기 카보네이트 전구체는 포스겐(카보닐 클로라이드), 카보닐 브로마이드, 비스할로 포르메이트, 디페닐 카보네이트, 디메틸 카보네이트로 또는 이들의 조합으로 이루어진 군으로부터 선택되는 것일 수 있다.In one embodiment, the carbonate precursor may be selected from the group consisting of phosgene (carbonyl chloride), carbonyl bromide, bishalo formate, diphenyl carbonate, dimethyl carbonate, or a combination thereof.
일 구체예에 따르면, 본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 1몰당 폴리카보네이트 반복 단위의 몰비는 0.9 이상, 0.95 이상, 또는 0.98 이상일 수 있고, 또한 1.1 이하, 1.05 이하 또는 1.02 이하일 수 있다. According to one embodiment, in the copolymer of the present invention, the molar ratio of polycarbonate repeating units per 1 mol of all diol component-derived repeating units may be 0.9 or more, 0.95 or more, or 0.98 or more, and also 1.1 or less, 1.05 or less, or 1.02 or less. can
본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 대비, 폴리카보네이트 반복 단위의 상대적 함량이 상기 수준보다 지나치게 적으면, 공중합체의 열 안정성이 악화되거나, 원하는 수준의 분자량을 얻지 못할 수 있고, 반대로 상기 수준보다 지나치게 많으면, 공중합체 성형시에 유독성 가스가 발생하거나, 분해의 원인이 될 수 있다.In the copolymer of the present invention, if the relative content of the polycarbonate repeating unit compared to all the diol component-derived repeating units is too low, the thermal stability of the copolymer may be deteriorated or a desired level of molecular weight may not be obtained, Conversely, if the amount exceeds the above level, toxic gas may be generated during molding of the copolymer or it may cause decomposition.
일 구체예에서, 본 발명의 공중합체의 점도평균 분자량은 10,000 내지 80,000일 수 있으나, 이에 한정되지 않는다. 공중합체의 점도평균 분자량이 상기 수준보다 지나치게 적으면 충격강도, 인장강도 등의 기계적 물성이 저하될 수 있고, 반대로 상기 수준보다 지나치게 많으면, 성형성이 저하될 수 있다.In one embodiment, the viscosity average molecular weight of the copolymer of the present invention may be 10,000 to 80,000, but is not limited thereto. If the viscosity average molecular weight of the copolymer is excessively less than the above level, mechanical properties such as impact strength and tensile strength may be deteriorated, and conversely, if it is excessively greater than the above level, moldability may be deteriorated.
본 발명의 공중합체는 랜덤 공중합체로서, 본 기술이 속하는 기술분야에서 통상의 지식을 가진 자에게 널리 알려진 중합 방법을 이용하여 제조할 수 있다. 예를 들면 에스테르 교환에 의한 용융 중합 방법 또는 포스겐 중합 방법을 이용하여 제조할 수 있다. The copolymer of the present invention is a random copolymer and can be prepared using a polymerization method widely known to those skilled in the art. For example, it can manufacture using the melt polymerization method by transesterification or the phosgene polymerization method.
따라서, 본 발명의 다른 측면에 따르면, 치환되거나 비치환된 디알릴 비스페놀계 화합물 및 치환되거나 비치환된 플루오렌계 디올 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하는, 폴리카보네이트 공중합체의 제조방법이 제공된다.Accordingly, according to another aspect of the present invention, a diol component including a substituted or unsubstituted diallyl bisphenol-based compound and a substituted or unsubstituted fluorene-based diol compound; And a carbonic acid diester compound or a carbonate precursor; a method for producing a polycarbonate copolymer comprising the step of copolymerizing is provided.
본 발명의 바람직한 일 구체예에서, 상기 공중합체의 제조방법은, 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함한다.In a preferred embodiment of the present invention, the method for preparing the copolymer includes a diol component including the compound represented by Formula 1 and the compound represented by Formula 2; And a carbonic acid diester compound or a carbonate precursor; It includes the step of copolymerizing.
본 발명의 일 구체예에 따르면, 상기 디올 성분은, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물) 및 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 이외의 디올 화합물(“추가의 디올 화합물”)을 더 포함할 수 있다.According to one embodiment of the present invention, the diol component is a substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 1) and a substituted or unsubstituted fluorene-based diol compound (more specifically, It may further include a diol compound (“additional diol compound”) other than the compound of Formula 2).
본 발명에 따른 공중합체의 제조방법에서 사용 가능한, 치환되거나 비치환된 디알릴 비스페놀계 화합물(보다 구체적으로는 화학식 1의 화합물), 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 2의 화합물), 추가의 디올 화합물, 탄산 디에스테르 화합물 및 카보네이트 전구체의 구체적인 종류 및 사용량에 대해서는 앞서 설명한 바와 같다.A substituted or unsubstituted diallyl bisphenol-based compound (more specifically, a compound of Formula 1), a substituted or unsubstituted fluorene-based diol compound (more specifically, a compound of Formula 1) usable in the method for preparing a copolymer according to the present invention The compound of 2), the specific types and amounts of the additional diol compound, carbonic acid diester compound and carbonate precursor are as described above.
상기 공중합 반응의 조건에는 특별한 제한이 없으며, 예컨대, 실온(예컨대, 20-30℃) 또는 승온(예컨대, 150~300℃) 하에서 수행될 수 있으나, 이에 한정되지는 않는다.Conditions for the copolymerization reaction are not particularly limited, and may be carried out at room temperature (eg, 20-30 °C) or elevated temperature (eg, 150-300 °C), but are not limited thereto.
일 구체예에서, 상기 공중합체의 제조방법은 촉매의 존재하에 수행될 수 있다.In one embodiment, the preparation method of the copolymer may be performed in the presence of a catalyst.
상기 촉매로는 중합 촉매 및/또는 상전이 촉매가 사용될 수 있다. 중합 촉매로는, 예를 들어 염기 촉매, 보다 구체적으로는 트리에틸아민(triethylamine, TEA)과 같은 유기아민 촉매를 사용할 수 있으며, 상전이 촉매로는, 예를 들어 하기 화학식 5의 화합물을 사용할 수 있다.As the catalyst, a polymerization catalyst and/or a phase transfer catalyst may be used. As the polymerization catalyst, for example, a base catalyst, more specifically, an organic amine catalyst such as triethylamine (TEA) may be used, and as a phase transfer catalyst, for example, a compound represented by Formula 5 may be used. .
[화학식 5][Formula 5]
(R7)4Q+Z- (R 7 ) 4 Q + Z -
상기 화학식 5에서, R7는 탄소수 1~10의 알킬기를 나타내고, Q는 질소 또는 인을 나타내며, Z는 할로겐 원자 또는 -OR8을 나타낸다. 여기서, R8은 수소 원자, 탄소수 1~18의 알킬기 또는 탄소수 6~18의 아릴기를 나타낸다.In Formula 5, R 7 represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Z represents a halogen atom or -OR 8 . Here, R 8 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
구체적으로, 상기 상전이 촉매는, 예를 들어 [CH3(CH2)3]4NZ, [CH3(CH2)3]4PZ, [CH3(CH2)5]4NZ, [CH3(CH2)6]4NZ, [CH3(CH2)4]4NZ, CH3[CH3(CH2)3]3NZ 또는 CH3[CH3(CH2)2]3NZ일 수 있다. 상기 화학식들에서, Z는 Cl, Br 또는 -OR8을 나타내며, 여기서 R8은 수소 원자, 탄소수 1~18의 알킬기 또는 탄소수 6~18의 아릴기를 나타낸다. 상전이 촉매 사용시 그 함량은, 결과 공중합체의 투명도 측면에서 0.01 중량% 이상인 것이 바람직하나, 이에 한정되는 것은 아니다.Specifically, the phase transfer catalyst is, for example, [CH 3 (CH 2 ) 3 ] 4 NZ, [CH 3 (CH 2 ) 3 ] 4 PZ, [CH 3 (CH 2 ) 5 ] 4 NZ, [CH 3 (CH 2 ) 6 ] 4 NZ, [CH 3 (CH 2 ) 4 ] 4 NZ, CH 3 [CH 3 (CH 2 ) 3 ] 3 NZ or CH 3 [CH 3 (CH 2 ) 2 ] 3 NZ there is. In the above formulas, Z represents Cl, Br or -OR 8 , where R 8 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. When using a phase transfer catalyst, its content is preferably 0.01% by weight or more in terms of transparency of the resulting copolymer, but is not limited thereto.
일 구체예에서, 상기 공중합체의 제조방법에서는 분자량 조절제가 사용될 수 있다.In one embodiment, a molecular weight modifier may be used in the method for preparing the copolymer.
상기 분자량 조절제로는 폴리카보네이트 제조에 사용되는 모노머와 유사한 단일 작용성 물질(monofunctional compound)이 사용될 수 있다. 상기 단일 작용성 물질은, 예를 들어 p-이소프로필페놀, p-tert-부틸페놀(p-tert-butylphenol, PTBP), p-큐밀(cumyl)페놀, p-이소옥틸페놀 및 p-이소노닐페놀과 같은 페놀을 기본으로 하는 유도체, 또는 지방족 알코올류일 수 있다. 바람직하게는, p-tert-부틸페놀(PTBP)이 사용될 수 있다.As the molecular weight modifier, a monofunctional compound similar to a monomer used in preparing polycarbonate may be used. The monofunctional substances are, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl. It may be a derivative based on phenol, such as phenol, or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) may be used.
일 구체예에서, 상기 공중합체의 제조방법은, 공중합 반응이 완료된 후 결과 혼합물에서 유기상을 추출하는 단계를 더 포함할 수 있다.In one embodiment, the method for preparing the copolymer may further include extracting an organic phase from the resultant mixture after the copolymerization reaction is completed.
일 구체예에 따르면, 공중합체를 제조한 다음, 메틸렌클로라이드에 분산된 유기상을 알칼리 세정한 후 분리시킨다. 계속해서 상기 유기상을 0.1N 염산 용액을 사용하여 세척한 후 증류수로 2 내지 3회 반복하여 세정한다. 세정이 완료되면 메틸렌클로라이드에 분산된 상기 유기상의 농도를 일정하게 조정하고, 30 내지 100℃ 범위에서, 바람직하게는 60 내지 80℃ 범위에서 일정량의 순수를 이용하여 조립화(Granulation)한다. 순수의 온도가 30℃ 미만이면 조립속도가 늦어져 조립시간이 매우 길어질 수 있으며, 순수의 온도가 100℃를 초과하면 일정한 크기로 폴리카보네이트의 형상을 얻는 것이 어려워질 수 있다. 조립이 완결되면 100 내지 120℃에서 5 내지 10시간 동안 건조시키는 것이 바람직하며, 더욱 바람직하게는 1차로 100 내지 110℃에서 5 내지 10시간 동안 건조시키고, 2차로 110 내지 120℃에서 5 내지 10시간 동안 건조시킬 수 있다.According to one embodiment, after preparing the copolymer, the organic phase dispersed in methylene chloride is washed with alkali and then separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then washed with distilled water 2 to 3 times repeatedly. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of pure water in the range of 30 to 100 ° C., preferably in the range of 60 to 80 ° C. If the temperature of the pure water is less than 30 ° C, the assembly speed may be slowed and the assembly time may be very long. When assembly is completed, it is preferable to dry at 100 to 120 ° C for 5 to 10 hours, more preferably first at 100 to 110 ° C for 5 to 10 hours, and secondly at 110 to 120 ° C for 5 to 10 hours. can be dried during
본 발명의 폴리카보네이트 공중합체는 내충격성 및 투명성을 우수하게 유지하면서도 향상된 내스크래치성 및 고굴절률을 나타내기 때문에, 이를 포함하는 성형품(예컨대, 필름, 시트, 렌즈, 커버글라스, 내외장재 등)은 다양한 산업에서 광학적 용도 및 자재 경량화 대체품의 용도에 매우 적합하게 사용될 수 있다.Since the polycarbonate copolymer of the present invention exhibits improved scratch resistance and high refractive index while maintaining excellent impact resistance and transparency, molded products including it (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) It can be used very suitably for optical use in industry and for use as a substitute for lightweight materials.
따라서, 본 발명의 또 다른 측면에 따르면, 본 발명의 폴리카보네이트 공중합체를 포함하는 성형품이 제공된다. 본 발명에서 '성형품'은 압출, 사출, 또는 기타 가공에 의한 성형품을 의미한다. Accordingly, according to another aspect of the present invention, a molded article comprising the polycarbonate copolymer of the present invention is provided. In the present invention, 'molded article' means a molded article by extrusion, injection, or other processing.
이하, 실시예 및 비교예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 본 발명의 범위가 이에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereby.
[실시예][Example]
<공중합체의 제조><Preparation of Copolymer>
실시예 1: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 1: Preparation of terpolymer using phosgene polymerization
3L 3구 반응기에서 비스페놀 A 114.15g(전체 디올 총 합계 1 몰 기준 0.50 몰), 4,4'-(9-플루오레닐리덴)디페놀 [4,4′] 115.64g(전체 디올 총 합계 1 몰 기준 0.33 몰) 및 디알릴 비스페놀 A 52.43g(전체 디올 총 합계 1 몰 기준 0.17 몰)을 5.6 중량% 수산화나트륨 수용액 1,250ml에 용해시킨 후, 포스겐 118.43g을 메틸렌 클로라이드에 포집하여 테프론 튜브(5 mm)를 통하여 천천히 투입하면서 반응시켰다. 외부 온도는 0℃로 유지하였다. 관형 반응기를 통과한 반응물을 질소 분위기 하에서 약 10분 간 계면 반응시켰다. 반응이 끝난 후, 반응 결과물 1L를 취해서 p-tert-부틸페놀(PTBP) 2.98 g 및 트리메틸아민(trimethylamine) 촉매 0.24 ml를 혼합하고, 1 시간 동안 계면 반응시켰다. 층 분리 후, 유기 상을 취하여 수산화나트륨 14g을 증류수 140g에 용해시켜 제조된 수산나트륨 수용액과 메틸렌 클로라이드 255g을 혼합하고, 트리에틸아민을 250㎕ 투입하여 1시간 30분 동안 반응시켰다. 반응이 끝난 후, 증류수를 투입하여 알칼리 세정하고, 유기 상만을 분리하였다. 상기 유기 상을 0.1N 염산 용액으로 세정한 후, 증류수로 3회 반복하여 세정하였다. 세정이 완료된 후, 상기 유기 상의 농도를 일정하게 한 후, 80℃에서 일정 량의 증류수를 이용하여 조립하였다. 조립이 완료된 후, 105℃에서 12 시간 동안 건조함으로써, 삼원 공중합체 약 344g을 수득하였다.Bisphenol A 114.15 g (0.50 mol based on 1 mol total diol total), 4,4'-(9-fluorenylidene) diphenol [4,4'] 115.64 g (total diol total 1 mol) in 3L 3-necked reactor 0.33 mol based on mole) and 52.43 g of diallyl bisphenol A (0.17 mol based on total diol total 1 mole) were dissolved in 1,250 ml of 5.6% by weight aqueous sodium hydroxide solution, and then 118.43 g of phosgene was collected in methylene chloride and placed in a Teflon tube (5 mm) and reacted while slowly introducing it. The external temperature was maintained at 0°C. The reactants passing through the tubular reactor were subjected to an interfacial reaction for about 10 minutes under a nitrogen atmosphere. After the reaction was completed, 1 L of the reaction product was taken, and 2.98 g of p-tert-butylphenol (PTBP) and 0.24 ml of a trimethylamine catalyst were mixed and interfacially reacted for 1 hour. After layer separation, the organic phase was taken, and an aqueous solution of sodium hydroxide prepared by dissolving 14 g of sodium hydroxide in 140 g of distilled water was mixed with 255 g of methylene chloride, and 250 µl of triethylamine was added thereto and reacted for 1 hour and 30 minutes. After the reaction was finished, distilled water was added to alkali wash, and only the organic phase was separated. The organic phase was washed with 0.1 N hydrochloric acid solution and then washed with distilled water three times repeatedly. After washing was completed, the concentration of the organic phase was kept constant, and then granulated using a certain amount of distilled water at 80 °C. After completion of assembly, about 344 g of a terpolymer was obtained by drying at 105° C. for 12 hours.
실시예 2: 용융 중합법을 이용한 삼원 공중합체의 제조Example 2: Preparation of terpolymer using melt polymerization
2L 3구 축합 반응기에 디페닐 카보네이트 107.11g, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′] 115.64g(전체 디올 총 합계 1 몰 기준 0.33 몰), 디알릴 비스페놀 A 52.43g(전체 디올 총 합계 1 몰 기준 0.17 몰), 비스페놀 A 114.15g(전체 디올 총 합계 1 몰 기준 0.5 몰) 및 세슘 카보네이트 0.0001g을 넣고, 질소 가스 분위기 하에서 천천히 180℃로 승온하면서 교반하였다. 이후 1시간에 걸쳐 압력을 점차적으로 50 torr까지 낮추고, 반응기 온도를 260℃까지 승온시켜서 부반응물인 페놀을 제거하면서 반응을 계속 진행하였다. 추가로 1시간 동안 압력을 0.1 torr로 낮추면서 잔량의 페놀을 제거하고 반응을 종결시킴으로써 삼원 공중합체 약 295g을 수득하였다.107.11 g of diphenyl carbonate, 115.64 g of 4,4'-(9-fluorenylidene)diphenol [4,4'] (0.33 mol based on 1 mol of total diol), diallyl bisphenol in a 2L three-necked condensation reactor 52.43 g of A (0.17 mol based on 1 mol of the total diol), 114.15 g of bisphenol A (0.5 mol based on 1 mol of the total diol), and 0.0001 g of cesium carbonate were added, and the mixture was stirred while slowly raising the temperature to 180° C. under a nitrogen gas atmosphere. . Then, over 1 hour, the pressure was gradually lowered to 50 torr, and the temperature of the reactor was raised to 260° C. to continue the reaction while removing phenol as a side reactant. About 295 g of a terpolymer was obtained by removing residual amount of phenol while lowering the pressure to 0.1 torr for an additional 1 hour to terminate the reaction.
실시예 3: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 3: Preparation of terpolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 91.32g(전체 디올 총 합계 1 몰 기준 0.4 몰)으로 변경하고, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′]의 함량을 115.64g에서 105.13g(전체 디올 총 합계 1 몰 기준 0.3 몰)으로 변경하며, 디알릴 비스페놀 A의 함량을 52.43g에서 92.52g(전체 디올 총 합계 1 몰 기준 0.3 몰) 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 351g을 수득하였다.The content of bisphenol A was changed from 114.15 g to 91.32 g (0.4 mole based on the total amount of all diols), and the content of 4,4'-(9-fluorenylidene) diphenol [4,4'] was changed to 115.64 g to 105.13 g (0.3 mole based on the total sum of all diols), and the content of diallyl bisphenol A was changed from 52.43 g to 92.52 g (0.3 mole based on the total sum of all diols). In the same manner as in Example 1, about 351 g of a terpolymer was obtained.
실시예 4: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 4: Preparation of terpolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 159.8g(전체 디올 총 합계 1 몰 기준 0.7 몰)으로 변경하고, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′]의 함량을 115.64g에서 73.59g(전체 디올 총 합계 1 몰 기준 0.21 몰)으로 변경하며, 디알릴 비스페놀 A의 함량을 52.43g에서 27.76g(전체 디올 총 합계 1 몰 기준 0.09 몰)으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 323g을 수득하였다.The content of bisphenol A was changed from 114.15 g to 159.8 g (0.7 mole based on the total amount of all diols), and the content of 4,4'-(9-fluorenylidene) diphenol [4,4'] was changed to 115.64 g to 73.59 g (0.21 mole based on the total sum of all diols), and the content of diallyl bisphenol A was changed from 52.43 g to 27.76 g (0.09 mole based on the total sum of all diols). In the same manner as in Example 1, about 323 g of a terpolymer was obtained.
실시예 5: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 5: Preparation of terpolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 45.66g(전체 디올 총 합계 1 몰 기준 0.2 몰)으로 변경하고, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′]의 함량을 115.64g에서 196.24g(전체 디올 총 합계 1 몰 기준 0.56 몰)으로 변경하며, 디알릴 비스페놀 A의 함량을 52.43g에서 74.02g(전체 디올 총 합계 1 몰 기준 0.24 몰)으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 378g을 수득하였다.The content of bisphenol A was changed from 114.15 g to 45.66 g (0.2 mol based on 1 mol of the total diol total), and the content of 4,4'-(9-fluorenylidene) diphenol [4,4'] was changed to 115.64 g to 196.24 g (0.56 mole based on the total sum of all diols), and the content of diallyl bisphenol A was changed from 52.43 g to 74.02 g (0.24 mole based on the total sum of all diols). In the same manner as in Example 1, about 378 g of a terpolymer was obtained.
실시예 6: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 6: Preparation of terpolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 136.97g(전체 디올 총 합계 1 몰 기준 0.6 몰)으로 변경하고, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′의 함량을 115.64g에서 112.13g(전체 디올 총 합계 1 몰 기준 0.32 몰)으로 변경하며, 디알릴 비스페놀 A의 함량을 52.43g에서 24.67g(전체 디올 총 합계 1 몰 기준 0.08 몰)으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 336g을 수득하였다.The content of bisphenol A was changed from 114.15 g to 136.97 g (0.6 mole based on the total amount of all diols), and the content of 4,4'-(9-fluorenylidene) diphenol [4,4' was changed to 115.64 g. to 112.13 g (0.32 mole based on the total sum of all diols), and the content of diallyl bisphenol A was changed from 52.43 g to 24.67 g (0.08 mole based on the total sum of all diols). In the same manner as in Example 1, about 336 g of a terpolymer was obtained.
비교예 1: 열가소성 방향족 폴리카보네이트(선형 폴리카보네이트) 수지의 제조Comparative Example 1: Preparation of thermoplastic aromatic polycarbonate (linear polycarbonate) resin
통상적인 계면 중합법으로 점도평균분자량이 21,000인 선형 폴리카보네이트를 제조하였다.A linear polycarbonate having a viscosity average molecular weight of 21,000 was prepared by a conventional interfacial polymerization method.
비교예 2: 포스겐 중합법을 이용한 폴리카보네이트 공중합체의 제조Comparative Example 2: Preparation of polycarbonate copolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 159.80g(전체 디올 총 합계 1 몰 기준 0.7 몰)으로 변경하고, 디알릴 비스페놀 A의 함량을 52.43g에서 92.52g(전체 디올 총 합계 1 몰 기준 0.3 몰)으로 변경하며, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′을 사용하지 않고, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 315g을 수득하였다.The content of bisphenol A was changed from 114.15g to 159.80g (0.7 mole based on the total sum of all diols), and the content of diallyl bisphenol A was changed from 52.43g to 92.52g (0.3 mole based on the total sum of all diols) and about 315 g of a terpolymer was obtained in the same manner as in Example 1 without using 4,4′-(9-fluorenylidene)diphenol [4,4′].
비교예 3: 포스겐 중합법을 이용한 폴리카보네이트 공중합체의 제조Comparative Example 3: Preparation of polycarbonate copolymer using phosgene polymerization
비스페놀 A의 함량을 114.15g에서 159.80g(전체 디올 총 합계 1 몰 기준 0.7 몰)으로 변경하고, 4,4'-(9-플루오레닐리덴)디페놀 [4,4′]의 함량을 115.64g에서 105.12g(전체 디올 총 합계 1 몰 기준 0.3 몰)으로 변경하며, 디알릴 비스페놀 A를 사용하지 않고, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체 약 327g을 수득하였다.The content of bisphenol A was changed from 114.15 g to 159.80 g (0.7 mole based on the total amount of all diols), and the content of 4,4'-(9-fluorenylidene) diphenol [4,4'] was changed to 115.64 g to 105.12 g (0.3 mole based on 1 mole of the total diol), and without using diallyl bisphenol A, the same method as in Example 1 was performed to obtain about 327 g of a terpolymer.
[물성 측정 방법][How to measure physical properties]
(1) 연필 경도(내스크래치성)(1) Pencil hardness (scratch resistance)
야스타 세이키(YASUDA SEIKI)사의 No. 553-M1 연필 경도 시험기를 사용하여 실시예 및 비교예에서 제조된 각 시편의 연필 경도를 측정하였다. 구체적으로 시편의 도막을 45° 각도에서 긁어서 도막이 파열하여 흠이 생기기 직전의 가장 단단한 연필 농도 기호를 연필 경도 값으로 나타내었다. YASUDA SEIKI's No. The pencil hardness of each specimen prepared in Examples and Comparative Examples was measured using a 553-M1 pencil hardness tester. Specifically, the coating film of the specimen was scratched at an angle of 45 °, and the hardest pencil density symbol immediately before the coating film was ruptured and scratched was indicated as the pencil hardness value.
연필 경도는 9H(가장 높음)-8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-2B-3B-4B-5B-6B-7B-8B-9B(가장 낮음)의 순서로 경도가 낮아진다.The pencil hardness is in the order of 9H (highest)-8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-2B-3B-4B-5B-6B-7B-8B-9B (least). hardness decreases with
(2) 충격 강도(내충격성)(2) Impact strength (impact resistance)
ASTM D256에 의거하여, 실시예 및 비교예의 각 시편에 노치(notch)를 내어 평가하였고, 최종 시험 결과는 각 시편에 대한 10회의 측정 값을 얻어 이들의 평균값을 계산하였다.In accordance with ASTM D256, each specimen of Examples and Comparative Examples was evaluated by notching, and as a final test result, 10 measurement values for each specimen were obtained and the average value thereof was calculated.
(3) 굴절률(3) refractive index
엘립소미터(모델명: Elli-SE, 제조사: Ellipsotechnology) 장비를 사용하여, 실시예 및 비교예의 각 시편에 대한 굴절율(파장: 470nm)을 측정하였다.Using an ellipsometer (model name: Elli-SE, manufacturer: Ellipsotechnology) equipment, the refractive index (wavelength: 470 nm) of each specimen of Examples and Comparative Examples was measured.
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 1 내지 6의 경우, 연필 경도가 F 이상으로 우수하면서도, 동시에 충격 강도가 30 kgf cm/cm 이상으로 양호하게 유지되고, 또한 굴절률도 1.60 이상의 고굴절성을 가지고 있어, 내스크래치성, 내충격성 및 고굴절성의 균형 잡힌 물성을 확보할 수 있었다.As shown in Table 1, in the case of Examples 1 to 6 according to the present invention, while the pencil hardness is excellent at F or higher, the impact strength is maintained at 30 kgf cm/cm or higher, and the refractive index is 1.60 or higher. Since it has high refractive index, it was possible to secure balanced physical properties of scratch resistance, impact resistance, and high refractive index.
반면, 종래의 선형 폴리카보네이트 수지인 비교예 1의 경우, 연필 경도가 2B이면서, 굴절률이 1.59 이하여서 내스크래치성이 매우 열악하고, 굴절률이 저조하였다. 또한 디올 화합물로서 플루오렌계 디올 화합물이 사용되지 않은 비교예 2의 경우, 연필 경도가 B로 내스크래치성이 매우 열악하였고, 굴절률 또한 1.59 이하로 저조하였으며, 디올 화합물로서 디알릴 비스페놀계 화합물이 사용되지 않은 비교예 3의 경우에도 연필 경도가 HB로 내스크래치성이 열악하였다. On the other hand, in the case of Comparative Example 1, which is a conventional linear polycarbonate resin, the pencil hardness was 2B and the refractive index was 1.59 or less, so the scratch resistance was very poor and the refractive index was low. In addition, in the case of Comparative Example 2 in which the fluorene-based diol compound was not used as the diol compound, the pencil hardness was B, and the scratch resistance was very poor, the refractive index was also low to 1.59 or less, and a diallyl bisphenol-based compound was used as the diol compound Even in the case of Comparative Example 3, which was not prepared, the pencil hardness was HB and the scratch resistance was poor.
Claims (13)
치환되거나 비치환된 플루오렌계 디올 화합물로부터 유래된 반복 단위; 및
폴리카보네이트 반복 단위;를 포함하는,
폴리카보네이트 공중합체.Repeating units derived from substituted or unsubstituted diallyl bisphenol-based compounds;
repeating units derived from substituted or unsubstituted fluorene-based diol compounds; and
Polycarbonate repeating unit; including,
polycarbonate copolymer.
[화학식 1]
상기 화학식 1에서,
R1 및 R2는 각각 독립적으로, 수소 원자, 탄소수 1 내지 30의 알킬기, 탄소수 3 내지 30의 사이클로알킬기, 또는 탄소수 6 내지 30의 아릴기를 나타내고,
m 및 n은 각각 독립적으로, 0 내지 3의 정수를 나타내며;
[화학식 2]
상기 화학식 2에서,
R3 및 R4는 각각 독립적으로, 수소 원자; 탄소수 1 내지 30의 알킬기; 탄소수 3 내지 30의 사이클로알킬기; 또는 탄소수 6 내지 30의 아릴기를 나타내고,
q 및 r은 각각 독립적으로, 0 내지 4의 정수를 나타낸다.The method of claim 1, wherein the repeating unit is derived from a compound represented by Formula 1; a repeating unit derived from a compound represented by Formula 2 below; And a polycarbonate repeating unit; containing, a polycarbonate copolymer:
[Formula 1]
In Formula 1,
R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;
m and n each independently represents an integer of 0 to 3;
[Formula 2]
In Formula 2,
R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,
q and r each independently represent an integer of 0 to 4;
[화학식 3]
상기 화학식 3에서,
A는 작용기를 갖지 않는 직선형, 분지형 또는 환형 알킬렌기; 또는 설파이드기, 에테르기, 설폭사이드기, 설폰기, 케톤기, 페닐기, 이소부틸페닐기 또는 나프틸기로 이루어진 군으로부터 선택되는 하나 이상의 작용기를 포함하는 직선형, 분지형 또는 환형 알킬렌기를 나타내고,
R5 및 R6은 각각 독립적으로, 할로겐 원자; 또는 직선형, 분지형 또는 환형 알킬기를 나타내며,
o 및 p는 각각 독립적으로, 0 내지 4의 정수를 나타낸다.The polycarbonate copolymer according to claim 4, wherein the dihydric phenolic compound is a compound having a structure represented by the following formula (3):
[Formula 3]
In Formula 3,
A is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a phenyl group, an isobutylphenyl group or a naphthyl group,
R 5 and R 6 are each independently a halogen atom; or represents a straight, branched or cyclic alkyl group;
o and p each independently represents an integer of 0 to 4;
[화학식 1]
상기 화학식 1에서,
R1 및 R2는 각각 독립적으로, 수소 원자, 탄소수 1 내지 30의 알킬기, 탄소수 3 내지 30의 사이클로알킬기, 또는 탄소수 6 내지 30의 아릴기를 나타내고,
m 및 n은 각각 독립적으로, 0 내지 3의 정수를 나타내며;
[화학식 2]
상기 화학식 2에서,
R3 및 R4는 각각 독립적으로, 수소 원자; 탄소수 1 내지 30의 알킬기; 탄소수 3 내지 30의 사이클로알킬기; 또는 탄소수 6 내지 30의 아릴기를 나타내고,
q 및 r은 각각 독립적으로, 0 내지 4의 정수를 나타낸다.The method of claim 11, wherein the diol component including a compound represented by the following formula (1) and a compound represented by the following formula (2); and copolymerizing a carbonic acid diester compound or carbonate precursor;
[Formula 1]
In Formula 1,
R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;
m and n each independently represents an integer of 0 to 3;
[Formula 2]
In Formula 2,
R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,
q and r each independently represent an integer of 0 to 4;
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