CN118475637A - Polycarbonate resin and method for producing the same - Google Patents
Polycarbonate resin and method for producing the same Download PDFInfo
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- CN118475637A CN118475637A CN202380015849.3A CN202380015849A CN118475637A CN 118475637 A CN118475637 A CN 118475637A CN 202380015849 A CN202380015849 A CN 202380015849A CN 118475637 A CN118475637 A CN 118475637A
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- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 157
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 157
- 238000004519 manufacturing process Methods 0.000 title description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims description 182
- 150000001875 compounds Chemical class 0.000 claims description 94
- 229920005989 resin Polymers 0.000 claims description 87
- 239000011347 resin Substances 0.000 claims description 87
- 125000003118 aryl group Chemical group 0.000 claims description 63
- 125000000217 alkyl group Chemical group 0.000 claims description 55
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 125000001072 heteroaryl group Chemical group 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 41
- 125000002947 alkylene group Chemical group 0.000 claims description 30
- 229920000515 polycarbonate Polymers 0.000 claims description 29
- 239000004417 polycarbonate Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 28
- 230000003287 optical effect Effects 0.000 claims description 27
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 11
- 125000000732 arylene group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000005549 heteroarylene group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000003275 alpha amino acid group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 description 68
- -1 1-methylpentyl Chemical group 0.000 description 39
- 125000002950 monocyclic group Chemical group 0.000 description 34
- 239000000178 monomer Substances 0.000 description 32
- 125000003367 polycyclic group Chemical group 0.000 description 32
- 125000001424 substituent group Chemical group 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000001746 injection moulding Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 230000009477 glass transition Effects 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000012788 optical film Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 235000003642 hunger Nutrition 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000005304 optical glass Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 102100027324 2-hydroxyacyl-CoA lyase 1 Human genes 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 101001009252 Homo sapiens 2-hydroxyacyl-CoA lyase 1 Proteins 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000005104 aryl silyl group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- UAXNXOMKCGKNCI-UHFFFAOYSA-N 1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 UAXNXOMKCGKNCI-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- CYXGBTZYTXLVDN-UHFFFAOYSA-N 1-octoxyphosphonoyloxyoctane Chemical compound CCCCCCCCOP(=O)OCCCCCCCC CYXGBTZYTXLVDN-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MGDKDCPSGRWOIZ-UHFFFAOYSA-N C(CCC)C=1C(=C(C(=C(C1)CCCCCCCCCCCC)CCCC)CCCC)CCCC Chemical compound C(CCC)C=1C(=C(C(=C(C1)CCCCCCCCCCCC)CCCC)CCCC)CCCC MGDKDCPSGRWOIZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000002720 diazolyl group Chemical group 0.000 description 1
- 125000005509 dibenzothiophenyl group Chemical group 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 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
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- XFUSKHPBJXJFRA-UHFFFAOYSA-N dihexyl hydrogen phosphite Chemical compound CCCCCCOP(O)OCCCCCC XFUSKHPBJXJFRA-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IVQOVYWBHRSGJI-UHFFFAOYSA-N hexyl 4-methylbenzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 IVQOVYWBHRSGJI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CHJUOCDSZWMLRU-UHFFFAOYSA-N oxo(dipropoxy)phosphanium Chemical compound CCCO[P+](=O)OCCC CHJUOCDSZWMLRU-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005887 tetrahydrobenzofuranyl group Chemical group 0.000 description 1
- 125000005886 tetrahydrobenzothienyl group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to polycarbonate resins having a relaxation time of 2 seconds to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less.
Description
Technical Field
The present application claims priority and rights of korean patent application nos. 10-2022-0127550 and 10-2022-0141544, filed in the korean intellectual property office on day 5 of 2022 and day 28 of 2022, respectively, the entire contents of which are incorporated herein by reference.
The present specification relates to polycarbonate resins and methods of making the same.
Background
Optical glass or optical resin is used as an optical material for plastic optical products and optical films such as various lenses, prisms, optical disk substrates, and optical fibers. Although the optical glass has excellent heat resistance, transparency, dimensional stability and chemical resistance, the optical glass has problems of high material cost, poor moldability and low productivity.
Meanwhile, optical materials including optical resins can be mass-produced by injection molding. As the optical resin, a polycarbonate resin, a polyester-polycarbonate resin, or the like is used.
However, the optical resin has a disadvantage in that workability is deteriorated due to insufficient fluidity thereof. Therefore, it may be difficult to apply the optical resin to injection molding of an article requiring the aforementioned precision. In order to apply the resin to injection molding, it is necessary to raise the molding temperature, the mold temperature, etc., but the molding cycle becomes long, so that the molding cost increases, or the resin deteriorates, the color deteriorates, etc. during molding.
In order to solve this problem, examples of a method of improving the fluidity of a resin during molding of an optical material include a method of lowering viscosity, lowering weight average molecular weight, adding a low molecular weight oligomer, widening a molecular weight distribution, and the like, but excellent physical properties inherent to the resin such as heat resistance and impact resistance tend to deteriorate.
Accordingly, continuous efforts have been made to improve the processability while maintaining the advantages of the resin.
Disclosure of Invention
Technical problem
One exemplary embodiment of the present specification is directed to providing a polycarbonate resin and a method for preparing the same.
Another exemplary embodiment of the present specification is directed to providing a polycarbonate resin composition including the above polycarbonate resin and a molded article prepared from the polycarbonate resin composition.
Technical proposal
An exemplary embodiment of the present invention provides a polycarbonate resin having a relaxation time of 2 seconds to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less.
An exemplary embodiment of the present specification provides a polycarbonate resin having a relaxation time of 1 second to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less, and comprising a first unit of the following chemical formula 1; a second unit of the following chemical formula 2; and a third unit of the following chemical formula 3.
[ Chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
P is an integer of 1 to 6,
When m, n and p are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
X5 to X8 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
R13 and R14 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
Z3 and Z4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
M 'and n' are each integers of 0 to 6,
P' is an integer of 1 to 6,
R13 and r14 are each an integer of 1 to 4,
When r13, r14, m ', n ' and p ' are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
X9 to X12 are identical to or different from each other and are each independently O or S,
Z5 and Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R15 and R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
M 'and n' are each integers from 0 to 6,
P' is an integer from 1 to 6,
R15 and r16 are each an integer of 1 to 6,
When r15, r16, m ", n", and p "are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin.
Further, an exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing the above polycarbonate resin, the composition for preparing the above polycarbonate resin comprising: a compound of the following chemical formula 1 a; a compound of the following chemical formula 2 a; a compound of the following chemical formula 3 a; and a polycarbonate precursor.
[ Chemical formula 1a ]
In the chemical formula 1a, a radical of formula 1a,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
When m and n are each 2 or more, two or more structures in each bracket are the same or different from each other,
[ Chemical formula 2a ]
[ Chemical formula 3a ]
In the chemical formulas 2a and 3a,
X5 to X12 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
Z3 to Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R13 to R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
R13 and r14 are each an integer of 1 to 4,
R15 and r16 are each an integer of 1 to 6,
M ', m ", n' and n" are each integers from 0 to 6, and
When r13 to r16, m ', m ", n' and n" are each 2 or more, two or more structures in each bracket are the same or different from each other.
Another exemplary embodiment of the present specification provides a polycarbonate resin composition including the polycarbonate resin according to the above exemplary embodiment.
Still another exemplary embodiment of the present specification provides a molded article comprising the polycarbonate resin composition according to the above-described exemplary embodiment.
Advantageous effects
The polycarbonate resin according to one exemplary embodiment of the present specification has a shorter molecular relaxation time and a shorter cooling time in an injection mold than those of the polycarbonate resin in the related art, and thus has excellent processability. In addition, the polycarbonate resin has a small molecular weight drop during processing and has excellent processing stability.
By using the polycarbonate resin according to the exemplary embodiments of the present specification, an excellent optical lens, optical film, optical resin, optical fiber, or LED package having a small thickness can be obtained.
Detailed Description
Hereinafter, the present specification will be described in more detail.
The polycarbonate resin according to an exemplary embodiment of the present specification has a relaxation time of 2 seconds to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less.
An exemplary embodiment of the present specification provides a polycarbonate resin having a relaxation time of 1 second to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less, and comprising a first unit of chemical formula 1; a second unit of chemical formula 2; and a third unit of chemical formula 3.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a relaxation time of 1 second to 15 seconds at 250 ℃. Or a relaxation time of 2 seconds to 15 seconds at 250 ℃. The relaxation time is specifically 2.5 seconds to 14.5 seconds, and more specifically 3.39 seconds to 14.2 seconds at 250 ℃.
When the polycarbonate resin satisfies the relaxation time at the temperature, the cooling time in the mold during injection molding is short due to the relatively short molecular relaxation time, the processing load is low, and the time between filling cycles is reduced, so that the relaxation time is reduced. Therefore, phenomena such as weld lines, cracks, warpage, birefringence, and starving during injection molding are reduced.
For the relaxation time according to an exemplary embodiment of the present specification, any method used in the art may be used without limitation, but the relaxation time is specifically measured using a mixed rheometer (HR-2) at 250 ℃ and 0.1Hz to 100 Hz. When the strain became 30% by applying a shear force at 250 ℃, and then removing the force, the viscoelastic behavior of the polymer occurring at high temperature (250 ℃) was measured by measuring the speed at which the applied shear force was recovered to 1Pa (=1N/m 2). The shearing force is maximally applied to the extent to which the molten polymer moves, and in this case, the stress is 100Pa or more. Thereafter, the stress was rapidly removed to measure the time taken to recover to 1Pa, and the time taken for the stress to recover to the above level means the relaxation time.
In one exemplary embodiment of the present specification, the important reason for the relaxation time is that problems such as physical damage due to weak external force may occur when the resin is cooled with residual stress during cooling of the injection molded product in a mold during injection molding of the resin. Therefore, when the relaxation time according to one exemplary embodiment of the present specification is provided, the residual stress is small, so that the problem during the resin injection molding is significantly reduced. However, the longer the relaxation time, the larger the residual stress is present, and thus physical damage may easily occur even if the external force is weak.
When the residual phenol content of the polycarbonate resin according to one embodiment of the present specification is 3,000ppm or less, the polycarbonate resin has a small molecular weight reduction during processing, and the polycarbonate resin has excellent processing stability. However, when the phenol content exceeds the above range, strength and physical properties are deteriorated due to a decrease in molecular weight of the polycarbonate resin, and problems such as cracking of an injection molded product during processing may occur. Therefore, the residual phenol content is preferably 3,000ppm or less.
According to an exemplary embodiment of the present specification, the polycarbonate resin has a residual phenol content of 3,000ppm or less. The residual phenol content of the polycarbonate resin is specifically 10ppm to 3,000ppm, 50ppm to 3,000ppm, and 100ppm to 3,000ppm, and more specifically 200ppm to 2,000ppm, 200ppm to 1,200ppm, or 470ppm to 720ppm.
In the present specification, the content (concentration) of the residual phenol can be calculated as follows. First, after 1.0g of pellets was dried and 1g of solid resin was dissolved in 12ml of Methylene Chloride (MC) and 18ml of methanol (MeOH), the resulting solution was filtered with a filter having a pore size of 0.2 μm, and then HPLC/UV was measured to calculate the content of residual phenol. ( Measurement wavelength: 200 μm HPCL, mobile phase A: acetonitrile, mobile phase B: h 2 O, column: CAPCELLPAK C18 (4.6 mm ID. Times.50 mm,5 μm), column temperature: 40 ℃, flow rate: 1 ml/min, injection volume: 5 μl, run time: for 10 minutes )
In this specification, when a portion "includes/includes" one constituent element, unless specifically described otherwise, this is not intended to exclude another constituent element, but is intended to mean that another constituent element may also be included/included.
Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Although methods and materials similar or equivalent to those described herein can be used in practice or testing of exemplary embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety and in the event of a conflict, the present specification, including definitions, will control unless a particular paragraph is mentioned. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃. When the polycarbonate resin has the high shear viscosity at the temperature, the processing load is low, so that phenomena such as weld lines, cracks, warpage, birefringence, and starving during injection molding are reduced.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃. The polycarbonate resin has a high shear viscosity of preferably 30 Pa-sec to 200 Pa-sec, more preferably 50 Pa-sec to 190 Pa-sec, and even more preferably 60.7 Pa-sec to 146 Pa-sec.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 10Hz or 63 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 10 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 63 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at any one or more of 250 ℃ and 10Hz and 250 ℃ and 63 Hz.
According to one exemplary embodiment of the present disclosure, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10Hz and/or 250 ℃ and 63 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10Hz and 250 ℃ and 63 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10Hz or 250 ℃ and 63 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10 Hz.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 63 Hz.
In the present specification, when the polycarbonate resin has the above-mentioned high shear viscosity at the above-mentioned frequency, there is an advantage of convenience in processing due to excellent flowability during processing of extrusion/injection molding using a thermoplastic polymer.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at any one or more of 250 ℃ and 10Hz and 250 ℃ and 63 Hz. The polycarbonate resin has a high shear viscosity of preferably 30 Pa-sec to 200 Pa-sec, more preferably 50 Pa-sec to 190 Pa-sec, and even more preferably 60.7 Pa-sec to 146 Pa-sec.
According to one exemplary embodiment of the present disclosure, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10Hz and/or 250 ℃ and 63 Hz. The polycarbonate resin has a high shear viscosity of preferably 30 Pa-sec to 200 Pa-sec, more preferably 50 Pa-sec to 190 Pa-sec, and even more preferably 60.7 Pa-sec to 146 Pa-sec.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 10 Hz. The polycarbonate resin has a high shear viscosity of preferably 30 Pa-sec to 200 Pa-sec, more preferably 50 Pa-sec to 190 Pa-sec, and even more preferably 76.3 Pa-sec to 146 Pa-sec.
According to one exemplary embodiment of the present specification, the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at 250 ℃ and 63 Hz. The polycarbonate resin has a high shear viscosity of preferably 30 Pa-sec to 200 Pa-sec, more preferably 50 Pa-sec to 190 Pa-sec, and even more preferably 60.7 Pa-sec to 99.4 Pa-sec.
According to one exemplary embodiment of the present specification, a polycarbonate resin includes a first unit of the following chemical formula 1; a second unit of the following chemical formula 2; and a third unit of the following chemical formula 3.
[ Chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
P is an integer of 1 to 6,
When m, n and p are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
X5 to X8 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
R13 and R14 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
Z3 and Z4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
M 'and n' are each integers of 0 to 6,
P' is an integer of 1 to 6,
R13 and r14 are each an integer of 1 to 4,
When r13, r14, m ', n ' and p ' are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
X9 to X12 are identical to or different from each other and are each independently O or S,
Z5 and Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R15 and R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
M 'and n' are each integers from 0 to 6,
P' is an integer from 1 to 6,
R15 and r16 are each an integer of 1 to 6,
When r15, r16, m ", n", and p "are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin.
When the polycarbonate resin includes the first unit of chemical formula 1, the polycarbonate resin includes a relatively small isopropylidene group as compared to a large substituent such as fluorene, so that the process is economical and the possibility of processing defects is reduced because the cooling time in the mold during injection molding is short due to the short relaxation time of the polycarbonate resin, and the processability of the polycarbonate resin is excellent.
According to one exemplary embodiment of the present specification, the polycarbonate resin includes two or more second units of chemical formula 2.
According to one exemplary embodiment of the present specification, the polycarbonate resin includes two or more of the second units of chemical formula 2.
According to an exemplary embodiment of the present specification, a polycarbonate resin is provided comprising a first unit of chemical formula 1; two or more second units of chemical formula 2; and a polycarbonate resin of the third unit of chemical formula 3.
According to an exemplary embodiment of the present specification, in the polycarbonate resin, chemical formula 2 and chemical formula 3 may complement the glass transition temperature (Tg) of the first unit of chemical formula 1 or make the chain behavior of the first unit of chemical formula 1 flexible, and there is a technical effect of facilitating injection molding of molded articles.
In one exemplary embodiment of the present description, the weight average molecular weight of the polycarbonate resin is 3,000g/mol to 500,000g/mol, preferably 5,000g/mol to 300,000g/mol, 7,000g/mol to 250,000g/mol, 8,000g/mol to 200,000g/mol. The weight average molecular weight of the polycarbonate resin is more preferably 9,000g/mol to 150,000g/mol, 10,000g/mol to 100,000g/mol, 12,000g/mol to 80,000g/mol, and 13,000g/mol to 60,000g/mol.
In one exemplary embodiment of the present invention, the polycarbonate resin has a number average molecular weight of 2,000 to 300,000g/mol, 3,000 to 200,000g/mol, 4,000 to 150,000g/mol, 4,500 to 100,000g/mol, preferably 5,000 to 80,000g/mol.
When the polycarbonate resin satisfies the above weight average molecular weight and number average molecular weight ranges, the polycarbonate resin may have optimal flowability and processability.
In the present specification, the weight average molecular weight (Mw) of the polycarbonate resin and the oligomer used in the preparation thereof can be measured by Gel Permeation Chromatography (GPC) using Polystyrene (PS) standards using Agilent 1200 series. Specifically, the weight average molecular weight can be measured using an Agilent 1200 series device using Polymer Laboratorie s PLgel MIX-B300 mm length columns, and in this case the measurement temperature is 40 ℃, the solvent used is Tetrahydrofuran (THF), and the flow rate is 1 mL/min. Samples of polycarbonate resin or oligomer were each prepared at a concentration of 10mg/10mL, then fed in an amount of 10 μl, and weight average molecular weight (Mw) values were derived using a calibration curve formed using polystyrene standards. In this case, nine types of polystyrene standard products having a molecular weight (g/mol) of 2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 are used.
According to an exemplary embodiment of the present specification, the refractive index of the polycarbonate resin is 1.6 to 1.8 at 587 nm. The refractive index may preferably be 1.6 to 1.75, more preferably 1.6 to 1.72, and more preferably 1.660 to 1.669. When the resin satisfies the above refractive index, a thin and lightweight optical lens can be manufactured when the resin is applied to a molded article such as an optical lens.
In one exemplary embodiment of the present specification, the abbe number of the polycarbonate resin measured and calculated at wavelengths of 486nm, 587nm and 656nm may be 5 to 45. Preferably, the abbe number may be 10 to 25.
When the polycarbonate resin satisfies the above abbe number range, there are effects of reduced dispersion and increased sharpness when the resin is applied to molded articles such as optical lenses.
The Abbe number can be obtained from the following equations by specifically measuring refractive indices (nD, nF, and nC) at wavelengths D (587 nm), F (486 nm), and C (656 nm), respectively, at 25 ℃.
Abbe number= (nD-1)/(nF-nC)
The refractive index may be measured by a prism coupling method, and for example, SPA-3DR manufactured by SAIRON Technology Inc. may be used, but is not limited thereto.
The refractive index of the resin can be calculated by measuring the change in the amount of light reflected from the prepared sample, in which the resin was flattened by placing the slide on a heated plate of 200 c, using a prism coupler. When a prepared sample is brought into contact with a prism and then laser light is made incident on the prism, most of the incident laser light is totally reflected, but when a specific angle of incidence and conditions are satisfied, light is coupled because an evanescent field (EVANESCENT FIELD) is generated at the boundary surface. By measuring the angle at which coupling occurs (and as a result, the intensity of the light detected by the detector drops sharply), the refractive index of the film can be automatically calculated by the prism coupler from the parameters related to the polarization mode of the light and the refractive indices of the prism and the substrate.
In one exemplary embodiment of the present specification, the glass transition temperature (Tg) of the polycarbonate resin may be 90 to 200 ℃. The glass transition temperature may preferably be 100 ℃ to 190 ℃, 120 ℃ to 170 ℃, and 130 ℃ to 160 ℃, and even more preferably 141 ℃ to 142 ℃.
When the polycarbonate resin satisfies the above glass transition temperature range, the glass transition temperature is easily adjusted when the polycarbonate resin composition is prepared by mixing with a resin having excellent heat resistance and injection moldability and having a glass transition temperature different from the above range, so that the physical properties desired in the present specification can be satisfied.
The glass transition temperature (Tg) can be measured by a Differential Scanning Calorimeter (DSC). Specifically, the glass transition temperature can be measured from a graph obtained by: a sample of 5.5mg to 8.5mg of the polycarbonate resin was heated to 270 ℃ under a nitrogen atmosphere, and then scanned while the resin sample was heated at a heating rate of 10 ℃/minute during the second heating after cooling.
According to one exemplary embodiment of the present specification, the Melt Index (MI) of the polycarbonate resin is 5 to 150, specifically 10 to 100, and even more specifically 20 to 80 or 41 to 53. The above MI can be measured by a method used in the art, specifically, using a melt index meter (MI 2.2) manufactured by Goettfert co., ltd. The sample was dried in an oven at 120℃for 5 hours or more, the dried sample was put into a device and melted at a measurement temperature (260 ℃) for 5 minutes, and then the weight of the sample passing through a nozzle in 5 seconds was measured when a pressure of 2.16kg was applied, and converted into g/10 minutes units to calculate a Melt Index (MI).
When the polycarbonate resin has the aforementioned melt index, the polycarbonate resin exhibits characteristics suitable for injection molding due to maintaining proper fluidity.
Examples of substituents in the present specification will be described below, but are not limited thereto.
In the present description of the invention,Meaning the parts to be connected.
The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound becomes an additional substituent, and a position to be substituted is not limited as long as the position is a position where the hydrogen atom is substituted (i.e., a position where a substituent may be substituted), and when two or more are substituted, two or more substituents may be the same as or different from each other.
In the present specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; a hydroxyl group; cyano group; an alkyl group; cycloalkyl; an alkoxy group; alkenyl groups; an aryloxy group; arylthio; alkylthio; a silyl group; an aryl group; and heteroaryl, substituted with substituents linked with two or more of the exemplified substituents, or not having substituents.
In this specification, the fact that two or more substituents are linked means that hydrogen of any substituent is linked to another substituent. For example, when two substituents are attached to each other, the phenyl and naphthyl groups may be attached to each other to become substituentsFurther, the case where three substituents are connected to each other includes not only the case where (substituent 1) to (substituent 2) to (substituent 3) are sequentially connected to each other but also the case where (substituent 2) and (substituent 3) are connected to (substituent 1). For example, phenyl, naphthyl and isopropyl groups may be linked to each other to become substituentsThe above definition also applies to the case where four or more substituents are linked to each other.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 30. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl and the like, but are not limited thereto.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30. Specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 30. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, and the aryl group may be monocyclic or polycyclic.
When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Specific examples of the monocyclic aryl group include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto.
When the aryl group is a polycyclic aryl group, the number of carbon atoms thereof is not particularly limited, but is preferably 10 to 50. Specific examples of polycyclic aryl groups include naphthyl, anthryl, phenanthryl, triphenylene, pyrenyl, phenalkenyl, and,A base group,A radical, a fluorenyl radical, etc., but is not limited thereto.
In the present specification, a fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.
Examples of fluorenyl groups include
Etc., but is not limited thereto.
In the present specification, an "adjacent" group may mean a substituent substituted for an atom directly connected to an atom substituted with a corresponding substituent, a substituent positioned most closely to the corresponding substituent in space, or another substituent substituted for an atom substituted with a corresponding substituent. For example, two substituents substituted in the ortho position of the benzene ring and two substituents substituted for the same carbon in the aliphatic ring may be interpreted as groups "adjacent" to each other.
In the present specification, the heteroaryl group contains one or more atoms other than carbon, i.e., one or more heteroatoms, and in particular, the heteroatoms may include one or more atoms selected from O, N, se, S and the like. The number of carbon atoms thereof is not particularly limited, but is preferably 2 to 30, and the heteroaryl group may be monocyclic or polycyclic. Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,An azolyl group,Diazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl quinoxalinyl, phthalazinyl, pyridopyrimidinyl, and pyridopyrazinyl radical pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, and benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthridinyl, phenanthrolinyl, and isozylOxazolyl, thiadiazolyl, dibenzofuranyl, dibenzosilol, and phenoneThioyl, phenoneOxazinyl, phenothiazinyl, indanocarbazolyl, spirofluorenxanthenyl, spirofluorenothioyl, tetrahydronaphtothienyl, tetrahydronaphtofuranyl, tetrahydrobenzothienyl, tetrahydrobenzofuranyl, and the like, but are not limited thereto.
In the present specification, the silyl group may be an alkylsilyl group, arylsilyl group, alkylarylsilyl group, heteroarylsilyl group or the like. The above examples of alkyl groups may be applied to alkyl groups in alkylsilyl groups, the above examples of aryl groups may be applied to aryl groups in arylsilyl groups, the examples of alkyl and aryl groups may be applied to alkyl and aryl groups in alkylarylsilyl groups, and the examples of heterocyclic groups may be applied to heteroaryl groups in heteroarylsilyl groups.
In the present specification, an aryloxy group may be represented by —oro, and the description about the above aryl group applies to Ro.
In the present specification, arylthio groups may be represented by-SRs 1, and the description about the above aryl groups applies to Rs1.
In the present specification, alkylthio groups may be represented by-SRs 2, and the description of the above alkyl groups applies to Rs2.
In the present specification, alkylene means a group having two bonding positions in an alkyl group, i.e., a divalent group. The above description of alkyl groups may be applied to alkylene groups, except that the alkylene groups are divalent.
In the present specification, cycloalkylene means a group having two bonding positions in cycloalkyl, i.e., a divalent group. The above description of cycloalkyl groups can be applied to cycloalkylene groups, except that the cycloalkylene group is divalent.
An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition for preparing a polycarbonate resin comprising a compound of the following chemical formula 1 a; a compound of the following chemical formula 2 a; a compound of the following chemical formula 3 a; and a polycarbonate precursor.
[ Chemical formula 1a ]
In the chemical formula 1a, a radical of formula 1a,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
When m and n are each 2 or more, two or more structures in each bracket are the same or different from each other,
[ Chemical formula 2a ]
[ Chemical formula 3a ]
In the chemical formulas 2a and 3a,
X5 to X12 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
Z3 to Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R13 to R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
R13 and r14 are each an integer of 1 to 4,
R15 and r16 are each an integer of 1 to 6,
M ', m ", n' and n" are each integers from 0 to 6, and
When r13 to r16, m ', m ", n' and n" are each 2 or more, two or more structures in each bracket are the same or different from each other.
An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition for preparing a polycarbonate resin comprising a compound of formula 1 a; a compound of formula 2 a; a compound of formula 3 a; and a polycarbonate precursor.
An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition for preparing a polycarbonate resin comprising a compound of formula 1 a; two or more compounds of formula 2 a; a compound of formula 3 a; and a polycarbonate precursor.
The relaxation time and residual phenol content of the polycarbonate resin are as described above.
According to one exemplary embodiment of the present description, X1 is O.
According to one exemplary embodiment of the present description, X2 is O.
According to one exemplary embodiment of the present description, X3 is O.
According to one exemplary embodiment of the present description, X4 is O.
According to one exemplary embodiment of the present description, X5 is O.
According to one exemplary embodiment of the present description, X6 is O.
According to one exemplary embodiment of the present description, X7 is O.
According to one exemplary embodiment of the present description, X8 is O.
According to one exemplary embodiment of the present description, X9 is O.
According to one exemplary embodiment of the present description, X10 is O.
According to one exemplary embodiment of the present description, X11 is O.
According to one exemplary embodiment of the present description, X12 is O.
According to one exemplary embodiment of the present description, X1 is S.
According to an exemplary embodiment of the present description, X2 is S.
According to an exemplary embodiment of the present description, X3 is S.
According to an exemplary embodiment of the present description, X4 is S.
According to an exemplary embodiment of the present description, X5 is S.
According to one exemplary embodiment of the present description, X6 is S.
According to an exemplary embodiment of the present description, X7 is S.
According to an exemplary embodiment of the present description, X8 is S.
According to an exemplary embodiment of the present description, X9 is S.
According to one exemplary embodiment of the present description, X10 is S.
According to an exemplary embodiment of the present description, X11 is S.
According to an exemplary embodiment of the present description, X12 is S.
According to one exemplary embodiment of the present description, Z1 and Z2 are identical to or different from each other and are each independently a linear or branched alkylene group having from 1 to 30 carbon atoms.
According to one exemplary embodiment of the present description, Z1 and Z2 are identical or different from each other and are each independently a linear or branched alkylene group having from 1 to 20 carbon atoms.
According to one exemplary embodiment of the present specification, Z1 and Z2 are the same or different from each other and are each independently a linear or branched alkylene group having 1 to 10 carbon atoms.
According to one exemplary embodiment of the present description, Z1 and Z2 are ethylene.
According to one exemplary embodiment of the present specification, Z3 to Z4 are identical to or different from each other and are each independently a linear or branched alkylene group having 1 to 30 carbon atoms.
According to one exemplary embodiment of the present specification, Z3 to Z4 are identical to or different from each other and are each independently a linear or branched alkylene group having 1 to 20 carbon atoms.
According to one exemplary embodiment of the present specification, Z3 to Z4 are identical to or different from each other and are each independently a linear or branched alkylene group having 1 to 10 carbon atoms.
According to one exemplary embodiment of the present description, Z3 and Z4 are ethylene.
According to one exemplary embodiment of the present specification, Z5 and Z6 are the same or different from each other and are each independently a linear or branched alkylene group having 1 to 30 carbon atoms.
According to one exemplary embodiment of the present specification, Z5 and Z6 are the same or different from each other and are each independently a linear or branched alkylene group having 1 to 20 carbon atoms.
According to one exemplary embodiment of the present specification, Z5 and Z6 are the same or different from each other and are each independently a linear or branched alkylene group having 1 to 10 carbon atoms.
According to one exemplary embodiment of the present description, Z5 and Z6 are ethylene.
According to an exemplary embodiment of the present specification, L1 and L2 are identical to or different from each other and are each independently a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, which is unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
According to an exemplary embodiment of the present specification, L1 and L2 are identical to or different from each other and are each independently a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms, which is unsubstituted or substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
According to an exemplary embodiment of the present specification, L1 and L2 are the same or different from each other and are each independently phenylene which is unsubstituted or substituted by methyl, phenyl or naphthyl; or a divalent naphthyl group.
According to an exemplary embodiment of the present specification, R1 to R4 are the same or different from each other and are each independently hydrogen; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted by cyano, a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 2 to 30 carbon atoms, or a monocyclic or polycyclic heterocyclic group having 2 to 30 carbon atoms; a condensed ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a polycyclic heteroaryl group having 6 to 30 carbon atoms.
According to an exemplary embodiment of the present specification, R1 to R4 are the same or different from each other and are each independently hydrogen; a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted by cyano, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or a monocyclic or polycyclic heterocyclic group having 2 to 20 carbon atoms; a condensed ring group of a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms and a monocyclic or polycyclic aliphatic hydrocarbon ring having 3 to 20 carbon atoms; or a polycyclic heteroaryl group having 6 to 20 carbon atoms.
According to an exemplary embodiment of the present specification, R1 to R4 are the same or different from each other and are each independently hydrogen; phenyl which is unsubstituted or substituted by cyano or methyl; unsubstituted or cyano-substituted naphthyl; indanyl; or quinolinyl.
According to one exemplary embodiment of the present specification, R11 and R12 are the same or different from each other and are each independently a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; or monocyclic or polycyclic heteroaryl groups having 2 to 30 carbon atoms, or are bonded to each other to form a monocyclic or polycyclic aliphatic hydrocarbon ring having 6 to 30 carbon atoms which is unsubstituted or substituted by a linear or branched alkyl group having 1 to 30 carbon atoms.
According to one exemplary embodiment of the present specification, R11 and R12 are the same or different from each other and are each independently a linear or branched alkyl group having 1 to 20 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; monocyclic or polycyclic aryl groups having 6 to 20 carbon atoms; or monocyclic or polycyclic heteroaryl groups having 2 to 20 carbon atoms, or are bonded to each other to form a monocyclic or polycyclic aliphatic hydrocarbon ring having 6 to 20 carbon atoms which is unsubstituted or substituted by a linear or branched alkyl group having 1 to 20 carbon atoms.
According to one exemplary embodiment of the present description, R11 and R12 are the same or different from each other and are each independently methyl or phenyl, or are bonded to each other to form unsubstituted or methyl-substituted cyclohexane; or cyclododecane.
According to an exemplary embodiment of the present description, R13 and R14 are the same or different from each other and are each independently hydrogen or aryl having 6 to 30 carbon atoms, or are bonded to adjacent groups to form a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms.
According to an exemplary embodiment of the present description, R13 and R14 are the same or different from each other and are each independently hydrogen or aryl having 6 to 20 carbon atoms, or are bonded to adjacent groups to form a monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms.
According to an exemplary embodiment of the present description, R13 and R14 are the same or different from each other and are each independently hydrogen; a phenyl group; or naphthyl, or bonded to an adjacent group to form benzene.
According to one exemplary embodiment of the present description, R15 and R16 are the same or different from each other and are each independently hydrogen or aryl having 6 to 30 carbon atoms.
According to an exemplary embodiment of the present description, R15 and R16 are the same or different from each other and are each independently hydrogen or aryl having 6 to 20 carbon atoms.
According to an exemplary embodiment of the present specification, R15 and R16 are the same or different from each other and are each independently hydrogen; a phenyl group; or a naphthyl group.
According to one exemplary embodiment of the present specification, chemical formula 1a is any one of the following compounds.
According to one exemplary embodiment of the present specification, chemical formula 2a is any one of the following compounds.
According to one exemplary embodiment of the present specification, chemical formula 3a is any one of the following compounds.
According to one exemplary embodiment of the present specification, the method for preparing the polycarbonate resin includes the compound of chemical formula 1a, the compound of chemical formula 2a, and the compound of chemical formula 3a, and the compound of chemical formula 1a, the compound of chemical formula 2a, and the compound of chemical formula 3a are included in an amount of 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%. Specifically, the compound of chemical formula 1a, the compound of chemical formula 2a, and the compound of chemical formula 3a are included in an amount of 0.1 mol% to 99.8 mol% to 0.1 mol% to 99.8 mol%, 1 mol% to 98 mol%, 5 mol% to 90 mol%.
According to one exemplary embodiment of the present specification, a method for preparing a polycarbonate resin includes a compound of chemical formula 1a, two or more compounds of chemical formula 2a, and a compound of chemical formula 3a, and the compound of chemical formula 1a, the two or more compounds of chemical formula 2a, and the compound of chemical formula 3a are included in an amount of 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%. Specifically, the compound of chemical formula 1a, the two or more compounds of chemical formula 2a, the compound of chemical formula 3a are present in an amount of 0.1 to 99.8 mol%: an amount of 0.1 mol% to 99.8 mol%, 1 mol% to 98 mol% to 1 mol% to 98 mol%, 5 mol% to 90 mol% to 5 mol% to 90 mol% is included.
When chemical formulas 1a, 2a and 3a are included in the above amounts, the processability of the polycarbonate resin is excellent, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, so that there is a technical effect that is advantageous for injection molding of molded articles.
According to one exemplary embodiment of the present specification, the polycarbonate precursor is contained in an amount of 50 to 150 parts by mole, preferably 100 parts by mole, with respect to 100 parts by mole of the sum of the compound of chemical formula 1a, the compound of chemical formula 2a below, and the compound of chemical formula 3a below in the composition for preparing a polycarbonate resin.
According to one exemplary embodiment of the present specification, the polycarbonate precursor is contained in an amount of 50 to 150 parts by mol, preferably 100 parts by mol, with respect to 100 parts by mol of the sum of the compound of chemical formula 1a, two or more compounds of chemical formula 2a, and the compound of chemical formula 3a in the composition for preparing a polycarbonate resin.
When the polycarbonate precursor is contained in the above molar parts, a polycarbonate resin having excellent transparency, heat resistance, refractive index, birefringence and strength, and good processability can be prepared.
The composition for preparing the polycarbonate resin may further comprise a solvent.
The solvent may be, for example, diphenyl ether, dimethylacetamide or methanol, but is not limited thereto, and any solvent applied in the art may be suitably employed.
The solvent may be contained in an amount of 5 to 60 parts by weight with respect to 100 parts by weight of the composition for preparing a resin.
The solvent may be contained in an amount of preferably 5 to 50 parts by weight, 7 to 45 parts by weight, or 8 to 40 parts by weight with respect to 100 parts by weight of the composition for preparing a resin.
According to one exemplary embodiment of the present specification, the polycarbonate precursor is included in an amount of 50 to 150 parts by weight with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
When the polycarbonate precursor is contained in the above parts by weight, a polycarbonate resin having excellent transparency, heat resistance, refractive index, birefringence and strength, and good processability can be prepared.
In one exemplary embodiment of the present specification, the compound of chemical formula 1a may be included in an amount of 1 to 100 parts by weight or 1 to 99 parts by weight with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
The compound of chemical formula 1a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
In one exemplary embodiment of the present specification, the compound of chemical formula 2a may be included in an amount of 0 to 99 parts by weight, or 1 to 99 parts by weight, with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
The compound of chemical formula 2a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
The two or more compounds of chemical formula 2a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
In one exemplary embodiment of the present specification, the compound of chemical formula 3a may be included in an amount of 0 to 99 parts by weight, or 1 to 99 parts by weight, with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
The compound of chemical formula 3a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, with respect to 100 parts by weight of the composition for preparing a polycarbonate resin.
According to one exemplary embodiment of the present specification, the polycarbonate precursor is a compound of the following chemical formula a.
[ Chemical formula A ]
In the chemical formula a, the amino acid sequence of the formula a,
Rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; or a substituted or unsubstituted aryl group, and
A1 and a2 are each 0 or 1.
According to one exemplary embodiment of the present description, rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a substituted or unsubstituted, linear or branched alkyl group having 1 to 30 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
According to one exemplary embodiment of the present description, rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
According to one exemplary embodiment of the present description, rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.
According to one exemplary embodiment of the present description, rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a linear or branched alkyl group having 1 to 20 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 6 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.
According to one exemplary embodiment of the present description, rb1 and Rb2 are the same or different from each other and are each independently-C1; a methyl group; an ethyl group; n-propyl; n-butyl; an isopropyl group; an isobutyl group; or phenyl.
According to one exemplary embodiment of the present specification, formula a is any one selected from the following compounds.
Other specific examples of the polycarbonate precursor that may be used in addition to the compound represented by chemical formula a include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, xylene carbonate, bis (chlorophenyl) carbonate, m-toluene carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dihaloformate, etc., if necessary, and any one or a mixture of two or more thereof may be used.
In one exemplary embodiment of the present specification, it is more preferable that the polycarbonate resin is polymerized from the compound of chemical formula 1a, the compound of chemical formula 2a, the compound of chemical formula 3a, and the polycarbonate precursor of chemical formula a.
In one exemplary embodiment of the present specification, it is more preferable that the polycarbonate resin is polymerized from the compound of chemical formula 1a, two or more compounds of chemical formula 2a, the compound of chemical formula 3a, and the polycarbonate precursor of chemical formula a.
The unit of the above chemical formula 1 may be formed by polymerizing the compound of the chemical formula 1a and the polycarbonate precursor of the chemical formula a, the unit of the above chemical formula 2 may be formed by polymerizing the compound of the chemical formula 2a and the polycarbonate precursor of the chemical formula a, and the unit of the above chemical formula 3 may be formed by polymerizing the compound of the chemical formula 3a and the polycarbonate precursor of the chemical formula a.
The unit of the above chemical formula 1 can be formed by polymerizing the compound of chemical formula 1a and the polycarbonate precursor of chemical formula a.
The compound of chemical formula 1a may be used in an amount of 1 to 100 parts by mol, 1 to 99 parts by mol, with respect to 100 parts by mol of all monomers constituting the polycarbonate resin including the unit of chemical formula 1.
The polycarbonate precursor of chemical formula a may be used in an amount of 50 to 150 parts by mol with respect to 100 parts by mol of all monomers of the compound of chemical formula 1a constituting the resin.
The unit of chemical formula 2 described above can be formed by polymerizing the compound of chemical formula 2a and the polycarbonate precursor of chemical formula a.
The compound of chemical formula 2a may be used in an amount of 1 to 100 parts by mol, 1 to 99 parts by mol, with respect to 100 parts by mol of all monomers constituting the polycarbonate resin including the unit of chemical formula 2.
The polycarbonate precursor of chemical formula a may be used in an amount of 50 to 150 parts by mol with respect to 100 parts by mol of all monomers of the compound of chemical formula 2a constituting the resin.
The unit of the above chemical formula 3 can be formed by polymerizing the compound of chemical formula 3a and the polycarbonate precursor of chemical formula a.
The compound of chemical formula 3a may be used in an amount of 1 to 100 parts by mol, 1 to 99 parts by mol, with respect to 100 parts by mol of all monomers constituting the polycarbonate resin including the unit of chemical formula 3.
The polycarbonate precursor of chemical formula a may be used in an amount of 50 to 150 parts by mol with respect to 100 parts by mol of all monomers of the compound of chemical formula 3a constituting the resin.
The polycarbonate precursor of chemical formula a may be used in an amount of 50 to 150mol parts with respect to 100mol parts of the sum of the compound of chemical formula 1a, the compound of chemical formula 2a below, and the compound of chemical formula 3a constituting the resin.
The polycarbonate precursor of chemical formula a may be used in an amount of 50 to 150 parts by mol with respect to 100 parts by mol of the sum of the compound of chemical formula 1a, two or more compounds of chemical formula 2a, and the compound of chemical formula 3a constituting the resin.
For the polymerization of the resin according to the present specification, methods known in the art may be used.
Preferably, the polymerization is carried out by melt polycondensation.
In the melt polycondensation method, a composition for preparing a polycarbonate resin is used, a catalyst may also be applied as needed, and the melt polycondensation may be performed under heating and further under normal pressure or reduced pressure while removing by-products by transesterification. As the catalyst, materials commonly used in the art can be used.
Specifically, in the melt polycondensation method, it is preferable to cause the compound of chemical formula 1 a; a compound of formula 2 a; a compound of formula 3; and the polycarbonate precursor is melted in the reaction vessel and then reacted in a state where the byproduct compound is allowed to remain.
More specifically, in the melt polycondensation method, it is preferable to cause the compound of chemical formula 1 a; two or more compounds of formula 2 a; a compound of formula 3; and the polycarbonate precursor is melted in the reaction vessel and then reacted in a state where the byproduct compound is allowed to remain.
To allow the byproduct compounds to stay, the reaction apparatus may be shut down, or the pressure may be controlled by decreasing the pressure or increasing the pressure.
The reaction time of the process is 20 minutes or more and 600 minutes or less, preferably 40 minutes or more and 450 minutes or less, and more preferably 60 minutes or more and 350 minutes or less.
In this case, when the byproduct compound is distilled off immediately after production, the finally obtained resin has a small content of high molecular weight substances. However, when the byproduct compound is allowed to stay in the reaction vessel for a certain period of time, the finally obtained resin is obtained as a high molecular weight substance having a large content.
The melt polycondensation process may be carried out continuously or in a batch mode. The reaction apparatus for carrying out the reaction may be a vertical type equipped with a soken impeller, an anchor impeller, a maxbend impeller, a spiral belt impeller, or the like, may be a horizontal type equipped with a paddle blade, a grid blade, a spectacle blade, or the like, and may be an extruder type equipped with a screw. Further, in view of the viscosity of the polymer, it is desirable to perform using a reaction apparatus in which these reaction apparatuses are appropriately combined.
In the method for preparing a polycarbonate resin used in the present specification, the catalyst may be removed or deactivated after completion of the polymerization reaction to maintain thermal stability and hydrolytic stability. The method of inactivating the catalyst by adding an acidic substance known in the art may be preferably performed.
As the acidic substance, for example, esters such as butyl benzoate are preferably used; aromatic sulfonic acids such as p-toluene sulfonic acid; aromatic sulfonates such as butyl and hexyl p-toluenesulfonate; phosphoric acids, such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites, such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite and monooctyl phosphite; phosphates such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate and monooctyl phosphate; phosphonic acids, such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonates such as diethyl phenylphosphonate; phosphines, such as triphenylphosphine and bis (diphenylphosphino) ethane; boric acids, such as boric acid and phenylboric acid; aromatic sulfonates, e.g. tetrabutyl dodecylbenzene sulfonateA salt; organic halides such as stearic acid chloride, benzoyl chloride and p-toluenesulfonic acid chloride; alkyl sulfuric acids, such as dimethyl sulfuric acid; organic halides such as benzyl chloride; etc.
The acidic substance may be used in an amount of 0.1 to 5 parts by mol, preferably 0.1 to 1 part by mol, with respect to 100 parts by mol of the catalyst.
When the amount of the acidic substance is less than 0.1mol part, the effect of inactivation becomes insufficient, which is not preferable. Further, when the amount exceeds 5mol parts, the heat resistance of the resin is deteriorated, and the molded article is easily colored, which is not preferable.
The process of devolatilizing the low boiling compounds in the resin may also be performed at a pressure of 0.1mmHg to 1mmHg and a temperature of 200 ℃ to 350 ℃ after the deactivation of the catalyst. In this process, a horizontal type apparatus equipped with stirring blades (e.g., paddle blades, grille blades, and spectacle blades) having excellent surface renewal capacity, or a thin film evaporator is preferably used.
The content of the foreign matter in the resin in the present specification is preferably as small as possible, and filtration of the molten raw material, filtration of the catalyst solution, and the like are preferably performed.
The mesh of the filter for filtration is preferably 5 μm or less, and more preferably 1 μm or less. In addition, filtration of the produced resin using a polymer filter is preferably performed. The mesh of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. Further, the process of obtaining the resin pellets needs to be performed in a low-dust environment, and the environment is preferably 6 grades or less, and more preferably 5 grades or less.
Further, examples of the method of molding the molded article comprising the polycarbonate resin include, but are not limited to, compression molding, roll processing, extrusion molding, stretching, and the like, in addition to injection molding.
Another exemplary embodiment of the present specification provides a polycarbonate resin composition comprising the resin according to the above exemplary embodiment.
In one exemplary embodiment of the present specification, the polycarbonate resin may be included in an amount of 1 to 80 parts by weight based on 100 parts by weight of the polycarbonate resin composition.
In one exemplary embodiment of the present specification, the polycarbonate resin composition may further include a solvent. The solvent may be, for example, dimethylacetamide or 1, 2-dichlorobenzene.
The solvent may be contained in an amount of 20 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.
The polycarbonate resin composition may further include an additional monomer in addition to the compound of chemical formula 1 a. The other monomer is not particularly limited, and a monomer commonly used in the field related to polycarbonate may be suitably employed as long as the main physical properties of the polycarbonate resin composition are not changed. The additional monomer may be used in an amount of 1 to 50 parts by mol with respect to 100 parts by mol of all monomers constituting the resin including the unit of chemical formula 1.
If necessary, the polycarbonate resin composition may further include one or more selected from the following additives in addition to the resin including the unit of chemical formula 1: such as antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, UV absorbers, inorganic additives, pigments and dyes.
The additive may be contained in an amount of 1 to 99 parts by weight based on 100 parts by weight of the polycarbonate resin composition.
The types of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, UV absorbers, inorganic additives, pigments or dyes are not particularly limited, and those applied in the art may be suitably employed.
Still another exemplary embodiment of the present specification provides a molded article comprising the resin composition according to the above-described exemplary embodiment.
In one exemplary embodiment of the present specification, a molded article may be prepared from the polycarbonate resin composition or a cured product thereof.
As an example of a method of preparing a molded article, it may include: the polycarbonate resin and the additive are well mixed using a mixer, the resulting mixture is prepared into pellets by extrusion molding the mixture using an extruder, the pellets are dried, and then the pellets are injection molded using an injection molding machine.
In one exemplary embodiment of the present description, the molded article is an optical lens.
In one exemplary embodiment of the present specification, the optical lens has a thickness of 0.1 μm to 30mm.
The optical lens according to one exemplary embodiment of the present specification has a high refractive index, and thus an optical lens having a small thickness can be realized.
The optical lens is manufactured using the polycarbonate resin, has a small thickness, a high refractive index, and a high transparency, and can be preferably applied to cameras, cellular phones, vehicles, and autopilot sensor lenses.
In one exemplary embodiment of the present specification, the molded article is an optical fiber.
In one exemplary embodiment of the present description, the molded article is an optical film or an optical film. The optical film or optical thin film is manufactured using a polycarbonate resin, has a small thickness and excellent light capturing effect and light diffusing effect, and can be preferably applied to a backlight module of a liquid crystal display, a planar lens, a super lens (meta lens), and the like.
In one exemplary embodiment of the present specification, the optical film or optical thin film has a thickness of 0.1nm to 10mm.
In one exemplary embodiment of the present specification, the molded article is an optical resin. The optical resin is manufactured using a polycarbonate resin and has low optical loss due to its small thickness, high refractive index, and low birefringence.
In one exemplary embodiment of the present description, the molded article is an LED package.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
Hereinafter, the present specification will be exemplified in more detail by examples.
Preparation example 1.
3.423G (0.015 mol) of monomer 1-1, 14.177g (0.024 mol) of monomer 2-1, 8.618g (0.016 mol) of monomer 2-2, 16.837g (0.045 mol) of monomer 3-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, resin 1, which is a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Preparation example 2.
1.072G (0.0047 mol) of monomer 1-1, 5.907g (0.01 mol) of monomer 2-1, 15.243g (0.0283 mol) of monomer 2-2, 21.326g (0.057 mol) of monomer 3-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, resin 2, which is a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Preparation example 3.
22.829G (0.100 mol) of monomer 1-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative example resin 1, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to generate an atmospheric pressure atmosphere.
Preparation example 4.
37.415G (0.100 mol) of monomer 3-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative example resin 2, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to generate an atmospheric pressure atmosphere.
Preparation example 5.
53.864G (0.100 mol) of monomer 2-2 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative resin 3, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to generate an atmospheric pressure atmosphere.
Preparation example 6.
59.072G (0.100 mol) of monomer 2-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative example resin 4, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Preparation example 7.
11.41G (0.05 mol) of monomer 1-1, 26.931g (0.05 mol) of monomer 2-2 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative example resin 5, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Preparation example 8.
6.846G (0.03 mol) of monomer 1-1, 37.703g (0.07 mol) of monomer 2-2 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative resin 6, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to create an atmospheric pressure atmosphere.
Preparation example 9.
11.41G (0.05 mol) of monomer 1-1, 18.707g (0.05 mol) of monomer 3-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative resin 7, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Preparation 10.
26.931G (0.05 mol) of monomer 2-2, 18.707g (0.05 mol) of monomer 3-1 and 21.422g (0.100 mol) of diphenyl carbonate were melted and reacted at 250℃for 5 hours. As the reaction proceeded, phenol was produced as a by-product, and the degree of depressurization was adjusted to 1 torr to remove phenol. After the completion of the reaction, comparative example resin 8, which was a polymer melt resin polymerized, was obtained by blowing nitrogen into the reactor to produce an atmospheric pressure atmosphere.
Examples
For each of the resin samples polymerized in the above preparation examples, the molecular relaxation time, high shear viscosity, residual phenol content, melt Index (MI), refractive index, and glass transition temperature were measured. Molecular relaxation times were measured using a mixed rheometer (HR-2) at 250℃and 0.1Hz to 100 Hz. When the strain was brought to 30% by applying a shear force at 250 ℃, and then the force was removed, the viscoelastic behavior of the polymer occurring at high temperature (250 ℃) was measured by measuring the speed at which the applied shear force was recovered to 1Pa (=1N/m 2). The shearing force is maximally applied to the extent to which the molten polymer moves, and in this case, the stress is 100Pa or more. Thereafter, the time taken for recovery to 1Pa was measured by rapidly removing the stress, and the results are shown in table 2 below.
The high shear viscosity was measured at 250℃and 10Hz to 63Hz by placing 2g to 5g of the resin sample into a mixing rheometer (discovery (HR-2)), and the results are shown in Table 2 below.
For residual phenol content, after 1g of solid resin was dissolved in 12ml of Methylene Chloride (MC) and 18ml of methanol (MeOH), the resulting solution was filtered by using a filter having a pore size of 0.2 μm, and then HPLC/UV was measured to calculate the residual phenol content, and it is shown in Table 2 below. ( Measurement wavelength: 200 μm HPCL, mobile phase A: acetonitrile, mobile phase B: h 2 O, column: CAPCELLPAK C18 (4.6 mm ID. Times.50 mm,5 μm), column temperature: 40 ℃, flow rate: 1 ml/min, injection volume: 5 μl, run time: for 10 minutes )
Melt Index (MI) was measured using a melt index meter (MI 2.2) manufactured by Goettfert inc. The resin sample was dried in an oven at 120℃for 5 hours or more, the dried sample was put into a device and melted for 5 minutes at a measurement temperature (260 ℃) and then the weight of the sample passing through the nozzle in 5 seconds was measured when a pressure of 2.16kg was applied and converted into g/10 minutes units to calculate a Melt Index (MI), and the melt index is shown in Table 2 below.
Differential Scanning Calorimeter (DSC) measurements to determine the glass transition temperature (Tg) of the resin. The glass transition temperature (Tg) is obtained on a graph obtained by: the resin samples were heated to 270 ℃ under a flow of N 2 mg to 8.5mg, cooled, and then scanned while being heated at a heating rate of 10 ℃/min during the second heating, and the glass transition temperatures (Tg) are shown in table 2 below.
The refractive index is measured by the prism coupler method. Refractive indices were measured at measurement wavelengths of 486nm, 587nm and 656nm, respectively, and the average values are shown in table 2 below. The refractive index measured at each of the wavelengths is the same.
TABLE 1
In table 1, the molar ratios of the monomers used in the polycarbonate resins used in the examples and comparative examples are shown.
TABLE 2
In table 2, tg means glass transition temperature, and MI means melt index.
In table 2, it can be seen that the resins of examples 1 and 2 (each of which is a polycarbonate resin according to one exemplary embodiment of the present specification) comprise a first unit, a second unit, and a third unit, and the polycarbonate resin has a relaxation time of 1 second to 15 seconds or 2 seconds to 15 seconds at 250 ℃ and a residual phenol content of less than 3,000 ppm. Specifically, the resins of examples 1 and 2 have relaxation times of 3.39 seconds to 14.2 seconds at 250 ℃ and residual phenol contents of 470ppm to 720 ppm.
In contrast, the polycarbonate resins of comparative examples 1 to 4 (which are resins each comprising the first unit, the second unit, or the third unit) and the polycarbonate resins of comparative examples 5 to 8 (which comprise only two of the first unit to the third unit) have a relaxation time of less than 1 second or more than 15 seconds and/or a residual phenol content of more than 3,000ppm at 250 ℃. When the relaxation time is less than 1 second, it can be determined that the viscosity is also low and the viscosity of the resin is low and the relaxation time is short, making it very difficult to process the resin, and when the relaxation time exceeds 15 seconds, it can be determined that the viscosity is high and the processing load increases due to the high viscosity and the long relaxation time of the resin, so that phenomena such as weld lines, cracks, warpage, birefringence, and starvation occur during injection molding.
In addition, when the residual phenol content exceeds 3,000ppm, many problems may be caused, such as deterioration of strength and physical properties due to a decrease in molecular weight of the polycarbonate resin, and cracking of the injection molded product during processing.
Although comparative examples 2,3, 6 and 8 have higher refractive indexes than examples 1 and 2, in comparative examples 2,3, 6 and 8, the relaxation time at 250 ℃ is less than 1 second or more than 15 seconds, making commercialization difficult because it is difficult to process the resin.
Further, although comparative examples 3 and 8 have higher refractive indexes than examples 1 and 2, in comparative examples 3 and 8, the residual phenol content exceeds 3,000ppm, so that many problems are caused, such as deterioration of strength and physical properties due to a decrease in molecular weight of the polycarbonate resin, and cracking of injection molded products during processing, resulting in deterioration of processing stability.
Thus, in the polycarbonate resin according to one exemplary embodiment of the present specification, since the relaxation time is 1 second to 15 seconds or 2 seconds to 15 seconds at 250 ℃ and the residual phenol content satisfies less than 3,000ppm, the molecular relaxation time is relatively short, so that the cooling time in the mold during injection molding is short and the processing load is low, and the time between filling cycles is reduced, resulting in a reduction in the relaxation time. In addition, since the residual phenol content is 3,000ppm or less, the decrease in molecular weight during processing is small. Therefore, phenomena such as weld lines, cracks, warpage, birefringence, and lack of glue are reduced during injection molding, and processing stability is excellent.
Claims (13)
1. A polycarbonate resin having a relaxation time of 2 seconds to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less.
2. A polycarbonate resin having a relaxation time of 1 second to 15 seconds at 250 ℃ and a residual phenol content of 3,000ppm or less, and
A first unit comprising the following chemical formula 1; a second unit of the following chemical formula 2; and a third unit of the following chemical formula 3:
[ chemical formula 1]
Wherein, in the chemical formula 1,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
P is an integer of 1 to 6,
When m, n and p are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
X5 to X8 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
R13 and R14 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
Z3 and Z4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
M 'and n' are each integers of 0 to 6,
P' is an integer of 1 to 6,
R13 and r14 are each an integer of 1 to 4,
When r13, r14, m ', n ' and p ' are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 3]
Wherein, in the chemical formula 3,
X9 to X12 are identical to or different from each other and are each independently O or S,
Z5 and Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R15 and R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
M 'and n' are each integers from 0 to 6,
P' is an integer from 1 to 6,
R15 and r16 are each an integer of 1 to 6,
When r15, r16, m ", n", and p "are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion linked to the main chain of the resin.
3. The polycarbonate resin of claim 1, wherein the polycarbonate resin comprises a first unit of the following chemical formula 1; a second unit of the following chemical formula 2; and a third unit of the following chemical formula 3:
[ chemical formula 1]
Wherein, in the chemical formula 1,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
P is an integer of 1 to 6,
When m, n and p are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
X5 to X8 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
R13 and R14 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
Z3 and Z4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
M 'and n' are each integers of 0 to 6,
P' is an integer of 1 to 6,
R13 and r14 are each an integer of 1 to 4,
When r13, r14, m ', n ' and p ' are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion connected to the main chain of the resin,
[ Chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
X9 to X12 are identical to or different from each other and are each independently O or S,
Z5 and Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R15 and R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
M 'and n' are each integers from 0 to 6,
P' is an integer from 1 to 6,
R15 and r16 are each an integer of 1 to 6,
When r15, r16, m ", n", and p "are each 2 or more, two or more structures in each bracket are the same or different from each other, and
* Means a portion linked to the main chain of the resin.
4. The polycarbonate resin of any of claims 1-3, wherein the polycarbonate resin has a high shear viscosity of 10 Pa-sec to 200 Pa-sec at any one or more of 250 ℃ and 10Hz and 250 ℃ and 63 Hz.
5. The polycarbonate resin of claim 2, wherein the polycarbonate resin has a relaxation time of 2 seconds to 15 seconds.
6. The polycarbonate resin of any of claims 1-3, wherein the polycarbonate resin has a Melt Index (MI) of 5 to 150.
7. The polycarbonate resin of claim 2 or 3, wherein the polycarbonate resin comprises two or more second units of chemical formula 2.
8. A method for preparing the polycarbonate resin of any of claims 1-3, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition for preparing a polycarbonate resin comprising: a compound of the following chemical formula 1 a;
a compound of the following chemical formula 2 a;
A compound of the following chemical formula 3 a; and
A polycarbonate precursor:
[ chemical formula 1a ]
Wherein, in the chemical formula 1a,
X1 to X4 are the same or different from each other and are each independently O or S,
R1 to R4 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; fused ring groups of substituted or unsubstituted aromatic hydrocarbon rings and aliphatic hydrocarbon rings; or a substituted or unsubstituted heteroaryl,
Z1 and Z2 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R11 and R12 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or bonded to each other to form a substituted or unsubstituted hydrocarbon ring,
R101 and R102 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl,
R101 is 1 or 2, and when R101 is 2, two R101 are the same or different from each other,
R102 is 1 or 2, and when R102 is 2, two R102 are the same or different from each other,
M and n are each integers from 0 to 6,
When m and n are each 2 or more, two or more structures in each bracket are the same or different from each other,
[ Chemical formula 2a ]
[ Chemical formula 3a ]
In the chemical formulas 2a and 3a,
X5 to X12 are identical to or different from each other and are each independently O or S,
L1 and L2 are the same or different from each other and are each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene,
Z3 to Z6 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group; or a substituted or unsubstituted cycloalkylene,
R13 to R16 are the same or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or a substituted or unsubstituted heteroaryl group, or a bond with an adjacent group to form a substituted or unsubstituted hydrocarbon ring,
R13 and r14 are each an integer of 1 to 4,
R15 and r16 are each an integer of 1 to 6,
M ', m ", n' and n" are each integers from 0 to 6, and
When r13 to r16, m ', m ", n' and n" are each 2 or more, two or more structures in each bracket are the same or different from each other.
9. The method of claim 8, wherein in the method for preparing the polycarbonate resin, the compound of formula 1a, the compound of formula 2a, and the compound of formula 3a are included in an amount of 0.01 mol% to 99.98 mol%: 0.01 mol% to 99.98 mol%.
10. The method of claim 8, wherein the polycarbonate precursor is a compound of formula a:
[ chemical formula A ]
In the chemical formula a, the amino acid sequence of the formula a,
Rb1 and Rb2 are the same or different from each other and are each independently a halogen group; a hydroxyl group; a substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl; or a substituted or unsubstituted aryl group, and
A1 and a2 are each 0 or 1.
11. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 3.
12. A molded article comprising the polycarbonate resin composition of claim 11.
13. The molded article of claim 12, wherein the molded article is an optical lens.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2022-0127150 | 2022-10-05 | ||
| KR20220141544 | 2022-10-28 | ||
| KR10-2022-0141544 | 2022-10-28 | ||
| PCT/KR2023/015162 WO2024076115A1 (en) | 2022-10-05 | 2023-10-04 | Polycarbonate resin and production method for same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118475637A true CN118475637A (en) | 2024-08-09 |
Family
ID=92169002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202380015849.3A Pending CN118475637A (en) | 2022-10-05 | 2023-10-04 | Polycarbonate resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118475637A (en) |
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2023
- 2023-10-04 CN CN202380015849.3A patent/CN118475637A/en active Pending
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