KR102601472B1 - Copolymer with improved scratch resistance and method for preparing the same - Google Patents
Copolymer with improved scratch resistance and method for preparing the same Download PDFInfo
- Publication number
- KR102601472B1 KR102601472B1 KR1020210089624A KR20210089624A KR102601472B1 KR 102601472 B1 KR102601472 B1 KR 102601472B1 KR 1020210089624 A KR1020210089624 A KR 1020210089624A KR 20210089624 A KR20210089624 A KR 20210089624A KR 102601472 B1 KR102601472 B1 KR 102601472B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- diol compound
- formula
- phenolphthalein
- compound
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title description 17
- -1 fluorene diol compound Chemical class 0.000 claims abstract description 110
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 42
- 150000002009 diols Chemical class 0.000 claims description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002220 fluorenes Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 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
- 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
- 150000002989 phenols Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 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
- 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 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 27
- 229920001897 terpolymer Polymers 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 13
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003287 optical 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
- YBLBHSSRHHJKEK-UHFFFAOYSA-N 3,3-bis(4-hydroxyphenyl)-2-phenylisoindol-1-one Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 YBLBHSSRHHJKEK-UHFFFAOYSA-N 0.000 description 2
- 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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 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
- 229910052794 bromium Inorganic materials 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
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920000642 polymer 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
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 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
- 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
- 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
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 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
- 239000003513 alkali Substances 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
- 239000001273 butane Substances 0.000 description 1
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 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
- 230000000694 effects Effects 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
- 238000013100 final test Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 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
- 239000001282 iso-butane Substances 0.000 description 1
- 238000002156 mixing Methods 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 238000005406 washing Methods 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
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides 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 내스크래치성이 향상된 공중합체 및 그 제조방법에 관한 것으로, 더욱 상세하게는, 플루오렌계 디올 화합물로부터 유래된 반복 단위; 페놀프탈레인계 디올 화합물 로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하며, 종래의 선형 폴리카보네이트 및 폴리카보네이트 공중합체 대비 향상된 내스크래치성을 가지면서도, 내충격성 및 내열성이 우수하게 유지되는 공중합체 및 그 제조방법에 관한 것이다.The present invention relates to a copolymer with improved scratch resistance and a method for producing the same, and more specifically, to a copolymer comprising a repeating unit derived from a fluorene diol compound; Repeating units derived from phenolphthalein-based diol compounds; and polycarbonate repeating units, and has improved scratch resistance compared to conventional linear polycarbonate and polycarbonate copolymers, while maintaining excellent impact resistance and heat resistance, and a method for producing the same.
Description
본 발명은 내스크래치성이 향상된 공중합체 및 그 제조방법에 관한 것으로, 더욱 상세하게는, 플루오렌계 디올 화합물로부터 유래된 반복 단위; 페놀프탈레인계 디올 화합물 로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하며, 종래의 선형 폴리카보네이트 및 폴리카보네이트 공중합체 대비 향상된 내스크래치성을 가지면서도, 내충격성 및 내열성이 우수하게 유지되는 공중합체 및 그 제조방법에 관한 것이다.The present invention relates to a copolymer with improved scratch resistance and a method for producing the same, and more specifically, to a copolymer comprising a repeating unit derived from a fluorene diol compound; Repeating units derived from phenolphthalein-based diol compounds; and polycarbonate repeating units, and has improved scratch resistance compared to conventional linear polycarbonate and polycarbonate copolymers, while maintaining excellent impact resistance and heat resistance, and a method for producing 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 is widely used for industrial purposes because it has excellent mechanical properties such as tensile strength and impact resistance, as well as excellent dimensional stability, heat resistance, and optical transparency. Research on various copolymers is continuing to improve the physical properties of polycarbonate. For example, polysiloxane-polycarbonate copolymer has been proposed to improve low-temperature impact resistance (U.S. 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 produced using bisphenol A and phosgene basically has hydroxyl groups at the end groups, and a new type of polymer can be produced by using a method of activating the hydroxyl groups of both end groups. At this time, polymerization may occur 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 those 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 the disadvantage of being less durable.
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. Republic of Korea Patent No. 10-1815930 discloses a polycarbonate copolymer with improved scratch resistance and water vapor anti-fog properties. The polycarbonate copolymer disclosed herein exhibits excellent water vapor anti-fog properties, but has poor scratch resistance. needs to be further improved.
따라서, 폴리카보네이트 고유의 물성인 투명성 및 내충격성과 내열성을 우수하게 유지하면서도 내스크래치성은 더욱 향상된 폴리카보네이트 공중합체의 개발이 요구되고 있다.Therefore, there is a need for the development of a polycarbonate copolymer with improved scratch resistance while maintaining excellent transparency, impact resistance, and heat resistance, which are the inherent physical properties of polycarbonate.
본 발명은 상기와 같은 종래기술의 문제점을 해결하고자 한 것으로, 종래의 선형 폴리카보네이트 및 종래의 폴리카보네이트 공중합체 대비 향상된 내스크래치성을 가지면서도, 내열성, 내충격성 및 투명성이 우수하게 유지되는 공중합체 및 그 제조방법을 제공하는 것을 기술적 과제로 한다.The present invention is intended to solve the problems of the prior art as described above, and is a copolymer that has improved scratch resistance compared to the conventional linear polycarbonate and the conventional polycarbonate copolymer, while maintaining excellent heat resistance, impact resistance, and transparency. The technical task is to provide and a manufacturing method thereof.
상기한 기술적 과제를 해결하고자, 본 발명의 일 측면은, 치환되거나 비치환된 플루오렌계 디올 화합물로부터 유래된 반복 단위; 치환되거나 비치환된 페놀프탈레인계 디올 화합물로부터 유래된 반복 단위; 및 폴리카보네이트 반복 단위;를 포함하는 공중합체를 제공한다. In order to solve the above-described technical problem, one aspect of the present invention is a repeating unit derived from a substituted or unsubstituted fluorene-based diol compound; Repeating units derived from substituted or unsubstituted phenolphthalein-based diol compounds; And it provides a copolymer comprising a polycarbonate repeating unit.
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, 공중합체를 제공한다:According to a preferred embodiment of the present invention, the present invention provides a repeating unit derived from a compound represented by the following formula (1); A repeating unit derived from a compound represented by the following formula (2); and polycarbonate repeat units; providing a 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 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,
m 및 n은 각각 독립적으로, 0 내지 4의 정수를 나타내며;m and n each independently represent an integer from 0 to 4;
[화학식 2][Formula 2]
HO-Z-OH HO-Z-OH
상기 화학식 2에서,In Formula 2,
Z는 치환되거나 비치환된 페놀프탈레인계 구조를 하나 이상 포함하는 2가의 기를 나타낸다.Z represents a divalent group containing one or more substituted or unsubstituted phenolphthalein-based structures.
본 발명의 다른 측면은, 치환되거나 비치환된 플루오렌계 디올 화합물 및 치환되거나 비치환된 페놀프탈레인계 디올 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하는, 공중합체의 제조방법을 제공한다. Another aspect of the present invention is a diol component including a substituted or unsubstituted fluorene-based diol compound and a substituted or unsubstituted phenolphthalein-based diol compound; and a carbonate diester compound or carbonate precursor.
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, 공중합체의 제조방법을 제공한다.According to a preferred embodiment of the present invention, the present invention provides a diol component comprising a compound represented by Formula 1 and a compound represented by Formula 2; and a carbonate diester compound or carbonate precursor.
본 발명의 또 다른 측면은, 본 발명에 따른 공중합체를 포함하는 성형품을 제공한다.Another aspect of the present invention provides a molded article comprising the copolymer according to the present invention.
본 발명에 따른 공중합체는 우수한 내충격성 및 내열성을 유지하면서도, 향상된 내스크래치성을 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 copolymer according to the present invention exhibits improved scratch resistance while maintaining excellent impact resistance and heat resistance, molded products containing it (e.g., films, sheets, lenses, cover glasses, interior and exterior materials, etc.) have optical uses in various industries. And it can be very suitable for use as a lightweight replacement product.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 공중합체는, 치환되거나 비치환된 플루오렌계 디올 화합물로부터 유래된 반복 단위; 치환되거나 비치환된 페놀프탈레인계 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 fluorene-based diol compound; Repeating units derived from substituted or unsubstituted phenolphthalein-based diol compounds; and polycarbonate repeat units.
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, “substituted” for any compound, group, or structure means that the compound, group, or structure is substituted with a halogen atom (e.g., F, Cl, or Br), a hydroxy group, an alkyl group (e.g., 1 to 10 carbon atoms, or 1 to 10 carbon atoms). alkyl group having 1 to 6 carbon atoms), alkoxy group (e.g., alkoxy group having 1 to 10 carbon atoms, or alkoxy group having 1 to 6 carbon atoms), cycloalkyl group (e.g., 3 to 10 carbon atoms, or cycloalkyl group having 3 to 6 carbon atoms), aryl group ( For example, it means being substituted by one or more substituents selected from the group consisting of 6 to 12 carbon atoms, or an aryl group with 6 carbon atoms) or a combination thereof.
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 this specification, a fluorene-based diol compound refers to a compound containing one or more “fluorene” structures and having hydroxy groups at both ends, and the fluorene-based diol compound may be substituted or unsubstituted.
본 명세서에서, 페놀프탈레인계 디올 화합물은 하나 이상의 “페놀프탈레인계” 구조를 함유하면서, 양 말단에 히드록시기를 갖는 화합물을 의미하며, 상기 페놀프탈레인계 디올 화합물은 치환되거나, 비치환된 것일 수 있다. In this specification, a phenolphthalein-based diol compound refers to a compound containing one or more “phenolphthalein-based” structures and having hydroxy groups at both ends, and the phenolphthalein-based diol compound may be substituted or unsubstituted.
본 발명의 바람직한 일 구체예에서, 상기 공중합체는, 하기 화학식 1로 표시되는 화합물 유래 반복 단위; 하기 화학식 2로 표시되는 화합물 유래 반복 단위; 및 폴리카보네이트 반복 단위;를 포함한다:In a preferred embodiment of the present invention, the copolymer includes a repeating unit derived from a compound represented by the following formula (1); A repeating unit derived from a compound represented by the following formula (2); and polycarbonate repeat units;
[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 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,
m 및 n은 각각 독립적으로, 0 내지 4의 정수를 나타내며;m and n each independently represent an integer from 0 to 4;
[화학식 2][Formula 2]
HO-Z-OH HO-Z-OH
상기 화학식 2에서,In Formula 2,
Z는 치환되거나 비치환된 페놀프탈레인계 구조를 하나 이상 포함하는 2가의 기를 나타낸다.Z represents a divalent group containing one or more substituted or unsubstituted phenolphthalein-based structures.
본 발명의 일 구체예에 따르면, 상기 화학식 1에서, According to one embodiment of the present invention, in Formula 1,
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 구체적으로는, 수소 원자; 탄소수 1 내지 10의 알킬기; 탄소수 3 내지 10의 사이클로알킬기; 또는 탄소수 6 내지 12의 아릴기를 나타낸다.R 1 and R 2 are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; Cycloalkyl group having 3 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms, and more specifically, a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; Or it represents an aryl group having 6 to 12 carbon atoms.
본 발명의 일 구체예에 따르면, 상기 화학식 2로 표시되는 화합물은 하기 화학식 2-1로 표시되는 화합물일 수 있다: According to one embodiment of the present invention, the compound represented by Formula 2 may be a compound represented by the following Formula 2-1:
[화학식 2-1][Formula 2-1]
상기 화학식 2-1에서,In Formula 2-1,
R3은 수소 원자, 알킬기, 사이클로알킬기, 사이클로알킬알킬기 또는 아릴기를 나타내고, 보다 구체적으로는 수소 원자, 탄소수 1 내지 4의 알킬기, 탄소수 3 내지 6의 사이클로알킬기, 탄소수 4 내지 10의 사이클로알킬알킬기, 또는 탄소수 6 내지 10의 아릴기를 나타내며,R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, or an aryl group, and more specifically, a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms, a cycloalkylalkyl group with 4 to 10 carbon atoms, Or represents an aryl group having 6 to 10 carbon atoms,
X는 산소 원자 또는 NR4를 나타내고, 여기서 R4는 수소 원자, 알킬기, 사이클로알킬기, 사이클로알킬알킬기 또는 아릴기를 나타내며, 보다 구체적으로는 수소 원자, 탄소수 1 내지 4의 알킬기, 탄소수 3 내지 6의 사이클로알킬기, 탄소수 4 내지 10의 사이클로알킬알킬기 또는 탄소수 6 내지 10의 아릴기를 나타낸다. Where _ It represents an alkyl group, a cycloalkylalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms.
본 발명의 일 구체예에 따르면, 본 발명의 공중합체는, 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 및 치환되거나 비치환된 페놀프탈레인계 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 includes a substituted or unsubstituted fluorene-based diol compound (more specifically, the compound of Formula 1) and a substituted or unsubstituted phenolphthalein-based diol compound (more specifically, the compound of Formula 1). may further include a repeating unit derived from a diol compound (hereinafter also referred to as “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 phenol type compound.
보다 구체적으로, 상기 2가 페놀류 화합물은 하기 화학식 3의 구조를 갖는 화합물일 수 있다:More specifically, the dihydric phenol compound may be a compound having the structure of Formula 3 below:
[화학식 3][Formula 3]
상기 화학식 3에서,In Formula 3 above,
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 without a functional group; Or a straight, branched or cyclic alkylene group (e.g., having 1 carbon atom) containing one or more functional groups selected from the group consisting of sulfide group, ether group, sulfoxide group, sulfone group, ketone group, phenyl group, isobutylphenyl group or naphthyl group. a straight alkylene group having 3 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms),
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 with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, or a cyclic alkyl group with 3 to 10 carbon atoms),
o 및 p는 각각 독립적으로, 0 내지 4의 정수를 나타낸다.o and p each independently represent an integer from 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 is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4) -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-hydr) Roxyphenyl)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. A representative example is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). For other functional dihydric phenols, see US Pat. can be used
일 구체예에 따르면, 본 발명의 공중합체에 있어서, 치환되거나 비치환된 페놀프탈레인계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위 1몰당 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위의 몰비는 0.1 초과, 0.11 이상, 0.13 이상, 0.15 이상, 0.17 이상, 0.19 이상 또는 0.2 이상일 수 있고, 또한 5.5 미만, 5.4 이하, 5.3 이하, 5.2 이하, 5.1 이하 또는 5 이하일 수 있다. 구체적으로는, 예컨대, 화학식 2의 화합물 유래 반복 단위 1몰당 화학식 1의 화합물 유래 반복 단위의 몰비는 0.1 초과 내지 5.5 미만일 수 있고, 보다 구체적으로는, 0.15 내지 5.4, 0.2 내지 5.4, 또는 0.2 내지 5일 수 있다.According to one embodiment, in the copolymer of the present invention, a substituted or unsubstituted fluorene-based diol compound (more specifically, a substituted or unsubstituted fluorene-based diol compound per mole of repeating unit derived from a substituted or unsubstituted phenolphthalein-based diol compound (more specifically, the compound of Formula 2)) Specifically, the molar ratio of the repeating unit derived from the compound of formula (1) may be greater than 0.1, greater than 0.11, greater than 0.13, greater than 0.15, greater than 0.17, greater than 0.19, or greater than 0.2, and may also be less than 5.5, less than 5.4, less than 5.3, less than 5.2, It may be 5.1 or less or 5 or less. Specifically, for example, the mole ratio of repeating units derived from the compound of Formula 1 per mole of repeating units derived from the compound of Formula 2 may be greater than 0.1 and less than 5.5, and more specifically, 0.15 to 5.4, 0.2 to 5.4, or 0.2 to 5. It can be.
본 발명의 공중합체에 있어서, 치환되거나 비치환된 페놀프탈레인계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위 대비, 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위의 상대적 함량이 상기 수준보다 지나치게 적으면, 공중합체의 경도상승 효과가 미미할 수 있고, 반대로 그 사용량이 상기 수준 초과일 경우 반응성이 낮아져 원하는 공중합체의 수평균분자량을 달성하기 어려울 수도 있다.In the copolymer of the present invention, compared to the repeating unit derived from the substituted or unsubstituted phenolphthalein diol compound (more specifically, the compound of Formula 2), the substituted or unsubstituted fluorene diol compound (more specifically, the compound of Formula 1) Compound) If the relative content of the derived repeating unit is excessively less than the above level, the effect of increasing the hardness of the copolymer may be minimal, and conversely, if the amount used exceeds the above level, the reactivity will be lowered, making it difficult to achieve the desired number average molecular weight of the copolymer. It may be possible.
일 구체예에 따르면, 본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 1몰당 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위와 치환되거나 비치환된 페놀프탈레인계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 합계 몰비는 0.1 초과, 0.11 이상, 0.12 이상, 0.13 이상, 0.14 이상 또는 0.15 이상일 수 있고, 또한 0.65 미만, 0.64 이하, 0.63 이하, 0.62 이하, 0.61 이하 또는 0.6 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 0.1 초과 내지 0.65 미만일 수 있고, 보다 구체적으로는, 0.12 내지 0.63, 0.15 내지 0.63, 또는 0.15 내지 0.6일 수 있다.According to one embodiment, in the copolymer of the present invention, per mole of repeating units derived from all diol components, a substituted or unsubstituted repeating unit derived from a fluorene-based diol compound (more specifically, the compound of Formula 1) and a substituted or unsubstituted repeating unit are used. The total molar ratio of repeating units derived from the phenolphthalein-based diol compound (more specifically, the compound of Formula 2) may be greater than 0.1, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, or 0.15 or more, and may also be less than 0.65, 0.64 or less, and 0.63. It may be 0.62 or less, 0.61 or less, or 0.6 or less. Specifically, per 1 mole of repeating units derived from all diol components, for example, the total molar ratio of the repeating units derived from the compound of Formula 1 and the repeating units derived from the compound of Formula 2 may be greater than 0.1 and less than 0.65, and more specifically, 0.12 to 0.63, It may be 0.15 to 0.63, or 0.15 to 0.6.
본 발명의 공중합체에 있어서, 전체 디올 성분 유래 반복 단위 대비, 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 유래 반복 단위와 치환되거나 비치환된 페놀프탈레인계 디올 화합물(보다 구체적으로는 화학식 2의 화합물) 유래 반복 단위의 합계의 상대적 함량이 상기 수준보다 지나치게 적으면, 공중합체의 내스크래치성이 열악할 수 있고, 반대로 상기 수준보다 지나치게 많으면, 공중합체의 내충격성이 저하될 수 있다.In the copolymer of the present invention, compared to the repeating units derived from all diol components, the repeating units derived from a substituted or unsubstituted fluorene diol compound (more specifically, the compound of Formula 1) and the substituted or unsubstituted phenolphthalein diol compound ( More specifically, if the relative content of the sum of the repeating units derived from the compound of Formula 2 is too much less than the above level, the scratch resistance of the copolymer may be poor, and conversely, if it is too much more than the above level, the impact resistance of the copolymer may be poor. may deteriorate.
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 carbonate 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 carbonate, diaryl carbonate, alkylene carbonate, or a combination 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 n-butyl carbonate, and ethyl isobutyl carbonate, and the dia Examples of the alkylene 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 and neopentylene carbonate.
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, and 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 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 preferably diphenyl carbonate or dimethyl carbonate.
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, bihalo 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 mole of repeating units derived from all diol components may be 0.9 or more, 0.95 or more, or 0.98 or more, and may also be 1.1 or less, 1.05 or less, or 1.02 or less. You 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 polycarbonate repeating units compared to the repeating units derived from all diol components is excessively less than the above level, the thermal stability of the copolymer may deteriorate or the desired level of molecular weight may not be obtained, On the other hand, if it exceeds the above level, toxic gas may be generated during copolymer molding 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 too much less than the above level, mechanical properties such as impact strength and tensile strength may be reduced, and conversely, if it is too much more than the above level, moldability may be reduced.
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 manufactured using a polymerization method widely known to those skilled in the art. For example, it can be produced using a melt polymerization method by transesterification or a phosgene polymerization method.
따라서, 본 발명의 다른 측면에 따르면, 치환되거나 비치환된 플루오렌계 디올 화합물 및 치환되거나 비치환된 페놀프탈레인계 디올 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하는, 공중합체의 제조방법이 제공된다.Therefore, according to another aspect of the present invention, a diol component comprising a substituted or unsubstituted fluorene-based diol compound and a substituted or unsubstituted phenolphthalein-based diol compound; A method for producing a copolymer is provided, including the step of copolymerizing a carbonate diester compound or a carbonate precursor.
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 producing the copolymer includes a diol component comprising a compound represented by Formula 1 and a compound represented by Formula 2; and a step of copolymerizing a carbonate diester compound or carbonate precursor.
본 발명의 일 구체예에 따르면, 상기 디올 성분은, 치환되거나 비치환된 플루오렌계 디올 화합물(보다 구체적으로는 화학식 1의 화합물) 및 치환되거나 비치환된 페놀프탈레인계 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 fluorene-based diol compound (more specifically, the compound of formula 1) and a substituted or unsubstituted phenolphthalein-based diol compound (more specifically, the compound of formula 1) It may further include diol compounds (“additional diol compounds”) other than the compound of 2).
본 발명에 따른 공중합체의 제조방법에서 사용 가능한, 치환되거나 비치환된 플루오렌계 디올(보다 구체적으로는 화학식 1의 화합물), 치환되거나 비치환된 페놀프탈레인계 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.Substituted or unsubstituted fluorene-based diols (more specifically, the compounds of Formula 1) and substituted or unsubstituted phenolphthalein-based diol compounds (more specifically, the compounds of Formula 2) that can be used in the method for producing the copolymer according to the present invention The specific types and usage amounts of compounds), additional diol compounds, carbonate diester compounds, and carbonate precursors 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.There is no particular limitation on the conditions of the copolymerization reaction, and for example, it may be carried out at room temperature (eg, 20-30°C) or elevated temperature (eg, 150-300°C), but is not limited thereto.
일 구체예에서, 상기 공중합체의 제조방법은 촉매의 존재하에 수행될 수 있다.In one embodiment, the method for producing 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 a polymerization catalyst, for example, a base catalyst, more specifically, an organic amine catalyst such as triethylamine (TEA) can be used, and as a phase transfer catalyst, for example, a compound of the following formula (5) can 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 the above 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 with 1 to 18 carbon atoms, or an aryl group with 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 with 1 to 18 carbon atoms, or an aryl group with 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 regulator may be used in the method for producing 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 regulator, a monofunctional compound similar to the monomer used in polycarbonate production may be used. The monofunctional substances include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl. It may be a phenol-based derivative such as phenol, or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) can 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 producing the copolymer may further include extracting the organic phase from the resulting 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, 2차로 110 내지 120℃에서 5 내지 10시간 동안 건조시킨다.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 using 0.1N hydrochloric acid solution and then washed repeatedly 2 to 3 times with distilled water. When washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, 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 pure water is less than 30℃, the assembly speed may slow down and the assembly time may be very long. If the temperature of pure water exceeds 100℃, it may become difficult to obtain the shape of polycarbonate with a certain size. Once assembly is complete, it is preferable to dry at 100 to 120°C for 5 to 10 hours, more preferably firstly at 100 to 110°C for 5 to 10 hours and secondly at 110 to 120°C for 5 to 10 hours. .
본 발명의 공중합체는 우수한 내충격성, 내열성 및 투명성을 유지하면서, 향상된 내스크래치성을 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 copolymer of the present invention exhibits improved scratch resistance while maintaining excellent impact resistance, heat resistance, and transparency, molded products containing it (e.g., films, sheets, lenses, cover glasses, interior and exterior materials, etc.) are used in optical applications in various industries. It can be used very well for purposes and as a lightweight alternative to materials.
따라서, 본 발명의 또 다른 측면에 따르면, 본 발명의 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 copolymer of the present invention is provided. In the present invention, ‘molded product’ refers to a molded product obtained 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 thereto.
[실시예][Example]
<공중합체의 제조><Preparation of copolymer>
실시예 1: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 1: Preparation of terpolymer using phosgene polymerization method
3L 3구 반응기에서 비스페놀 A(BPA) 91.3g(전체 디올 총 합계 1 몰 기준 0.4 몰)과, 플루오렌계 디올 화합물로서 9,9-비스(4-히드록시페닐)플루오렌[9,9-bis(4-hydroxyphenyl)fluorine] 35g 및 페놀프탈레인 159.2g(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.6 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 0.2:1)을 5.6 중량% 수산화나트륨 수용액 900ml에 용해시킨 후, 포스겐 98g을 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 10분간 계면 반응시켰다. 반응이 끝난 후, 반응 결과물 1L를 취해서 p-tert-부틸페놀(PTBP) 2.98g 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 공중합체를 수득하였다. In a 3L three-neck reactor, 91.3 g of bisphenol A (BPA) (0.4 mol based on 1 mol of total diol) and 9,9-bis(4-hydroxyphenyl)fluorene[9,9-] as a fluorene-based diol compound. bis(4-hydroxyphenyl)fluorine] 35g and phenolphthalein 159.2g (total of 0.6 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole of total diol, molar ratio of fluorene-based diol compound and phenolphthalein-based diol compound = 0.2 :1) was dissolved in 900 ml of 5.6% by weight aqueous sodium hydroxide solution, and then 98 g of phosgene was collected in methylene chloride and slowly added through a Teflon tube (5 mm) for reaction. The external temperature was maintained at 0°C. The reactants that passed through the tubular reactor were subjected to an interfacial reaction for about 10 minutes under a nitrogen atmosphere. After the reaction was completed, 1L of the reaction product was mixed with 2.98 g of p-tert-butylphenol (PTBP) and 0.24 ml of trimethylamine catalyst and subjected to an interfacial reaction for 1 hour. After separation of the layers, the organic phase was mixed with an aqueous solution of sodium hydroxide prepared by dissolving 14 g of sodium hydroxide in 140 g of distilled water and 255 g of methylene chloride, and 250 μl of triethylamine was added and reacted for 1 hour and 30 minutes. After the reaction was completed, distilled water was added to alkaline wash, and only the organic phase was separated. The organic phase was washed with 0.1N hydrochloric acid solution and then washed three times with distilled water. After cleaning was completed, the concentration of the organic phase was kept constant and then assembled using a certain amount of distilled water at 80°C. After assembly was completed, the terpolymer was obtained by drying at 105°C for 12 hours.
실시예 2: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 2: Preparation of terpolymer using phosgene polymerization method
비스페놀 A의 함량을 91.3g에서 114g(전체 디올 총 합계 1 몰 기준 0.5 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 35g에서 50.1g으로, 페놀프탈레인 함량을 159.2g에서 113.7g으로(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.5 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 0.4:1) 변경하고, p-tert-부틸페놀(PTBP)의 함량을 2.98g에서 2.8g으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다.The content of bisphenol A was changed from 91.3g to 114g (0.5 mol based on 1 mole of total diol total), the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 35g to 50.1g, and the phenolphthalein content was changed to Changed from 159.2g to 113.7g (total of 0.5 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole of total diol, molar ratio of fluorene-based diol compound and phenolphthalein-based diol compound = 0.4:1), p A terpolymer was obtained in the same manner as in Example 1, except that the content of -tert-butylphenol (PTBP) was changed from 2.98 g to 2.8 g.
실시예 3: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 3: Preparation of terpolymer using phosgene polymerization method
비스페놀 A의 함량을 91.3g에서 137g(전체 디올 총 합계 1 몰 기준 0.6 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 35g에서 70.1g으로, 페놀프탈레인 함량을 159.2g에서 63.7g으로(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.4 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 1:1) 변경하고, p-tert-부틸페놀(PTBP)의 함량을 2.98g에서 1.98g으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다. The content of bisphenol A was changed from 91.3g to 137g (0.6 mol based on 1 mole of total diol total), the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 35g to 70.1g, and the phenolphthalein content was changed to Changed from 159.2g to 63.7g (total of 0.4 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole of total diol, molar ratio of fluorene-based diol compound and phenolphthalein-based diol compound = 1:1), p A terpolymer was obtained in the same manner as in Example 1, except that the content of -tert-butylphenol (PTBP) was changed from 2.98 g to 1.98 g.
실시예 4: 용융 중합법을 이용한 삼원 공중합체의 제조Example 4: Preparation of terpolymer using melt polymerization method
2L 3구 축합 반응기에 디페닐 카보네이트 214g, 플루오렌계 디올 화합물로서 9,9-비스(4-히드록시페닐)플루오렌[9,9-bis(4-hydroxyphenyl)fluorine] 75.1g 및 페놀프탈레인 27.3g(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.3 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 2.5:1), 비스페놀 A 160g(전체 디올 총 합계 1 몰 기준 0.7 몰) 및 세슘 카보네이트 0.0001g을 넣고, 질소 가스 분위기 하에서 천천히 180℃로 승온하면서 교반하였다. 이후 1 시간에 걸쳐 압력을 점차적으로 50 torr까지 낮추고, 반응기 온도를 260℃까지 승온시켜서 부반응물인 페놀을 제거하면서 반응을 계속 진행하였다. 추가로 1 시간 동안 압력을 0.1 torr로 낮추면서 잔량의 페놀을 제거하고 반응을 종결시킴으로써 삼원 공중합체를 수득하였다. In a 2L three-neck condensation reactor, 214 g of diphenyl carbonate, 75.1 g of 9,9-bis (4-hydroxyphenyl) fluorine as a fluorene diol compound, and 27.3 g of phenolphthalein. (0.3 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole total of all diols, molar ratio of fluorene-based diol compound and phenolphthalein-based diol compound = 2.5:1), 160 g of bisphenol A (total total of all diols 1 0.7 mole (based on mole) and 0.0001 g of cesium carbonate were added and stirred while slowly raising the temperature to 180°C under a nitrogen gas atmosphere. Afterwards, the pressure was gradually lowered to 50 torr over 1 hour, the reactor temperature was raised to 260°C, and the reaction continued while removing phenol, a side reactant. The remaining amount of phenol was removed while the pressure was lowered to 0.1 torr for an additional 1 hour, and the reaction was terminated to obtain a terpolymer.
실시예 5: 용융 중합법을 이용한 삼원 공중합체의 제조Example 5: Preparation of terpolymer using melt polymerization method
디페닐 카보네이트의 함량을 214g에서 215g으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 75.1g에서 146.0g으로, 페놀프탈레인의 함량을 27.3g에서 26.5g으로(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.5 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 5:1) 변경하고, 비스페놀 A의 함량을 160g에서 114g(전체 디올 총 합계 1 몰 기준 0.5 몰)으로 변경한 것을 제외하고는, 실시예 4와 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다. The content of diphenyl carbonate was changed from 214g to 215g, the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 75.1g to 146.0g, and the content of phenolphthalein was changed from 27.3g to 26.5g (total diol Based on a total of 1 mole, the total of the fluorene diol compound and the phenolphthalein diol compound is 0.5 mol, the molar ratio of the fluorene diol compound and the phenolphthalein diol compound = 5:1), and the content of bisphenol A is changed from 160 g to 114 g (total A terpolymer was obtained in the same manner as in Example 4, except that the total amount of diol was changed to 0.5 mol based on 1 mol.
실시예 6: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 6: Preparation of terpolymer using phosgene polymerization method
비스페놀 A의 함량을 91.3g에서 159.6g(전체 디올 총 합계 1 몰 기준 0.7 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 35g에서 75.1g으로, 페놀프탈레인계 디올 화합물로서 페놀프탈레인을 대신하여 하기 구조의 페놀프탈레인 아닐라이드[phenolphthalein anilide]를 33.7g으로(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.3 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 2.5:1) 변경하여 사용하고, p-tert-부틸페놀(PTBP)의 함량을 2.98g에서 1.86g으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다. The content of bisphenol A was changed from 91.3g to 159.6g (0.7 mol based on 1 mole of total diol total), the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 35g to 75.1g, and phenolphthalein-based Instead of phenolphthalein as a diol compound, 33.7 g of phenolphthalein anilide of the following structure (0.3 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole of total diol, fluorene-based diol compound and The molar ratio of the phenolphthalein diol compound (molar ratio = 2.5:1) was used differently, and the content of p-tert-butylphenol (PTBP) was changed from 2.98 g to 1.86 g, and was carried out in the same manner as in Example 1. A terpolymer was obtained.
[페놀프탈레인 아닐라이드][Phenolphthalein anilide]
실시예 7: 포스겐 중합법을 이용한 삼원 공중합체의 제조Example 7: Preparation of terpolymer using phosgene polymerization method
비스페놀 A의 함량을 91.3g에서 193.8g(전체 디올 총 합계 1 몰 기준 0.85 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 35g에서 26.3g으로, 페놀프탈레인의 함량을 159.2g에서 23.9g으로(전체 디올 총 합계 1 몰 기준 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 합계 0.15 몰, 플루오렌계 디올 화합물과 페놀프탈레인계 디올 화합물의 몰비 = 1:1) 변경하고, p-tert-부틸페놀(PTBP)의 함량을 2.98g에서 2.23g으로 변경한 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다. The content of bisphenol A was changed from 91.3g to 193.8g (0.85 mol based on 1 mole of total diol total), the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 35g to 26.3g, and phenolphthalein The content was changed from 159.2g to 23.9g (total of 0.15 mole of fluorene-based diol compound and phenolphthalein-based diol compound based on 1 mole of total diol, molar ratio of fluorene-based diol compound and phenolphthalein-based diol compound = 1:1) , A terpolymer was obtained in the same manner as in Example 1, except that the content of p-tert-butylphenol (PTBP) was changed from 2.98 g to 2.23 g.
비교예 1: 열가소성 방향족 폴리카보네이트(선형 폴리카보네이트) 수지의 제조Comparative Example 1: Preparation of thermoplastic aromatic polycarbonate (linear polycarbonate) resin
통상의 계면 중합법으로 점도평균분자량이 21,000인 선형 폴리카보네이트를 제조하였다. Linear polycarbonate with a viscosity average molecular weight of 21,000 was prepared using a conventional interfacial polymerization method.
비교예 2: 포스겐 중합법을 이용한 삼원 공중합체의 제조Comparative Example 2: Preparation of terpolymer using phosgene polymerization method
비스페놀 A의 함량을 91.3g에서 137g(전체 디올 총 합계 1 몰 기준 0.6 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌의 함량을 35g에서 140.2g(전체 디올 총 합계 1 몰 기준 0.4 몰)으로 변경하며, 페놀프탈레인을 사용하지 않은 것을 제외하고는, 실시예 1과 동일한 방법으로 수행하여 삼원 공중합체를 제조하였다. The content of bisphenol A was changed from 91.3 g to 137 g (0.6 mol based on 1 mol of total diols), and the content of 9,9-bis(4-hydroxyphenyl)fluorene was changed from 35 g to 140.2 g (total of all diols). A terpolymer was prepared in the same manner as in Example 1, except that phenolphthalein was not used.
비교예 3: 용융 중합법을 이용한 삼원 공중합체의 제조Comparative Example 3: Preparation of terpolymer using melt polymerization method
디페닐 카보네이트의 함량을 214g에서 215g으로 변경하고, 페놀프탈레인의 함량을 27.3g에서 159.2g(전체 디올 총 합계 1 몰 기준 0.5 몰)으로 변경하며, 비스페놀 A의 함량을 160g에서 114g(전체 디올 총 합계 1 몰 기준 0.5 몰)으로 변경하고, 9,9-비스(4-히드록시페닐)플루오렌을 사용하지 않은 것을 제외하고는, 실시예 4와 동일한 방법으로 수행하여 삼원 공중합체를 수득하였다. The content of diphenyl carbonate is changed from 214g to 215g, the content of phenolphthalein is changed from 27.3g to 159.2g (0.5 mol based on 1 mole of total diol total), and the content of bisphenol A is changed from 160g to 114g (total total of all diols) A terpolymer was obtained in the same manner as in Example 4, except that 0.5 mole based on 1 mole) was changed and 9,9-bis(4-hydroxyphenyl)fluorene was not used.
상기 실시예 1 내지 7 및 비교예 1 내지 3에서 각각 제조된 중합체를 L/D=40 및 =25mm 인 이축 용융 혼합 압출기를 사용하여 용융 및 혼련시켰다. 그 후 압출 다이를 통해 나온 용융물을 냉각하여 성형용 펠렛을 제조하였다. 상기 제조된 성형용 펠렛을 90~100℃의 온도에서 4 시간 이상 열풍 건조 후, 280~320℃의 온도에서 사출 성형하여 시편을 제조하였다. 상기 제조된 시편에 대한 물성들을 측정 및 평가하였고, 그 결과를 하기 표 1에 나타내었다.The polymers prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were L/D = 40 and It was melted and kneaded using a twin-screw melt mixing extruder with =25mm. Afterwards, the melt coming out through the extrusion die was cooled to produce pellets for molding. The prepared molding pellets were dried with hot air at a temperature of 90 to 100°C for more than 4 hours, and then injection molded at a temperature of 280 to 320°C to prepare a specimen. The physical properties of the prepared specimens were measured and evaluated, and the results are shown in Table 1 below.
[물성 측정 방법][Method of measuring physical properties]
(1) 연필경도(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 a 45° angle, and the hardest pencil concentration symbol just before the coating film ruptured and a scratch was created was expressed 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.Pencil hardness ranges from 9H (highest) to 8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-2B-3B-4B-5B-6B-7B-8B-9B (lowest). The hardness decreases.
(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 대하여 10회의 시험을 실시하여, 10회의 시험 결과치의 평균값을 계산하였다.In accordance with ASTM D256, each specimen of Examples and Comparative Examples was notched and evaluated, and the final test results were obtained by performing 10 tests on each specimen, and calculating the average value of the 10 test results.
(3) 유리전이온도(내열성)(3) Glass transition temperature (heat resistance)
시차주사 열량계(Perkin-Elmer사의 DSC-7 & Robotic)를 사용하여 실시예 및 비교예의 시편의 유리전이 온도를 측정하였다.The glass transition temperature of the specimens of Examples and Comparative Examples was measured using a differential scanning calorimeter (DSC-7 & Robotic from Perkin-Elmer).
상기 표 1에 나타난 바와 같이, 본 발명에 따른 실시예 1 내지 7의 경우, 연필 경도가 H 이상으로 우수하면서도, 유리전이 온도가 170℃ 이상이며, 동시에 충격 강도가 37 kgf cm/cm 이상으로 우수하게 유지되어, 내스크래치성, 내열성 및 내충격성의 균형 잡힌 물성을 확보할 수 있었다. As shown in Table 1, in the case of Examples 1 to 7 according to the present invention, the pencil hardness is excellent at H or higher, the glass transition temperature is at least 170° C., and at the same time, the impact strength is at least 37 kg f cm/cm. It was maintained excellently, ensuring balanced physical properties of scratch resistance, heat resistance, and impact resistance.
반면, 종래의 선형 폴리카보네이트 수지인 비교예 1의 경우, 연필 경도가 2B이면서, 유리전이 온도가 147℃로서, 내스크래치성 및 내열성이 모두 열악하였다. 또한 디올 화합물로서 페놀프탈레인계 디올 화합물이 사용되지 않은 비교예 2의 경우, 충격 강도가 22 kgf cm/cm로 내충격성이 매우 열악하였고, 플루오렌계 디올 화합물이 사용되지 않은 비교예 3의 경우, 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 glass transition temperature was 147°C, and both scratch resistance and heat resistance were poor. In addition, in the case of Comparative Example 2 in which the phenolphthalein-based diol compound was not used as the diol compound, the impact resistance was very poor with an impact strength of 22 kg f cm/cm, and in the case of Comparative Example 3 in which the fluorene-based diol compound was not used, The pencil hardness was HB and scratch resistance was poor.
Claims (13)
하기 화학식 2로 표시되는 페놀프탈레인계 디올 화합물로부터 유래된 반복 단위; 및
탄산 디에스테르 화합물 또는 카보네이트 전구체로부터 유래된 폴리카보네이트 반복 단위;를 포함하며,
상기 페놀프탈레인계 디올 화합물 유래 반복 단위 1몰당 상기 플루오렌계 디올 화합물 유래 반복 단위의 몰비가 0.2 내지 5이고,
전체 디올 성분 유래 반복 단위 1몰당 상기 플루오렌계 디올 화합물 유래 반복 단위와 상기 페놀프탈레인계 디올 화합물 유래 반복 단위의 합계 몰비가 0.15 내지 0.6인,
공중합체:
[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 4의 정수를 나타내며;
[화학식 2]
HO-Z-OH
상기 화학식 2에서,
Z는 치환되거나 비치환된 페놀프탈레인계 구조를 하나 이상 포함하는 2가의 기를 나타낸다.A repeating unit derived from a fluorene-based diol compound represented by the following formula (1);
A repeating unit derived from a phenolphthalein-based diol compound represented by the following formula (2); and
It includes a polycarbonate repeating unit derived from a carbonate diester compound or a carbonate precursor,
The molar ratio of the repeating units derived from the fluorene-based diol compound per mole of repeating units derived from the phenolphthalein-based diol compound is 0.2 to 5,
The total molar ratio of the repeating units derived from the fluorene-based diol compound and the repeating units derived from the phenolphthalein-based diol compound per mole of repeating units derived from all diol components is 0.15 to 0.6,
Copolymer:
[Formula 1]
In Formula 1,
R 1 and R 2 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,
m and n each independently represent an integer from 0 to 4;
[Formula 2]
HO-Z-OH
In Formula 2,
Z represents a divalent group containing one or more substituted or unsubstituted phenolphthalein-based structures.
[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 copolymer according to claim 3, wherein the dihydric phenol compound is a compound having the structure of the following formula (3):
[Formula 3]
In Formula 3 above,
A is a straight, branched or cyclic alkylene group without a functional group; or a straight, branched or cyclic alkylene group containing one or more functional groups selected from the group consisting of sulfide group, ether group, sulfoxide group, sulfone group, ketone group, phenyl group, isobutylphenyl group or 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 represent an integer from 0 to 4.
하기 화학식 1로 표시되는 플루오렌계 디올 화합물 및 하기 화학식 2로 표시되는 페놀프탈레인계 디올 화합물을 포함하는 디올 성분; 및 탄산 디에스테르 화합물 또는 카보네이트 전구체;를 공중합하는 단계를 포함하며,
상기 페놀프탈레인계 디올 화합물 1몰당 상기 플루오렌계 디올 화합물의 몰비가 0.2 내지 5이고,
전체 디올 성분 1몰당 상기 플루오렌계 디올 화합물과 상기 페놀프탈레인계 디올 화합물의 합계 몰비가 0.15 내지 0.6인,
공중합체의 제조방법:
[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 4의 정수를 나타내며;
[화학식 2]
HO-Z-OH
상기 화학식 2에서,
Z는 치환되거나 비치환된 페놀프탈레인계 구조를 하나 이상 포함하는 2가의 기를 나타낸다.As a method for producing a copolymer,
A diol component including a fluorene-based diol compound represented by the following formula (1) and a phenolphthalein-based diol compound represented by the following formula (2); and copolymerizing a carbonate diester compound or carbonate precursor,
The molar ratio of the fluorene-based diol compound per mole of the phenolphthalein-based diol compound is 0.2 to 5,
The total molar ratio of the fluorene-based diol compound and the phenolphthalein-based diol compound per 1 mole of all diol components is 0.15 to 0.6,
Method for producing copolymer:
[Formula 1]
In Formula 1,
R 1 and R 2 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,
m and n each independently represent an integer from 0 to 4;
[Formula 2]
HO-Z-OH
In Formula 2,
Z represents a divalent group containing one or more substituted or unsubstituted phenolphthalein-based structures.
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Citations (5)
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|---|---|---|---|---|
| US4210741A (en) | 1975-08-20 | 1980-07-01 | The Dow Chemical Company | Phenolphthalein-dihydroxy aromatic compound polycarbonates |
| JP2000111885A (en) * | 1998-09-30 | 2000-04-21 | Mitsubishi Chemicals Corp | Liquid crystal display element |
| JP2010256913A (en) | 2010-06-04 | 2010-11-11 | Teijin Chem Ltd | Method for manufacturing optical film, and optical film |
| US20170022360A1 (en) | 2014-04-15 | 2017-01-26 | Sabic Global Technologies B.V. | High heat polycarbonate compositions |
| JP2020158596A (en) * | 2019-03-26 | 2020-10-01 | 帝人株式会社 | Polycarbonate resin composition |
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| US20120245262A1 (en) * | 2011-03-23 | 2012-09-27 | Sabic Innovative Plastics Ip B.V. | Polycarbonate composition with improved impact strength |
| US20130261234A1 (en) * | 2012-03-30 | 2013-10-03 | Shiping Ma | Flame Retardant Polycarbonate Composition with High Pencil Hardness |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210741A (en) | 1975-08-20 | 1980-07-01 | The Dow Chemical Company | Phenolphthalein-dihydroxy aromatic compound polycarbonates |
| JP2000111885A (en) * | 1998-09-30 | 2000-04-21 | Mitsubishi Chemicals Corp | Liquid crystal display element |
| JP2010256913A (en) | 2010-06-04 | 2010-11-11 | Teijin Chem Ltd | Method for manufacturing optical film, and optical film |
| US20170022360A1 (en) | 2014-04-15 | 2017-01-26 | Sabic Global Technologies B.V. | High heat polycarbonate compositions |
| JP2020158596A (en) * | 2019-03-26 | 2020-10-01 | 帝人株式会社 | Polycarbonate resin composition |
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