CN108084425B - Polycarbonate and preparation method thereof, polycarbonate composition or blend and application thereof - Google Patents
Polycarbonate and preparation method thereof, polycarbonate composition or blend and application thereof Download PDFInfo
- Publication number
- CN108084425B CN108084425B CN201611021209.1A CN201611021209A CN108084425B CN 108084425 B CN108084425 B CN 108084425B CN 201611021209 A CN201611021209 A CN 201611021209A CN 108084425 B CN108084425 B CN 108084425B
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- CN
- China
- Prior art keywords
- polycarbonate
- formula
- hydroxyphenyl
- bis
- dihydroxy
- Prior art date
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 56
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000000732 arylene group Chemical group 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims abstract description 3
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims description 13
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 11
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 10
- -1 flow aids Substances 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- XHASMJXNUHCHBL-UHFFFAOYSA-N 4-(1-phenylethyl)phenol Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=CC=C1 XHASMJXNUHCHBL-UHFFFAOYSA-N 0.000 claims description 2
- ASURBSPIYIISGI-UHFFFAOYSA-N 4-(3,3,5-trimethylcyclohexyl)phenol Chemical compound C1C(C)(C)CC(C)CC1C1=CC=C(O)C=C1 ASURBSPIYIISGI-UHFFFAOYSA-N 0.000 claims description 2
- JNAUIOQFUDVUJP-UHFFFAOYSA-N 4-cyclododecylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCCCCCCCC1 JNAUIOQFUDVUJP-UHFFFAOYSA-N 0.000 claims description 2
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 125000003375 sulfoxide group Chemical group 0.000 claims description 2
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 claims 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 239000000654 additive Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 31
- 229930185605 Bisphenol Natural products 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000008346 aqueous phase Substances 0.000 description 15
- 239000004431 polycarbonate resin Substances 0.000 description 15
- 229920005668 polycarbonate resin Polymers 0.000 description 14
- 230000003068 static effect Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000006085 branching agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SPSSDDOTEZKOOV-UHFFFAOYSA-N 2,3-dichloroquinoxaline Chemical compound C1=CC=C2N=C(Cl)C(Cl)=NC2=C1 SPSSDDOTEZKOOV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
- 150000003252 quinoxalines Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- GZEGFNCRZUGIOB-UHFFFAOYSA-N 2,3,6-trichloroquinoxaline Chemical compound N1=C(Cl)C(Cl)=NC2=CC(Cl)=CC=C21 GZEGFNCRZUGIOB-UHFFFAOYSA-N 0.000 description 2
- UWSAFTDEEVGSAC-UHFFFAOYSA-N 2,3-dichloro-6-methylquinoxaline Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C)=CC=C21 UWSAFTDEEVGSAC-UHFFFAOYSA-N 0.000 description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KXIXHISTUVHOCY-UHFFFAOYSA-N 1-propan-2-ylpiperidine Chemical compound CC(C)N1CCCCC1 KXIXHISTUVHOCY-UHFFFAOYSA-N 0.000 description 1
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 1
- VPVTXVHUJHGOCM-UHFFFAOYSA-N 2,4-bis[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 VPVTXVHUJHGOCM-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- ZEKCYPANSOJWDH-UHFFFAOYSA-N 3,3-bis(4-hydroxy-3-methylphenyl)-1H-indol-2-one Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3NC2=O)C=2C=C(C)C(O)=CC=2)=C1 ZEKCYPANSOJWDH-UHFFFAOYSA-N 0.000 description 1
- SWCDJTVNCMYECT-UHFFFAOYSA-N 3-(4-hydroxy-3-methylphenyl)-1,3-dihydroindol-2-one Chemical compound C1=C(O)C(C)=CC(C2C3=CC=CC=C3NC2=O)=C1 SWCDJTVNCMYECT-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical group C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- MIJYTDQAOVQRRT-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylhept-2-en-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)=CC(C)(C=1C=CC(O)=CC=1)CC(C)(C)C1=CC=C(O)C=C1 MIJYTDQAOVQRRT-UHFFFAOYSA-N 0.000 description 1
- CIEGINNQDIULCT-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylheptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C)(C=1C=CC(O)=CC=1)CC(C)(C)C1=CC=C(O)C=C1 CIEGINNQDIULCT-UHFFFAOYSA-N 0.000 description 1
- LIDWAYDGZUAJEG-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 LIDWAYDGZUAJEG-UHFFFAOYSA-N 0.000 description 1
- BOCLKUCIZOXUEY-UHFFFAOYSA-N 4-[tris(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 BOCLKUCIZOXUEY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical group O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- QDMRCCGQLCIMLG-UHFFFAOYSA-N cyclobutane-1,2-dione Chemical group O=C1CCC1=O QDMRCCGQLCIMLG-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
- C08G64/1625—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
- C08G64/1641—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/226—General preparatory processes using carbonyl halides and alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Disclosed is a polycarbonate which comprises a structural unit derived from a dihydroxy compound represented by the following formula (I),wherein R is1Is H, halogen or C1-C6 alkyl, R2Is C1-C4 alkylene, C6-C10 arylene or C7-C12 arylene alkyl. It has the advantages of excellent heat resistance, chemical resistance, high refractive index and the like. The invention further relates to a method for producing said polycarbonates, and to mixtures of said polycarbonates with fillers, dyes, conventional additives, thermoplastic polymers, and to finished products and uses.
Description
Technical Field
The invention relates to a polycarbonate containing a quinoxaline structure, a preparation method thereof, a composition and a blend which are manufactured by using the polycarbonate, and application thereof.
Background
The bisphenol A polycarbonate has the advantages of high transparency, high impact strength, good heat resistance, stable size, low hygroscopicity, easy molding and the like, and is an engineering plastic with excellent comprehensive performance. However, bisphenol a polycarbonate is still insufficient in heat resistance, weather resistance, chemical resistance, refractive index and other properties in new applications such as automobile weight reduction, mobile device housings, image sensor microlenses and the like.
In the research of high performance of copolycarbonate, many studies have been made to improve the performance of one aspect, and it is difficult to improve the above-mentioned overall performance, for example:
U.S. Pat. No. 5,126,428 reports that copolycarbonate containing bisphenol TMC structure has better heat resistance, but the heat resistance stability is reduced, the weather resistance and chemical resistance are not improved, and the refractive index is reduced.
U.S. Pat. No. 4,426,514 discloses a copolycarbonate containing 4, 4' -dihydroxydiphenyl sulfide having a high refractive index, but having a reduced heat resistance and no improvement in weather resistance and chemical resistance.
U.S. Pat. No. 5,412,064 reports that copolycarbonates containing bisphenol fluorene structures have good heat resistance and high refractive index, but the refractive index is still insufficient, and the weather resistance and chemical resistance are not improved.
U.S. Pat. No. 5,530,083 reports that a copolycarbonate containing a polydimethylsiloxane structure has good weather resistance and chemical resistance, but also has reduced heat resistance and refractive index.
U.S. Pat. No. 8,445,624 reports that copolycarbonates containing isosorbide structures have improved weatherability and chemical resistance, but reduced heat resistance and refractive index.
Therefore, the prior art still needs to make a breakthrough in the polycarbonate with a novel structure, which has the advantages of comprehensive properties in the aspects of heat resistance, chemical resistance, weather resistance, high refractive index and the like.
The quinoxaline structure has high stability, can provide a series of advantages of excellent heat resistance, chemical resistance, weather resistance, high refractive index and the like, and is very beneficial to preparing high-performance polymer materials.
U.S. Pat. No. 4,797,467 discloses branched polycarbonates containing quinoxaline structures, but the quinoxaline structures are used only as branching agents and do not constitute molecular backbones for the polycarbonate, and the performance advantages of the quinoxaline structures are not shown, nor are they investigated.
Japanese patent JPH05222181A reports a series of polycarbonates with quinoxaline structure in the main chain, but mainly focuses on the application of the polycarbonates on photosensitive materials, and does not research on the improvement of other properties. In addition, the patent adopts a structural design that a benzene ring is directly connected with a quinoxaline ring, so that the polymer can absorb in a visible light region, and the polymer has a darker color. The above drawbacks will limit the application fields, especially for colorless transparent high refractive index optical materials.
Disclosure of Invention
The invention aims to provide a novel polycarbonate containing a quinoxaline structure, which has outstanding performance advantages in the aspects of heat resistance, chemical resistance, weather resistance, high refractive index and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polycarbonate comprising at least a structural unit derived from a dihydroxy compound represented by the following formula (I):
wherein R is1Is H, halogen or C1-C6 alkyl, R2Is a single bond, C1-C4 alkylene, C6-C10 arylene or C7-C12 arylene alkyl.
The compound containing a quinoxaline structure or a derivative thereof can be obtained by condensation reaction of a compound containing an ethylene diketone structure and o-phenylenediamine and a derivative thereof. This process is described in Chemistry of Heterocyclic Compounds, Volume5, Chemistry of Heterocyclic Compounds, Pyridazine and Pyrazine Rings (Cinnaolines, Phthalazines, and Quinoxalines), Part 3, John Wiley & Sons, Inc. And are therefore well known to researchers in the relevant field.
In the case of the structure of the general formula (I), if the above-mentioned route is employed, it is necessary to prepare the compound by reacting o-phenylenediamine and its derivative with a compound represented by the following formula (VI), which is difficult to prepare.
The preparation of the dihydroxy compound with the structure of the general formula (I) by adopting the raw material containing the quinoxaline structure in advance can avoid the difficulty in synthesis, and meanwhile, the product does not have amine residue which is easy to cause dark color, which is also beneficial to the final preparation of colorless and transparent polymers. The present invention thus provides a Williamson reaction of a quinoxaline derivative represented by the following formula (II) with an excess of a dihydroxy compound represented by the formula (III) to prepare a structure of the general formula (I). Excess dihydroxy compound is removed by solubility or differences in melting point, boiling point (references Chemistry of Heterocyclic Compounds, Volume5, Chemistry of Heterocyclic Compounds: Pyridazine and Pyrazine Rings: (Cinnaolines, Phthalazines, and Quinoxalines), Part 3, John Wiley & Sons, Inc).
HO-R2-OH (III)
Wherein R is1And R2The structure of the compound is as shown in the general formula (I), and X represents halogen.
The polycarbonate of the present invention preferably contains a structural unit derived from the dihydroxy compound represented by formula (IV) from the viewpoints of the properties of the polymer to be produced and the ease of obtaining raw materials.
The polycarbonate of the present invention may further comprise, in addition to the structural units derived from the dihydroxy compound represented by formula (I), structural units derived from hydroquinone, resorcinol, one or more dihydroxy aromatic compounds represented by formula (V):
wherein R is3Each occurrence is independently a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group; n and m independently represent an integer of 0 to 4; w represents a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfone group, a sulfoxide group, an alkylene group having from C1 to C8, an alkylidene group having from C2 to C8, a cycloalkylene group having from C5 to C15, or a cycloalkylidene group having from C5 to C15.
Preferred dihydroxy aromatic compounds include hydroquinone, resorcinol, 4 ' -dihydroxybiphenyl, 4 ' -dihydroxydiphenyl ether, 4 ' -dihydroxydiphenyl sulfide, 1-bis (4-hydroxyphenyl) phenylethane, 2-bis (4-hydroxyphenyl) propane, 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclododecane, 9-bis (4-hydroxyphenyl) fluorene. Further preferred is 2, 2-bis- (4-hydroxyphenyl) propane. The dihydroxy aromatic compound may be used alone or in combination of 2 or more.
In the present invention, the molar content of the dihydroxy compound represented by formula (I) is 1 to 100 mol%, preferably 5 to 90 mol%, and more preferably 10 to 80 mol% based on the total dihydroxy compounds constituting the polycarbonate.
The polycarbonates according to the invention can be prepared by interfacial polycondensation or by melt transesterification, which are known to the person skilled in the art.
The interfacial polycondensation method of the present invention comprises the following steps: the dihydroxy compound and/or dihydroxy aromatic compound is dissolved in an aqueous alkali metal hydroxide solution to form an aqueous phase and phosgene is dissolved in an inert organic solvent to form an organic phase. The aqueous phase is mixed with the phosgene-containing organic phase to effect photochemical reactions at the interface. The blocking agent and the catalyst are added simultaneously or after the photochemical reaction to carry out the blocking and the coupling reaction is accelerated, or the blocking agent is only added to carry out the reaction. The above process may be carried out continuously or semi-continuously or batchwise.
In the process of the present invention, the alkali metal hydroxide to be used may be sodium hydroxide, potassium hydroxide or the like, and sodium hydroxide is preferred. The concentration of the dihydroxy compound and/or dihydroxy aromatic compound in the aqueous phase is 5 to 25 wt%, preferably 10 to 20 wt%. The molar ratio of the alkali metal hydroxide to the dihydroxy compound and/or the dihydroxy aromatic compound added is 2.0 to 3.0: 1, preferably 2.0 to 2.8: 1. since acid is generated during the reaction and alkali metal hydroxide is continuously consumed, a part of alkali is usually added during the reaction to maintain the reaction system alkaline.
In the method of the invention, the inert organic solvent used can be one or a mixture of more of C1-C6 chlorinated or brominated aliphatic hydrocarbon, C4-C6 chlorinated or brominated alicyclic hydrocarbon, C6-C8 aromatic hydrocarbon, C6-C8 chlorinated or brominated aromatic hydrocarbon in any weight ratio. Among them, preferred is one or a combination of any two or more of dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, toluene, chlorobenzene, and carbon tetrachloride, and more preferred is dichloromethane. The concentration of phosgene in the inert organic phase is 3-20 wt%, preferably 5-15 wt%.
In the process according to the invention, the molar ratio of dihydroxy compound and/or dihydroxy aromatic compound to phosgene is 1: 1 to 1.50, preferably 1: 1.05 to 1.25. The pressure in the reaction system may be any of reduced pressure, normal pressure and increased pressure, and the reaction can be carried out smoothly under normal pressure. The reaction temperature is-20 to 100 ℃, preferably 0 to 80 ℃, and more preferably 10 to 40 ℃. In general, the reaction system is heated with the polymerization, and therefore, water cooling or ice cooling is preferable.
In the process of the present invention, tertiary amines and/or quaternary ammonium salts may be used as the catalyst. The tertiary amine may be triethylamine, tripropylamine, tributylamine, trioctylamine, N-ethylpiperidine, N-methylpiperidine, N-isopropylpiperidine, N-N-propylpiperidine, etc. The quaternary ammonium salt may be a hydroxide, chloride, bromide, hydrogen sulfate, tetrafluoroborate, or the like of tetrabutylammonium, tributylbenzylammonium, tetraethylammonium, or the like. The catalyst is preferably a tertiary amine, and more preferably triethylamine. The catalyst is used in an amount of 0.001 to 10 mol%, preferably 0.01 to 8 mol%, more preferably 0.05 to 5 mol%, based on the molar amount of the dihydroxy compound and/or dihydroxy aromatic compound used.
The end-capping reagent used in the method of the present invention may be a monophenol compound, a chloroformate of a monophenol or an acid chloride of a monocarboxylic acid. The monophenolic compound may be phenol or an alkylphenol, preferably phenol, p-tert-butylphenol, isooctylphenol, p-cumylphenol. Adopting phenolic compound as end capping agent, and phosgene or chloroformate end group must be existed in the reaction mixture; in the case of chloroformates or acid chloride compounds as the blocking agent, sufficient terminal hydroxyl groups must be present in the reaction mixture. The blocking agent may be added at any point of time simultaneously with or after the photochemical reaction, as long as the above conditions are satisfied. The amount of the end-capping agent is 0 to 10 mol%, preferably 0.1 to 5 mol%, relative to the molar amount of the dihydroxy compound and/or dihydroxy aromatic compound used.
In the process of the invention, branching agents or mixtures of branching agents may optionally be added to the synthesis process in the same manner. The branching agent is typically added before the end-capping agent. The branching agent may be a mixture of one or more of triphenols, tetraphenols, acid chloride compounds of tricarboxylic acids, acid chloride compounds of tetracarboxylic acids. The triphenol and the tetraphenol may be phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) -2-heptene, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2, 4-bis (4-hydroxyphenyl isopropyl) phenol, tetrakis (4-hydroxyphenyl) methane, 3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2, 3-dihydroindole, etc. Preferred branching agents are 3, 3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2, 3-dihydroindole and 1,1, 1-tris (4-hydroxyphenyl) ethane. The amount of the branching agent to be used is preferably 0.01 to 3 mol%, more preferably 0.1 to 1 mol%, based on the dihydroxy compound and/or the dihydroxy aromatic compound.
The molecular weight of the polycarbonate prepared in the present invention is not particularly limited, and Mw (weight average molecular weight, measured by GPC after calibration with polystyrene or polycarbonate calibration substances in advance) is preferably 5000-300000, more preferably 15000-80000, and still more preferably 20000-40000.
Furthermore, it is also possible to prepare polycarbonates by melt reaction of bisphenolic compounds and/or dihydroxy aromatic compounds with diaryl carbonates, usually diphenyl carbonate, by the melt transesterification process in the presence of catalysts, for example alkali metal salts, ammonium or phosphonium compounds.
Melt transesterification is described in Encyclopedia of polymer science, volume 10 (1969), Chemistry and physics of polycarbonates, polymer reviews, H.Schnell, volume 9, John Wiley and Sons, Inc. (1964), and is therefore well known to those skilled in the art.
The obtained reaction crude product can be subjected to post-treatment by various known separation and purification methods to obtain a polycarbonate resin having a desired purity.
The polycarbonate resin of the present invention may further contain known conventional additives to constitute a polycarbonate composition. The additive components may be mold release agents, flow aids, heat stabilizers, antioxidants, UV absorbers, IR absorbers, flame retardants, antistatic agents, dyes and pigments, fillers, and the like. The additive is present in an amount of from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, more preferably from 0.02 to 2% by weight, based on the total mass of the polycarbonate composition.
The polycarbonates of the invention may be blended, optionally with other thermoplastic polymers including but not limited to bisphenol a type PC, ABS, PET, PBT, PS, PMMA and/or with conventional additives, typically glass fibers, glass spheres, carbon fibers, inorganic fillers.
The polycarbonate compositions or blends of the present invention may be prepared by means of compounding. The components are mixed in a known manner and melt-compounded and extruded at temperatures of 240 ℃ to 330 ℃ in customary equipment, such as single-screw, twin-screw extruders, and granulated by means of a granulator.
The polycarbonate of the present invention can be used in any case where known resins such as polycarbonate, polyester carbonate and polyester are used.
Preferably, the polycarbonates according to the invention or the polycarbonate compositions or blends described above can be used for the production of shaped parts of any type. Various molded articles can be produced by injection molding the pellets produced by the above-described method, or sheets, films, profile extrusion molded articles, direct blow molded articles, and injection molded articles can be produced from the resin melt-kneaded by an extruder without passing through the pellets.
Further preferred is the use of the polycarbonates according to the invention for the production of transparent or translucent or opaque or coloured injection-molded parts, extrusion-molded parts such as sheets, films, profiles, and laminates from sheets, films and the like. Based on their performance characteristics, they are particularly suitable for outdoor applications where a high degree of weathering is required, such as automotive glazing or exterior trim, lamp housings and housings for lighting fixtures, and as panels for covering in the safety and protective sector.
The formed part prepared by the polycarbonate has good comprehensive properties of heat resistance, weather resistance, chemical resistance and the like.
Detailed Description
The following examples are intended to illustrate the invention, which is not limited to the scope of the examples, but also includes any other modifications within the scope of the claims of the invention.
The raw materials used in the following examples were respectively:
bisphenol A: industrial grade, purchased from the blue star new chemical materials, inc (tin-free resin plant); sodium hydroxide: analytically pure, purchased from chemical reagents ltd of miuiou, department of Tianjin; phosgene: industrial grade, wanhua chemical group, inc; dichloromethane: analytically pure, purchased from chemical reagents ltd of miuiou, department of Tianjin; p-tert-butylphenol: analytically pure, purchased from chemical research institute of Shandong province; triethylamine: analytically pure, purchased from chemical reagents ltd of miuiou, department of Tianjin; 2, 3-dichloroquinoxaline, 2, 3-dichloro-6-methylquinoxaline, 2,3, 6-trichloroquinoxaline: purchased from Hubei Jusheng technologies, Inc.; o-diphenylamine: purchased from Hubei Jusheng technologies, Inc.; hydroquinone; purchased from national drug agents; ethylene carbonate: purchased from Baishu chemical technology, Inc.
Synthesis of the dihydroxy Compound of formula (IV)
In a 5L reaction vessel with a nitrogen inlet and mechanical stirring, 440.44g of hydroquinone, 56.11g of potassium hydroxide and 2.2L of dimethyl sulfoxide were charged, 199.04g of 2, 3-dichloroquinoxaline were slowly added to the reaction system under nitrogen atmosphere at 70 ℃ and the reaction was continued for 6 hours after the completion of the addition. After the reaction is finished, pouring the reaction solution into excessive water, filtering, collecting precipitate to obtain a crude product, and recrystallizing the crude product with ethanol to obtain a final product, wherein the yield is about 92%.
Synthesis of dihydroxy Compound represented by the following formula (VII)
440.44g of hydroquinone, 56.11g of potassium hydroxide and 2.2L of dimethyl sulfoxide were charged into a mechanically stirred 5L reaction flask with a nitrogen inlet, 213.06g of 2, 3-dichloro-6-methylquinoxaline were slowly added to the reaction system under nitrogen at 70 ℃ and the reaction was continued for 8 hours after the completion of the addition. After the reaction is finished, the reaction solution is poured into excessive water, the precipitate is collected by filtration to obtain a crude product, and the crude product is recrystallized by ethanol to obtain a final product, wherein the yield is about 85%.
Synthesis of dihydroxy Compound represented by the following formula (VIII)
440.44g of hydroquinone, 56.11g of potassium hydroxide and 2.2L of dimethyl sulfoxide are added into a mechanically stirred 5L reaction bottle with a nitrogen inlet, 233.48g of 2,3, 6-trichloroquinoxaline are slowly added into the reaction system under nitrogen atmosphere at 70 ℃, and the reaction is continued for 8 hours after the addition is finished. After the reaction is finished, the reaction solution is poured into excessive water, the precipitate is collected by filtration to obtain a crude product, and the crude product is recrystallized by ethanol to obtain a final product, wherein the yield is about 83%.
Synthesis of dihydroxy Compound represented by the following formula (IX)
Into a 5L reaction flask having a nitrogen inlet and mechanically stirred, 248.28g of ethylene glycol, 56.11g of potassium hydroxide, 2.2L of dimethyl sulfoxide were charged, 199.04g of 2, 3-dichloroquinoxaline was slowly added to the reaction system under a nitrogen atmosphere at 70 ℃ and the reaction was continued for 6 hours after the completion of the addition. After the reaction is finished, pouring the reaction solution into excessive water, filtering, collecting precipitate to obtain a crude product, and recrystallizing with ethanol to obtain a final product with the yield of about 95%.
Comparative example 1
Synthesis of homopolycarbonate from bisphenol A
456.6 bisphenol A, 3500g water and 200g sodium hydroxide are respectively added into a mixing tank, and are mixed and dissolved to form a water phase; in a separate mixing tank 217.6g of liquid phosgene and 3000g of methylene chloride were added and mixed to form an organic phase. Adding the water phase and the organic phase into a photochemical reactor formed by a static mixer at the flow rates of 41.5g/min and 32.2g/min respectively, reacting at normal temperature and normal pressure, standing for 1.5min, then feeding into a coupling reactor formed by the static mixer, simultaneously adding a dichloromethane solution with the concentration of 5 wt% of p-tert-butylphenol, a dichloromethane solution with the concentration of 1.5 wt% of triethylamine and a sodium hydroxide solution with the concentration of 30 wt% into the reactor, wherein the flow rates of the three solutions are 1.8g/min, 1.3g/min and 2.2g/min respectively, and reacting for 15 min. Separating and purifying the reaction product and removing the organic solvent to obtain the bisphenol A polycarbonate resin.
Comparative example 2
Synthesis of copolycarbonates prepared from 50 mol% bisphenol A and 50 mol% bisphenol fluorene
Respectively adding 228.3g of bisphenol A, 350.4g of bisphenol fluorene, 3500g of water, 200g of sodium hydroxide and 1000g of dichloromethane into a mixing tank, and mixing and dissolving to form a mixed solution of an aqueous phase and dichloromethane; in a separate mixing tank 217.6g of liquid phosgene and 2000g of methylene chloride were added and mixed to form an organic phase. Adding the solutions of the two mixing tanks into a photochemical reactor composed of a static mixer at the flow rates of 52.8g/min and 22.2g/min respectively, reacting at normal temperature and normal pressure, standing for 1.5min, then feeding into a coupling reactor composed of the static mixer, simultaneously adding a dichloromethane solution with the concentration of 5 wt% of p-tert-butylphenol, a dichloromethane solution with the concentration of 1.5 wt% of triethylamine and a sodium hydroxide solution with the concentration of 30 wt% into the reactor, wherein the flow rates of the three solutions are 1.8g/min, 1.3g/min and 2.2g/min respectively, and reacting for 15 min. The reaction product is separated, purified and the organic solvent is removed to obtain the bisphenol fluorene copolycarbonate.
Example 1
Synthesis of a homopolycarbonate prepared by formula (IV)
692.7g of bisphenol with the structure of formula (IV), 3500g of water and 200g of sodium hydroxide are respectively added into a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. In a separate mixing tank 217.6g of liquid phosgene and 3000g of methylene chloride were added and mixed to form an organic phase. Adding the water phase and the organic phase into a photochemical reactor formed by a static mixer at the flow rates of 43.9g/min and 32.2g/min respectively, standing for 1.5min, then feeding into a coupling reactor formed by the static mixer, reacting at normal temperature and normal pressure, simultaneously adding a dichloromethane solution with the concentration of 5 wt% of p-tert-butylphenol, a dichloromethane solution with the concentration of 1.5 wt% of triethylamine and a sodium hydroxide solution with the concentration of 30 wt% into the reactor, wherein the flow rates of the three solutions are 1.8g/min, 1.3g/min and 2.2g/min respectively, and reacting for 15 min. And (3) separating the reaction crude product to remove a water phase, washing, separating and purifying an organic phase, and removing a dichloromethane solvent to obtain colorless polycarbonate resin with the number of A-1.
Example 2
Synthesis of a copolycarbonate prepared from 90 mol% of a bisphenol of formula (IV) and 10 mol% of bisphenol A
623.4g of bisphenol with a structure of formula (IV), 45.6g of bisphenol A, 3500g of water and 200g of sodium hydroxide are respectively added into a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. The aqueous phase was fed at a rate of 43.7g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was designated as No. A-2.
Example 3
Synthesis of a copolycarbonate prepared from 80 mol% of a bisphenol of formula (IV) and 20 mol% of bisphenol A
554.1g of bisphenol with the structure of formula (IV), 91.3g of bisphenol A, 3500g of water and 200g of sodium hydroxide are respectively added into a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. The aqueous phase was fed at a rate of 43.4g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was designated as No. A-3.
Example 4
Synthesis of a copolycarbonate prepared from 50 mol% of a bisphenol of formula (IV) and 50 mol% of bisphenol A
346.3g of bisphenol with a structure of formula (III), 228.3g of bisphenol A, 3500g of water and 200g of sodium hydroxide are respectively added into a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. The aqueous phase was fed at a rate of 42.7g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was designated as No. A-4.
Example 5
Synthesis of a copolycarbonate prepared from 10 mol% of a bisphenol of formula (IV) and 90 mol% of bisphenol A
69.27g of bisphenol having the structure of formula (IV), 410.9g of bisphenol A, 3500g of water and 200g of sodium hydroxide were added to a mixing tank, and mixed and dissolved to form a sodium phenolate aqueous phase. The aqueous phase was fed at a rate of 41.8g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was designated as No. A-5.
Example 6
Synthesis of a copolycarbonate prepared from 5 mol% of a bisphenol of formula (IV) and 95 mol% of bisphenol A
34.6g of bisphenol having a structure of formula (IV), 433.7g of bisphenol A, 3500g of water and 200g of sodium hydroxide were added to a mixing tank, and mixed and dissolved to form a sodium phenolate aqueous phase. The aqueous phase was fed at a rate of 41.7g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was designated as No. A-6.
Example 7
Synthesis of a copolycarbonate prepared from 50 mol% bisphenol of formula (VII) and 50 mol% bisphenol A
360.4g of bisphenol having a structure of formula (VII), 228.3g of bisphenol A, 3500g of water and 200g of sodium hydroxide were added to a mixing tank, and mixed and dissolved to form a sodium phenolate aqueous phase. The aqueous phase was fed at a rate of 42.9g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was numbered B.
Example 8
Synthesis of a copolycarbonate prepared from 50 mol% of a bisphenol of formula (VIII) and 50 mol% of bisphenol A
380.8g of bisphenol with the structure of formula (VIII), 228.3g of bisphenol A, 3500g of water and 200g of sodium hydroxide are respectively added into a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. The aqueous phase was fed at a rate of 43.1g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained was numbered C.
Example 9
Synthesis of a copolycarbonate prepared from 50 mol% of a bisphenol of formula (XI) and 50 mol% of bisphenol A
250.3g of bisphenol having the structure of formula (XI), 228.3g of bisphenol A, 3500g of water and 200g of sodium hydroxide were added to a mixing tank, and mixed and dissolved to form a sodium phenolate brine phase. The aqueous phase was fed at a rate of 43.1g/min into the photochemical reactor constituted by a static mixer, and the other steps were the same as in example 1. The colorless polycarbonate resin obtained is numbered D.
Example 10
Polycarbonate blends prepared from 50 wt% of A-1 polycarbonate and 50 wt% of bisphenol A type homopolycarbonate
50 parts by weight of the polycarbonate of type A-1 obtained in example 1 and 50 parts by weight of the bisphenol A homopolycarbonate obtained in comparative example 1 were mixed by means of a high-speed mixer for about 10 min. The mixture was then extruded using a 25mm co-rotating twin screw extruder with a barrel operating temperature of 240 ℃ and 280 ℃. The colorless polycarbonate resin obtained is numbered E.
The heat resistance of polycarbonate resins was evaluated by means of the glass transition temperature Tg, measured by dynamic differential thermal analysis (DSC) according to ASTM E1356.
The weathering resistance of the resins was evaluated by the UV ageing test, in which the resins were injection-molded into 9cm by 9cm square pieces using an injection-molding machine and aged in a UV lamp ageing oven under test conditions according to the standard ASTM D4329. After aging for 500h, the delta YI of the sample wafer before and after the test was measured.
The chemical resistance was evaluated by the environmental stress failure resistance method, with the test procedure according to standard ISO 22088-3, the resin samples were soaked with solvents 10% NaOH, 10% acetic acid, ethanol, 5% ammonia for 24h, and then the samples were subjected to the flexural strength test, according to ISO 178.
The refractive index n was measured by an Abbe refractometer using a 589nm wavelength polycarbonate film obtained by dissolving a polycarbonate resin in methylene chloride to prepare a 15 wt% solution, followed by spin coating, and the thickness was 100. mu.m.
The results of the characterization of the Tg, the YI after aging and the refractive index n for the comparative examples and the examples are shown in Table 1 below, and the results of the environmental stress crack resistance evaluation for the comparative examples and the examples for different solvents are shown in Table 2 below.
TABLE 1 comparison of Heat resistance, weather resistance and refractive index
Tg(℃) | ΔYI | n(589nm) | |
Comparative example 1 | 147 | 15.2 | 1.586 |
Comparative example 2 | 201 | 19.3 | 1.618 |
A-1 | 261 | 8.8 | 1.702 |
A-2 | 250 | 9.4 | 1.690 |
A-3 | 239 | 10.1 | 1.678 |
A-4 | 206 | 12.2 | 1.644 |
A-5 | 160 | 14.6 | 1.597 |
A-6 | 153 | 14.9 | 1.592 |
B | 213 | 10.9 | 1.641 |
C | 215 | 11.2 | 1.649 |
D | 208 | 9.3 | 1.626 |
E | 205 | 10.6 | 1.645 |
Table 2 bending strength test results after solvent immersion
The evaluation results show that the copolycarbonates of the present invention have improved heat resistance, aging resistance, chemical resistance, and high refractive index, relative to conventional bisphenol A type carbonates. The copolycarbonates of the invention (e.g., A-4, B, C, D) also have more outstanding properties relative to bisphenol fluorene copolycarbonate at the same 50 mol% comonomer content.
Claims (11)
1. A polycarbonate comprising a structural unit derived from a dihydroxy compound represented by formula (I),
wherein R is1Is H, halogen or C1-C6 alkyl, R2Is C1-C4 alkylene, C6-C10 arylene or C7-C12 arylene alkyl;
the compound with the structure of the general formula (I) is obtained by reacting quinoxaline derivatives shown in a formula (II) with excessive dihydroxy compounds shown in a formula (III),
HO-R2-OH (III)
wherein R is1Is H, halogen or C1-C6 alkyl, R2Is C1-C4 alkylene, C6-C10 arylene or C7-C12 arylene alkyl, and X represents halogen.
3. the polycarbonate of claim 1, further comprising structural units derived from hydroquinone, resorcinol, and at least one dihydroxy aromatic compound represented by formula (V),
wherein R is3Independently at each occurrenceIs a halogen atom, an alkyl group of C1-C6 or an alkoxy group of C1-C6; n and m independently represent an integer of 0 to 4; w represents a single bond, an ether bond, a thioether bond, a carbonyl group, a sulfone group, a sulfoxide group, an alkylene group having from C1 to C8, an alkylidene group having from C2 to C8, a cycloalkylene group having from C5 to C15, or a cycloalkylidene group having from C5 to C15.
4. The polycarbonate of claim 3, wherein the dihydroxy aromatic compound comprises hydroquinone, resorcinol, 4 ' -dihydroxybiphenyl, 4 ' -dihydroxydiphenyl ether, 4 ' -dihydroxydiphenyl sulfide, 1-bis (4-hydroxyphenyl) phenylethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclododecane, a diol, 9, 9-bis (4-hydroxyphenyl) fluorene.
5. The polycarbonate according to any one of claims 1 to 4, wherein the dihydroxy compound represented by formula (I) is contained in an amount of 1 to 100 mol% based on the total dihydroxy compounds constituting the polycarbonate.
6. The polycarbonate according to claim 5, wherein the dihydroxy compound represented by formula (I) is contained in an amount of 5 to 90 mol% based on the total dihydroxy compounds constituting the polycarbonate.
7. The polycarbonate according to claim 6, wherein the dihydroxy compound represented by formula (I) is contained in an amount of 10 to 80 mol% based on the total dihydroxy compounds constituting the polycarbonate.
8. A method for preparing the polycarbonate of any of claims 1-7, wherein the method is an interfacial phosgene method or a melt transesterification method.
9. A polycarbonate composition, characterized in that it comprises, in addition to the polycarbonate according to any of claims 1 to 7, from 0.01 to 10% by weight, based on the total mass of the polycarbonate composition, of one or more of the following components: mold release agents, flow aids, heat stabilizers, antioxidants, UV absorbers, IR absorbers, flame retardants, antistatic agents, dyes and pigments, fillers.
10. A blend of a polycarbonate according to any of claims 1 to 7 or obtained by the preparation process according to claim 8 with a thermoplastic polymer.
11. Use of the polycarbonate according to any of claims 1 to 7 or the polycarbonate composition according to claim 9 or the blend according to claim 10 for the preparation of transparent or translucent or opaque shaped parts, extrudates, laminates.
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US5374701A (en) * | 1991-11-04 | 1994-12-20 | Hay; Allan S. | Diarylacetylenes, enamines and acetylenic polymers and their production |
CN101318940A (en) * | 2007-06-07 | 2008-12-10 | 富士施乐株式会社 | Quinoxaline-containing compounds and polymers thereof |
CN102159617A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors |
CN105085891A (en) * | 2015-08-21 | 2015-11-25 | 万华化学集团股份有限公司 | High-refractive-index copolycarbonate |
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US5374701A (en) * | 1991-11-04 | 1994-12-20 | Hay; Allan S. | Diarylacetylenes, enamines and acetylenic polymers and their production |
CN101318940A (en) * | 2007-06-07 | 2008-12-10 | 富士施乐株式会社 | Quinoxaline-containing compounds and polymers thereof |
CN102159617A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors |
CN105085891A (en) * | 2015-08-21 | 2015-11-25 | 万华化学集团股份有限公司 | High-refractive-index copolycarbonate |
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