TW201827490A - 共聚碳酸酯和包含彼之組成物 - Google Patents
共聚碳酸酯和包含彼之組成物 Download PDFInfo
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- TW201827490A TW201827490A TW106135421A TW106135421A TW201827490A TW 201827490 A TW201827490 A TW 201827490A TW 106135421 A TW106135421 A TW 106135421A TW 106135421 A TW106135421 A TW 106135421A TW 201827490 A TW201827490 A TW 201827490A
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- Prior art keywords
- chemical formula
- copolycarbonate
- repeating unit
- unit represented
- alkyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims description 94
- 239000004417 polycarbonate Substances 0.000 claims description 28
- 229920000515 polycarbonate Polymers 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 125000000466 oxiranyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000006647 (C3-C15) cycloalkyl group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- -1 aromatic diol Chemical class 0.000 description 44
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 19
- 239000004205 dimethyl polysiloxane Substances 0.000 description 19
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 19
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 19
- 239000002243 precursor Substances 0.000 description 16
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 13
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 13
- 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 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229920005668 polycarbonate resin Polymers 0.000 description 6
- 239000004431 polycarbonate resin Substances 0.000 description 6
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 125000006681 (C2-C10) alkylene group Chemical group 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- GRNVJCVESFLAJP-UHFFFAOYSA-N 2,3,5,6-tetramethyl-1,4-dioxane Chemical compound CC1OC(C)C(C)OC1C GRNVJCVESFLAJP-UHFFFAOYSA-N 0.000 description 2
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 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
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HREXIBFZDJHFCF-UHFFFAOYSA-N 2,6-dibromo-4-propylphenol Chemical compound CCCC1=CC(Br)=C(O)C(Br)=C1 HREXIBFZDJHFCF-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- IEMXKEMFCFILAA-UHFFFAOYSA-N 2-docosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O IEMXKEMFCFILAA-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- QEMHBAGGYKJNSS-UHFFFAOYSA-N 2-icosylphenol Chemical compound CCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1O QEMHBAGGYKJNSS-UHFFFAOYSA-N 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- 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
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- LNNIPFBETXOKIA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(O)C=C1 LNNIPFBETXOKIA-UHFFFAOYSA-N 0.000 description 1
- GGVPQYSKQVREFR-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)hydrazinyl]phenol Chemical compound C1=CC(O)=CC=C1NNC1=CC=C(O)C=C1 GGVPQYSKQVREFR-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 241001134446 Niveas Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- RWYWPJMTQVQCGK-UHFFFAOYSA-N OC1=CC=C(C(=O)OCCC(=C)C)C=C1 Chemical compound OC1=CC=C(C(=O)OCCC(=C)C)C=C1 RWYWPJMTQVQCGK-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- RFDGKPHLJKJNIZ-UHFFFAOYSA-N [Br].C(=O)(Cl)Cl Chemical compound [Br].C(=O)(Cl)Cl RFDGKPHLJKJNIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 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
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
-
- 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
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
-
- 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
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本發明關於具有改善之流動性並同時於室溫和低溫下維持優異之耐衝擊強度之共聚碳酸酯和包括該共聚碳酸酯之組成物。
Description
本發明關於具有改善之流動性並同時於室溫和低溫下維持優異之耐衝擊強度之共聚碳酸酯和包括該共聚碳酸酯之組成物。
聚碳酸酯樹脂係藉由芳香族二醇(諸如雙酚A)與碳酸酯前驅物(諸如光氣)之縮合聚合反應製備且具有優異之耐衝擊強度、尺寸安定性、耐熱性及透明度。因此,該聚碳酸酯樹脂可應用於廣泛之用途,諸如作為電氣和電子產品、汽車零件、建築材料及光學元件之外部材料。 近來,為應用該聚碳酸酯樹脂於多種不同之領域,業已進行許多研究以藉由使2或多種彼此具有不同結構之芳香族二醇化合物共聚合並於聚碳酸酯之主鏈上導入具有不同結構之單元以得到所欲之物理性質。 特定地,業已進行於聚碳酸酯之主鏈上導入聚矽氧烷結構的研究,但是大多數該等技術具有下述缺點:生產成本高和當低溫下耐衝擊強度或耐化學性(特別是耐衝擊強度)增強時流動性惡化。 因此,本案發明人為解決上述之缺點業已研究具有改善之流動性並同時於室溫和低溫下維持優異之耐衝擊強度之共聚碳酸酯樹脂且業已發現於聚碳酸酯之主鏈上導入特定之聚矽氧烷結構和癸二醯基結構的如下所述之共聚碳酸酯能滿足上述條件,因而完成本發明。
本發明之目標係提供具有改善之流動性並同時於室溫和低溫下維持優異之耐衝擊強度之共聚碳酸酯。 本發明之另一目標係提供包括該共聚碳酸酯之組成物。 為達到上述目標,本發明提供包括化學式1所示之重複單元、化學式2所示之重複單元、化學式3所示之重複單元及化學式4所示之重複單元之共聚碳酸酯:於化學式1中, R1
至R4
各別獨立為氫、C1-10
烷基、C1-10
烷氧基或鹵素;且 Z1
係未經取代或經苯基取代之C1-10
伸烷基、未經取代或經C1-10
烷基取代之C3-15
伸環烷基、O、S、SO、SO2
或CO;於化學式2中, X1
各別獨立為C1-10
伸烷基; R5
各別獨立為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10
烷氧基、或C6-20
芳基取代之C1-15
烷基;鹵素;C1-10
烷氧基;烯丙基;C1-10鹵烷基
;或C6-20
芳基;且 n係10至200之整數;於化學式3中, X2
各別獨立為C1-10
伸烷基; Y1
各別獨立為氫、C1-6
烷基、鹵素、羥基、C1-6
烷氧基或C6-20
芳基; R6
各別獨立為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10
烷氧基、或C6-20
芳基取代之C1-15
烷基;鹵素;C1-10
烷氧基;烯丙基;C1-10鹵烷基
;或C6-20
芳基;且 m係10至200之整數;於化學式4中, Z2
係未經取代或經苯基取代之C1-10
伸烷基、未經取代或經C1-10
烷基取代之C3-15
伸環烷基、O、S、SO、SO2
或CO;且 l係1至10之整數。 聚碳酸酯樹脂係藉由芳香族二醇(諸如雙酚A)與碳酸酯前驅物(諸如光氣)之縮合聚合反應製備且本身具有優異之機械性質,但是取決於應用領域必須同時滿足多種不同之物理性質。特定地,藉由改變該聚碳酸酯樹脂之結構可改善該聚碳酸酯樹脂之特定物理性質。然而,於大多數情況下,當改善一種物理性質時,其他性質惡化。 於是,除了慣用之聚碳酸酯結構含有之該化學式1之重複單元外,本發明導入該化學式2、3及4之重複單元以改善流動性並同時於室溫和低溫下維持優異之耐衝擊強度。藉由導入該化學式2至4之重複單元,在未使其他物理性質惡化之情況下,可改善該聚碳酸酯之多種不同的物理性質。 隨後,將更為詳細地描述本發明之特定實施態樣的共聚碳酸酯和包括該共聚碳酸酯之組成物。 化學式1之重複單元 該化學式1所示之重複單元形成本發明之共聚碳酸酯樹脂的基本結構且係藉由芳香族二醇化合物與碳酸酯前驅物反應所生成。 於化學式1中,較佳地,R1
至R4
各別獨立為氫、甲基、氯或溴。 再者,Z1
較佳地為未經取代或經苯基取代之直鏈或支鏈C1-10
伸烷基且更佳地為伸甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯基乙烷-1,1-二基或二苯基伸甲基。再者,較佳地,Z1
係環己烷-1,1-二基、O、S、SO、SO2
或CO。 較佳地,該化學式1所示之重複單元可源自一或多種芳香族二醇化合物,該等芳香族二醇化合物選自雙(4-羥基苯基)甲烷、雙(4-羥基苯基)醚、雙(4-羥基苯基)碸、雙(4-羥基苯基)亞碸、硫化雙(4-羥基苯基)、雙(4-羥基苯基)酮、1,1-雙(4-羥基苯基)乙烷、雙酚A、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、2,2-雙(4-羥基-3,5-二溴苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-溴苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、雙(4-羥基苯基)二苯基甲烷及α,ω-雙[3-(o-羥基苯基)丙基]聚二甲基矽氧烷。 本文使用之“源自芳香族二醇化合物”表示芳香族二醇化合物之羥基與碳酸酯前驅物反應以生成該化學式1所示之重複單元。 例如,當為芳香族二醇化合物之雙酚A與為碳酸酯前驅物之三光氣聚合時,該化學式1所示之重複單元係如下化學式1-1所示:。 本文使用之碳酸酯前驅物可包括選自碳酸二甲酯、碳酸二乙酯、碳酸二丁酯、碳酸二環己酯、碳酸二苯酯、碳酸二甲苯酯、碳酸雙(氯苯酯)、碳酸二(間甲苯酚酯)、碳酸二萘酯、碳酸雙(二苯酯)、光氣、三光氣、雙光氣、溴光氣及二鹵甲酸酯中一或多者。較佳地,可使用三光氣或光氣。 化學式2之重複單元和化學式3之重複單元 該化學式2和3之重複單元具有聚有機矽氧烷結構且可被導入至共聚碳酸酯以改善多種不同之物理性質。 於化學式2中,X1
各別獨立較佳地為C2-10
伸烷基,更佳地C2-4
伸烷基且最佳地丙烷-1,3-二基。 亦較佳地,R5
各別獨立為氫、甲基、乙基、丙基、3-苯基丙基、2-苯基丙基、3-(環氧乙烷基甲氧基)丙基、氟、氯、溴、碘、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基或萘基。此外,R5
各別獨立較佳地為C1-10
烷基,更佳地C1-6
烷基,更佳地 C1-3
烷基且最佳地甲基。 較佳地,n係10或大於10、15或大於15、20或大於20、25或大於25、30或大於30、31或大於31、或32或大於32且係50或小於50、45或小於45、40或小於40、39或小於39、38或小於38、或37或小於37之整數。 於化學式3中,X2
各別獨立較佳地為C2-10
伸烷基,更佳地C2-6
伸烷基且最佳地伸異丁基。 再者,較佳地,Y1
係氫。 再者,較佳地,R6
各別獨立為氫、甲基、乙基、丙基、3-苯基丙基、2-苯基丙基、3-(環氧乙烷基甲氧基)丙基、氟、氯、溴、碘、甲氧基、乙氧基、丙氧基、烯丙基、2,2,2-三氟乙基、3,3,3-三氟丙基、苯基或萘基。再者,R6
各別獨立較佳地為C1-10
烷基,更佳地C1-6
烷基,更佳地C1-3
烷基且最佳地甲基。 較佳地,m係30或大於30、35或大於35、40或大於40、45或大於45、46或大於46、47或大於47、或48或大於48且係70或小於70、65或小於65、60或小於60、55或小於55、54或小於54、53或小於53、或52或小於52之整數。 該化學式2所示之重複單元和該化學式3所示之重複單元分別衍生自如下化學式2-1所示之矽氧烷化合物和如下化學式3-1所示之矽氧烷化合物:於化學式2-1中, X1
、R5
及n係如同前述定義者。於化學式3-1中, X2
、Y1
、R6
及m係如同前述定義者。 本文使用之“源自矽氧烷化合物”表示各別矽氧烷化合物之羥基與碳酸酯前驅物反應以生成該化學式2所示之重複單元和該化學式3所示之重複單元。再者,可用於生成該化學式2和3所示之重複單元的該等碳酸酯前驅物係如同上述可用於生成該化學式1所示之重複單元的該碳酸酯前驅物。 較佳地,該化學式2所示之重複單元係如下化學式2-2所示:於化學式2-2中,R5
和n係如同前述定義者。較佳地,R5
係甲基。 較佳地,該化學式3所示之重複單元係如下化學式3-2所示:於化學式3-2中,R6
和m係如同前述定義者。較佳地,R6
係甲基。 化學式4之重複單元 該化學式4所示之重複單元具有癸二醯基結構且可被導入至共聚碳酸酯以改善流動性。 於化學式4中,Z2
較佳地為未經取代或經苯基取代之直鏈或支鏈C1-10
伸烷基且更佳地為伸甲基、乙烷-1,1-二基、丙烷-2,2-二基、丁烷-2,2-二基、1-苯基乙烷-1,1-二基或二苯基伸甲基。再者,較佳地Z2
係環己烷-1,1-二基、O、S、SO、SO2
或CO。 較佳地,該化學式4所示之重複單元係如下化學式4-1所示:。 再者,藉由使包括如下化學式4-2所示之化合物、芳香族二醇化合物及碳酸酯前驅物之組成物反應以生成該化學式4所示之重複單元:於化學式4-2中, R'係氫、OH、C1-10
烷基或鹵素且l係如同前述定義者。 再者,該芳香族二醇化合物和該碳酸酯前驅物係如同上述可用於生成該化學式1所示之重複單元的該芳香族二醇化合物和該碳酸酯前驅物。 共聚碳酸酯 本發明之共聚碳酸酯包括該化學式1所示之重複單元、該化學式2所示之重複單元、該化學式3所示之重複單元及該化學式4所示之重複單元。較佳地,該共聚碳酸酯係無規共聚物。 此外,藉由控制每個重複單元之含量可同時改善該共聚碳酸酯之多種不同的性質。具有聚有機矽氧烷結構的該化學式2所示之重複單元和該化學式3所示之重複單元的重量比可為1:99至99:1。較佳地,該重量比係3:97至97:3且更佳地5:95至95:5。上述重複單元的重量比對應矽氧烷化合物(例如該化學式2-1所示之矽氧烷化合物和該化學式3-1所示之矽氧烷化合物)之重量比。 此外,該化學式1所示之重複單元與該化學式2和3所示之重複單元(即化學式1:(化學式2和3))之重量比可為1:0.001至1:0.2且更佳地1:0.01至1:0.1。上述重複單元之重量比對應用於生成該化學式1所示之重複單元的芳香族二醇化合物與用於生成該化學式2和3所示之重複單元的矽氧烷化合物之重量比。 此外,該化學式1所示之重複單元與該化學式4所示之重複單元的重量比可為1:99至99:1。較佳地,該重量比係2:98至98:2且更佳地3:97至97:3。上述重複單元的重量比對應該芳香族二醇化合物與該化學式4-2所示之化合物的重量比。 本發明之共聚碳酸酯可藉由包括下述步驟之方法製備:聚合該芳香族二醇化合物、該碳酸酯前驅物、該化學式2-1和3-1所示之2類矽氧烷化合物及該化學式4-2所示之化合物。 該芳香族二醇化合物、該碳酸酯前驅物及該矽氧烷化合物係如同前述描述者。 此外,較佳地藉由界面聚合方法實施該聚合反應。對此,有益的是可於大氣壓和低溫下實施該聚合反應且可易於控制分子量。 反應溫度較佳地係介於0℃至40℃且反應時間較佳地係介於10分鐘至5小時。此外,pH較佳地維持於9或大於9或於反應期間維持於11或大於11。 可用於該聚合反應之溶劑未特別受限,只要該溶劑係通常可用於聚碳酸酯之聚合反應的溶劑。例如,可使用鹵化烴,諸如二氯甲烷或氯苯。 再者,較佳地於酸結合劑之存在下進行該聚合反應且該酸結合劑可為鹼金屬氫氧化物(諸如氫氧化鈉或氫氧化鉀)或胺化合物(諸如吡啶)。 此外,可於分子量調節劑之存在下進行該聚合反應以控制該共聚碳酸酯之分子量。作為上述之分子量調節劑,可使用C1-20
烷基酚且特定地可使用對三級丁基酚、對枯基酚、癸基酚、十二烷基酚、十四烷基酚、十六烷基酚、十八烷基酚、二十烷基酚、二十二烷基酚或三十烷基酚。於起始該聚合反應之前、起始該聚合反應之期間或起始該聚合反應之後,可加入該分子量調節劑。以100重量份之該芳香族二醇化合物為基準計,該分子量調節劑之含量係例如0.01重量份或大於0.01重量份、0.1重量份或大於0.1重量份、或1重量份或大於1重量份且係例如10重量份或小於10重量份、6重量份或小於6重量份、或5重量份或小於5重量份且較佳地係0.1至6重量份。於此範圍內,可得到所要求之分子量。 此外,可進一步使用反應加速劑以加速該聚合反應,該反應加速劑係例如三級胺化合物(諸如三乙胺、溴化四(正丁基)銨及溴化四(正丁基)鏻)、四級銨化合物或四級鏻化合物。 此外,該共聚碳酸酯之重量平均分子量(g/莫耳)為1,000至100,000,較佳地30,000至70,000且更佳地40,000至60,000。 較佳地,依據ASTM D256(1/8吋;缺口衝擊試驗(Notched Izod))於23℃下測量的本發明之共聚碳酸酯的室溫下耐衝擊強度為800至1100 J/m。更佳地,該室溫下耐衝擊強度為820或大於820 J/m、或850或大於850 J/m。此外,無特定上限,因為室溫下較高之耐衝擊強度可被認為係較佳的。然而,該上限可為例如1050或低於1050、或1000或低於1000。 較佳地,依據ASTM D256(1/8吋;缺口衝擊試驗(Notched Izod))於-30℃下測量的本發明之共聚碳酸酯的低溫下耐衝擊強度為550至1000 J/m。更佳地,該低溫下耐衝擊強度為560或大於560 J/m、或570或大於570 J/m。此外,無特定上限,因為低溫下較高之耐衝擊強度可被認為係較佳的。然而,該上限可為例如950或低於950、或900或低於900。 較佳地,依據ASTM D1238 (300℃;1.2 kg條件)測量的本發明之共聚碳酸酯的熔融指數為7至30 g/10分鐘。更佳地,該熔融指數(g/10分鐘)係8或大於8、8.5或大於8.5、或9或大於9且係18或小於18、15或小於15、或13或小於13。 較佳地,依據迷你夾具測量方法測量的本發明之共聚碳酸酯的耐化學性為18至50分鐘。更佳地,該耐化學性(分鐘)係19或大於19、或20或大於20且係40或小於40、30或小於30、或28或小於28。 聚碳酸酯組成物 此外,本發明提供一種聚碳酸酯組成物,其包括上述之共聚碳酸酯和聚碳酸酯。 該共聚碳酸酯可單獨使用但可與所需之聚碳酸酯一起使用以控制該共聚碳酸酯之物理性質。 上述聚碳酸酯與本發明之共聚碳酸酯之區別在於聚矽氧烷結構並未導入至該聚碳酸酯之主鏈。 較佳地,上述聚碳酸酯包括如下化學式5所示之重複單元:於化學式5中, R'1
至R'4
各別獨立為氫、C1-10
烷基、C1-10
烷氧基或鹵素;且 Z1
'係未經取代或經苯基取代之C1-10
伸烷基、未經取代或經C1-10
烷基取代之C3-15
伸環烷基、O、S、SO、SO2
或CO。 此外,上述聚碳酸酯之重量平均分子量較佳地為1,000至100,000 g/莫耳且更佳地為20,000至60,000 g/莫耳。 藉由使芳香族二醇化合物與碳酸酯前驅物反應以生成該化學式5所示之重複單元。此處所使用之芳香族二醇化合物和碳酸酯前驅物係如同先前製備該化學式1所示之重複單元所描述者。 較佳地,該化學式5中R'1
至R'4
和Z1
'係分別如同先前該化學式1中R1
至R4
和Z1
所描述者。 再者,較佳地,該化學式5所示之重複單元係如下化學式5-1所示:。 此外,該聚碳酸酯組成物可另包括選自抗氧化劑、熱安定劑、光安定劑、塑化劑、抗靜電劑、成核劑、阻燃劑、潤滑劑、衝擊增強劑、螢光增白劑、紫外線吸收劑、顏料及染料中一或多者。 此外,本發明提供一種物件,其包括上述之聚碳酸酯組成物。較佳地,該物件係注塑成型物件。 製備該物件之方法可包括下述步驟:使用混合機混合本發明之聚碳酸酯組成物和如必要之添加劑;使用擠壓機使該混合物經擠出成型以生成小丸;乾燥該小丸;及,隨後使用射出成型機注射該乾燥之小丸。 如上述,本發明之共聚碳酸酯於該聚碳酸酯之主鏈上可導入除了該聚矽氧烷結構外之癸二醯基結構,因而改善流動性並同時維持該聚碳酸酯之優異的物理性質。
參照下述之實施例,將更詳細地說明本發明。然而,下述實施例僅係用於說明目的且本發明不受限於下述之實施例。 製備實施例1:AP-PDMS (n=34)令八甲基環四矽氧烷(47.60 g,160毫莫耳)與四甲基二矽氧烷(2.40 g,17.8毫莫耳)混合。隨後將該混合物和相對於100重量份八甲基環四矽氧烷之1重量份酸性黏土(DC-A3)一起置入燒瓶(3 L)並於60℃下經反應4小時。經反應完全後,令反應產物經乙酸乙酯稀釋並經寅氏鹽迅速過濾。經1
H NMR證實,所製備之未經改質的聚有機矽氧烷之重複單元(n)係34。 對所生成之終端未經改質的聚有機矽氧烷,加入2-烯丙基酚(4.81 g, 35.9毫莫耳)和Karstedt氏鉑觸媒(0.01 g, 50 ppm)並於90℃下經反應3小時。經反應完全後,於120℃和壓力1托之條件下,藉由蒸發除去未反應之矽氧烷。所製備之終端經改質的聚有機矽氧烷稱為AP-PDMS (n=34)。AP-PDMS係淡黃色油,並經使用Varian 500 MHz之1
H NMR證實,重複單元(n)係34且無需進一步純化。 製備實施例2:MBHB-PDMS (m=58)令八甲基環四矽氧烷(47.60 g,160毫莫耳)與四甲基二矽氧烷(1.5 g,11毫莫耳)混合。隨後將該混合物和相對於100重量份八甲基環四矽氧烷之1重量份酸性黏土(DC-A3)一起置入燒瓶(3 L)並於60℃下經反應4小時。經反應完全後,令反應產物經乙酸乙酯稀釋並經寅氏鹽迅速過濾。經1
H NMR證實,所製備之終端未經改質的聚有機矽氧烷之重複單元(m)係58。 對所生成之終端未經改質的聚有機矽氧烷,加入4-羥基苯甲酸3-甲基丁-3-烯酯(6.13 g,29.7毫莫耳)和Karstedt氏鉑觸媒(0.01 g,50 ppm)並於90℃下經反應3小時。經反應完全後,於120℃和壓力1托之條件下,藉由蒸發除去未反應之矽氧烷。所製備之終端經改質的聚有機矽氧烷稱為MBHB-PDMS (m=58)。MBHB-PDMS係淡黃色油,並經使用Varian 500 MHz之1
H NMR證實,重複單元(m)係58且無需進一步純化。 實施例1. 3.5% PDMS (95:5)與0.5% SBC共聚合 對配備氮氣淨化裝置和冷凝器並經使用循環裝置能維持於室溫下之主反應器(2 L)注入H2
O (620 g)、雙酚A (BPA;116.47 g)、製備實施例1製備之AP PDMS (5.5 g)、製備實施例2製備之MBHB PDMS (0.29 g)、癸二醯氯(0.93 g)、NaOH (102.5 g)及MeCl2
(200 ml)並隨後經攪拌數分鐘。 於中止氮氣清洗後,對圓底燒瓶(1 L)加入三光氣(62 g)和MeCl2
(120 g)以使三光氣溶解。隨後將溶解之三光氣溶液緩慢注入其中該BPA溶液溶解之主反應器。經注入完成後,加入PTBP (2.12 g)並隨後經攪拌約10分鐘。經攪拌完成後,加入40重量% NaOH水溶液(97 g)並進一步加入作為偶合劑之TEA (1.16 g)。此時,反應pH維持於11至13。經反應溶液靜置一段時間使反應充分後,加入HCl使pH下降至3至4以使反應中止。經停止攪拌後,聚合物層與水層分離並隨後除去該水層,且令殘餘物再次重複地經純水沖洗,該沖洗重複3至5次。 經沖洗完成後,僅有該聚合物層被萃取且藉由使用非溶劑(諸如甲醇、水或類似者)進行再沉澱以得到聚合物結晶。 據此,所製備之共聚碳酸酯的重量平均分子量為55,000 g/莫耳。 實施例2. 3.5% PDMS (95:5)與1.5% SBC共聚合 如同實施例1之方法,除了癸二醯氯之用量為2.92 g,製備共聚碳酸酯。 實施例3. 3.5% PDMS (90:10)與0.5% SBC共聚合 如同實施例1之方法,除了該AP PDMS之用量為5.24 g且該MBHB PDMS之用量為0.58 g,製備共聚碳酸酯。 比較實施例1. 7% PDMS (95:5)與NPC混合 令共聚碳酸酯(其係經如同實施例1之方法製備,除了該AP PDMS之用量為5.24 g,該MBHB PDMS之用量為0.58 g且未使用癸二醯氯)與聚碳酸酯(淨PC;重量平均分子量為55,000 g/莫耳;其係經如同實施例1之方法製備,除了未使用AP PDMS、MBHB PDMS及癸二醯氯)以重量比1:1混合並經擠壓。 比較實施例2. 3.5% PDMS (95:5) 如同實施例1之方法,除了未使用癸二醯氯,製備共聚碳酸酯。 實驗實施例 藉由下述方法測量每個性質。結果示於下述表1。 1) 重量平均分子量(Mw):藉由GPC並使用Agilent 1200系列之PS標準測量。 2) 室溫和低溫下耐衝擊強度:依據ASTM D256 (1/8吋;缺口衝擊試驗(Notched Izod))於室溫和-30℃(低溫)下測量。 3) 流動性(熔融指數;MI):依據ASTM D1238 (300℃;1.2 kg條件)測量。 4) 耐化學性(夾具測試):將13 mm×64 mm×1/8吋樣品緊密黏著迷你夾具(58.5R),將5 mm×13 mm棉布置於中央且隨後放置妮維雅防曬(Nivea Sun)噴霧(0.5 ml)。測量於黏著樣品出現裂痕之時間。參照表1,可證實:與比較實施例1之共聚碳酸酯(其中僅導入聚矽氧烷結構至聚碳酸酯之主鏈)和比較實施例2之共聚碳酸酯(其中比較實施例1之共聚碳酸酯與一般聚碳酸酯混合)相比較,實施例1至3製備之共聚碳酸酯(其中導入特定之聚矽氧烷結構和癸二醯基結構至聚碳酸酯之主鏈)不僅具有相同程度之室溫和低溫下耐衝擊強度且亦具有優異之流動性和流度。
Claims (12)
- 一種共聚碳酸酯,其包含: 化學式1所示之重複單元; 化學式2所示之重複單元; 化學式3所示之重複單元;及 化學式4所示之重複單元;於化學式1中, R1 至R4 各別獨立為氫、C1-10 烷基、C1-10 烷氧基或鹵素;且 Z1 係未經取代或經苯基取代之C1-10 伸烷基、未經取代或經C1-10 烷基取代之C3-15 伸環烷基、O、S、SO、SO2 或CO;於化學式2中, X1 各別獨立為C1-10 伸烷基; R5 各別獨立為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10 烷氧基、或C6-20 芳基取代之C1-15 烷基;鹵素;C1-10 烷氧基;烯丙基;C1-10鹵烷基 ;或C6-20 芳基;且 n係10至200之整數;於化學式3中, X2 各別獨立為C1-10 伸烷基; Y1 各別獨立為氫、C1-6 烷基、鹵素、羥基、C1-6 烷氧基或C6-20 芳基; R6 各別獨立為氫;未經取代或經環氧乙烷基、經環氧乙烷基取代之C1-10 烷氧基、或C6-20 芳基取代之C1-15 烷基;鹵素;C1-10 烷氧基;烯丙基;C1-10鹵烷基 ;或C6-20 芳基;且 m係10至200之整數;於化學式4中, Z2 係未經取代或經苯基取代之C1-10 伸烷基、未經取代或經C1-10 烷基取代之C3-15 伸環烷基、O、S、SO、SO2 或CO;且 l係1至10之整數。
- 如請求項1之共聚碳酸酯,其中該化學式1所示之重複單元係如下化學式1-1所示:。
- 如請求項1之共聚碳酸酯,其中該化學式2所示之重複單元係如下化學式2-2所示:。
- 如請求項3之共聚碳酸酯,其中R5 係甲基。
- 如請求項1之共聚碳酸酯,其中n係10至50之整數。
- 如請求項1之共聚碳酸酯,其中該化學式3所示之重複單元係如下化學式3-2所示:。
- 如請求項6之共聚碳酸酯,其中R6 係甲基。
- 如請求項1之共聚碳酸酯,其中m係30至70之整數。
- 如請求項1之共聚碳酸酯,其中該化學式4所示之重複單元係如下化學式4-2所示:。
- 如請求項1之共聚碳酸酯,其中重量平均分子量係1,000至100,000 g/莫耳。
- 一種聚碳酸酯組成物,其包含如請求項1至10中任一項之共聚碳酸酯和聚碳酸酯。
- 如請求項11之聚碳酸酯組成物,其中聚矽氧烷結構未導入該聚碳酸酯之主鏈。
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PL3406650T3 (pl) | 2021-12-13 |
KR20180043685A (ko) | 2018-04-30 |
CN108884220A (zh) | 2018-11-23 |
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JP2019515118A (ja) | 2019-06-06 |
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