CN114502615B - 生产改性聚碳酸酯的方法 - Google Patents
生产改性聚碳酸酯的方法 Download PDFInfo
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- CN114502615B CN114502615B CN202080068295.XA CN202080068295A CN114502615B CN 114502615 B CN114502615 B CN 114502615B CN 202080068295 A CN202080068295 A CN 202080068295A CN 114502615 B CN114502615 B CN 114502615B
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- polycarbonate
- amide
- modified
- melt
- modified polycarbonate
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 128
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 128
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 34
- 150000003140 primary amides Chemical class 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 30
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 150000001408 amides Chemical class 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- MHKBSCHWKVCLJL-WUKNDPDISA-N (e)-octadec-2-enamide Chemical compound CCCCCCCCCCCCCCC\C=C\C(N)=O MHKBSCHWKVCLJL-WUKNDPDISA-N 0.000 claims description 2
- MPQPXMRGNQJXGO-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxamide Chemical compound NC(=O)CC(O)(C(N)=O)CC(N)=O MPQPXMRGNQJXGO-UHFFFAOYSA-N 0.000 claims description 2
- RQTJHIZCVWJGDM-UHFFFAOYSA-N 8-methylnonanamide Chemical compound CC(C)CCCCCCC(N)=O RQTJHIZCVWJGDM-UHFFFAOYSA-N 0.000 claims description 2
- SFIHQZFZMWZOJV-UHFFFAOYSA-N Linolsaeure-amid Natural products CCCCCC=CCC=CCCCCCCCC(N)=O SFIHQZFZMWZOJV-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- BNBSCAZCQDLUDU-DOFZRALJSA-N arachidonoyl amine Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(N)=O BNBSCAZCQDLUDU-DOFZRALJSA-N 0.000 claims description 2
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical group CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 claims description 2
- 229940116335 lauramide Drugs 0.000 claims description 2
- SFIHQZFZMWZOJV-HZJYTTRNSA-N linoleamide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(N)=O SFIHQZFZMWZOJV-HZJYTTRNSA-N 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012170 montan wax Substances 0.000 claims description 2
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 claims description 2
- LTHCSWBWNVGEFE-UHFFFAOYSA-N octanamide Chemical compound CCCCCCCC(N)=O LTHCSWBWNVGEFE-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- YRPQTVNCCVPGFA-FPLPWBNLSA-N palmitoleamide Chemical compound CCCCCC\C=C/CCCCCCCC(N)=O YRPQTVNCCVPGFA-FPLPWBNLSA-N 0.000 claims description 2
- 229940037312 stearamide Drugs 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- WTHCRRXOPUNKAA-UHFFFAOYSA-N 16-methylheptadecan-1-amine Chemical compound CC(C)CCCCCCCCCCCCCCCN WTHCRRXOPUNKAA-UHFFFAOYSA-N 0.000 claims 1
- 238000010924 continuous production Methods 0.000 claims 1
- LUOABWGXXKLFGZ-UHFFFAOYSA-N hexacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LUOABWGXXKLFGZ-UHFFFAOYSA-N 0.000 claims 1
- UKISQBBASUVXLD-UHFFFAOYSA-N triacontanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O UKISQBBASUVXLD-UHFFFAOYSA-N 0.000 claims 1
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- -1 bisphenol A Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000011067 equilibration Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 150000003334 secondary amides Chemical class 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- KZVIUXKOLXVBPC-UHFFFAOYSA-N 16-methylheptadecanamide Chemical compound CC(C)CCCCCCCCCCCCCCC(N)=O KZVIUXKOLXVBPC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RWIUTHWKQHRQNP-ZDVGBALWSA-N (9e,12e)-n-(1-phenylethyl)octadeca-9,12-dienamide Chemical compound CCCCC\C=C\C\C=C\CCCCCCCC(=O)NC(C)C1=CC=CC=C1 RWIUTHWKQHRQNP-ZDVGBALWSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- YQSKUMSTUNJCFM-UHFFFAOYSA-N P(O)O.P(O)O Chemical group P(O)O.P(O)O YQSKUMSTUNJCFM-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 241001313099 Pieris napi Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- KZRJKMZQXATVEB-UHFFFAOYSA-N chlorophosphinous acid Chemical compound OPCl KZRJKMZQXATVEB-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229950008446 melinamide Drugs 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- ZNGANTDNNWGOIO-UHFFFAOYSA-N tris(hydroxymethyl) phosphite Chemical compound OCOP(OCO)OCO ZNGANTDNNWGOIO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—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
- C08G64/12—Aromatic polycarbonates not containing aliphatic unsaturation 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
- C08G64/42—Chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
- B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/20—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
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Abstract
本发明涉及生产改性聚碳酸酯的方法,所述方法包括在温度至少230℃下在熔融混合设备中使聚碳酸酯与至少一种伯酰胺反应至少0.5分钟。
Description
技术领域
本发明涉及生产改性聚碳酸酯的方法。
背景技术
聚碳酸酯在各种应用中是公知的材料,且由聚碳酸酯树脂制造产品的典型方法是注塑。已知注塑包括将熔融的树脂材料物流注入模具,然后冷却树脂。在树脂充分冷却后,则可以打开模具并移出产品。聚碳酸酯的缺点是它有可能会粘附在模具表面上,因此需要一定的力将注塑产品从模具中移出。
为了缓解该问题,通常已知使用脱模剂如季戊四醇四硬脂酸酯(PETS)、单硬脂酸甘油酯(GMS)或三硬脂酸甘油酯(GTS)。
US 2013/0216801公开了包含聚碳酸酯的热塑性组合物,其在300℃和1.2kg负载下按ASTM D1238定义的熔体流动指数为10-50g/10min,所述热塑性组合物包括聚碳酸酯,所述热塑性组合物包含20-80mol%指定的亚环己基桥连的碳酸酯单元和80-20mol%指定的其它碳酸酯单元。基质上有一层硬涂层为制品提供至少5H的铅笔硬度,所述硬度按JISK5400应用0.75kgf的负载测量。该文献公开了某些流动促进剂(包括芥酸酰胺),其可以与其中公开的聚碳酸酯一起应用。该参考文献没有教导或建议在某些条件下芥酸酰胺(或任何其它伯酰胺)可以用来使聚碳酸酯改性,即与聚碳酸酯反应,以使其具有特定的有利性能。
聚碳酸酯的另一个缺点是在有利于良好冲击性能的较高分子量情况下熔体相当粘稠。为了缓解这种高粘度,可以在较高温度下处理聚碳酸酯,这反过来可能会导致树脂劣化,可能造成颜色性能下降。
发明内容
因此,本发明的目的是提供具有良好的流动性能、冲击性能和脱模性能的聚碳酸酯。
在这种意义下,本发明涉及一种生产改性聚碳酸酯的方法,所述方法包括在温度至少230℃下在熔融混合设备中使聚碳酸酯与至少一种伯酰胺反应至少0.5分钟。
更具体地,本发明涉及一种生产改性聚碳酸酯的方法,所述方法包括在温度至少230℃下在熔融混合设备中使聚碳酸酯与至少一种伯酰胺反应至少0.5分钟,其中所述改性聚碳酸酯按ASTM D1238(300℃,1.2kg)测量的熔体体积速率比聚碳酸酯的熔体体积速率高至少10%。
已经令人惊奇地发现,相比于未改性的相同聚碳酸酯,按这里所公开的方法获得的聚碳酸酯表现出增大的熔体流动速率以及改进的脱模性能和可接受的韧性。
因此,应用本发明至少部分实现了上述目的。
聚碳酸酯
这里公开的方法原则上不限于特定类型的聚碳酸酯。因此,所述聚碳酸酯可以是均聚物或(嵌段)共聚物或者一种或多种均聚物、一种或多种共聚物或一种或多种共聚物和均聚物的混合物。但优选所述聚碳酸酯为芳族聚碳酸酯均聚物,更优选为芳族双酚A聚碳酸酯。
这种聚碳酸酯优选通过使双酚(如双酚A)与碳酸酯源(如光气)或二芳基碳酸酯(如二苯基碳酸酯)反应获得。因此,聚碳酸酯可以应用所谓的界面方法来制备,其中BPA与光气反应,或者通过所谓的熔融或直接酯交换法来制备,其中BPA与二苯基碳酸酯以熔融态反应。这两类聚碳酸酯对本领域熟练技术人员来说是已知的,且在这里也可以称为界面聚碳酸酯和熔融聚碳酸酯。本领域熟练技术人员已知这两类聚碳酸酯的区别在于Fries支链量(其只存在于熔融聚碳酸酯中)和终端羟基含量(其对于界面聚碳酸酯来说通常低得多)。
优选的是由于所述方法的原因,相比于熔融方法,通过界面方法获得的聚碳酸酯通常提供具有更少羟基链终端的聚碳酸酯。少量羟基链终端对于聚碳酸酯的热稳定性和颜色保持性能都有利。尽管如此,本发明中也不排除应用通过熔融方法获得的聚碳酸酯,即熔融聚碳酸酯。在一个实施方案中,聚碳酸酯为通过界面方法获得的至少一种聚碳酸酯和通过熔融方法获得的至少一种聚碳酸酯的混合物。
聚碳酸酯优选被选自如下的单酚封端:苯酚、叔丁基苯酚、对-异丙基苯酚、C1-C16烷基取代的苯酚或它们的任意混合物。对-异丙基苯酚是优选的封端剂。
优选地,聚碳酸酯的重均分子量应用聚碳酸酯标准通过GPC测量为15,000-60,000道尔顿。当聚碳酸酯为聚碳酸酯的混合物时,则这些聚碳酸酯各自的重均分子量均在该范围内。聚碳酸酯的玻璃转化温度(Tg)应用DSC测量为130-220℃。双酚A类聚碳酸酯的Tg通常为约147℃。
优选地,聚碳酸酯或聚碳酸酯混合物按ISO 1133(300℃,1.2kg)测量的熔体体积速率(MVR)为3-35cm3/10min,优选为6-25cm3/10min,更优选为14-21cm3/10min。为了避免疑义,应注意这里指的是按这里公开改性前聚碳酸酯的MVR。
在本发明的上下文中,优选至少部分聚碳酸酯为消费后回收的聚碳酸酯(PCR-PC)。因此,优选所述聚碳酸酯包含至少2wt%、优选至少5wt%、更优选至少10wt%的PCR-PC。在这种PCR-PC和原始聚碳酸酯的掺混物的情况下,所述掺混物可以包含10-90wt%的PCR-PC,如20-80wt%或40-60wt%,基于掺混物重量计。在一个实施方案中,所述掺混物可以包含至多20wt%的PCR-PC,如1-15wt%。
伯酰胺
在本发明方法中用于使聚碳酸酯改性的酰胺是伯酰胺。在这种意义下,本发明人发现仲或叔酰胺不能或在更低程度上提供改进流动性和脱模性能的技术效果。伯酰胺优选具有通式结构R-CO-NH2,其中R为有机基团。基团R可以为直链或支链基团,且可以包含或不包含杂原子。典型的杂原子包括氧、硫、磷和氮。R优选为具有10-50个碳原子的脂族基团。基团R可以包含不饱和键,即相邻碳原子间的双键,但优选基团R为饱和有机基团,优选为饱和的支链或直链脂族基团。因此,伯酰胺优选为具有小于100ppm(mol)、更优选为小于10ppm、最优选小于1ppm碳碳双链不饱和的烷基酰胺。
本发明中应用的伯酰胺的典型实例有丁酰胺、己酰胺、辛酰胺、柠檬酰胺、月桂酰胺、肉豆蔻酰胺、棕榈酰胺、硬脂酰胺、花生四烯酰胺、山嵛酰胺、ignoceramide、蜡酸酰胺(cerotamide)、褐煤蜡酰胺(montanamide)、蜂花酸酰胺(melissamide)、异-癸酰胺、异十八碳酰胺、棕榈油酰胺、油酰胺、十八碳烯酰胺、芥酸酰胺、亚麻酸酰胺、亚油酰胺、鳕油酰胺、gondoamide及前述伯酰胺中两种或更多种的混合物。
伯酰胺优选选自C10-C50直链羧基酰胺。如果酰胺的分子量太高,则酰胺的存在可能在组合物中造成雾度。
沸点高于200℃或甚至300℃的酰胺可能是优选的。
酰胺最优选选自异十八碳酰胺、芥酸酰胺、山嵛酰胺以及至少两种前述伯酰胺的混合物。
改性聚碳酸酯
本发明还涉及通过这里公开的方法获得或可获得的改性聚碳酸酯。虽然本发明人已经发现酰胺与聚碳酸酯反应,但改性后的确切结构尚不清楚。但除了改善熔体流动和脱模性能外,所述方法还生成更多的对-羟基苯酚基团,使极性增加,而产生的化学改性聚合物的邻-羟基酚端基含量变化很少或没有变化。所述方法产生包含邻-和对-羟基酚端基两者的改性聚碳酸酯,其中对-酚端基占主导地位,和酚端基的总量大于80ppm,而在其它情况下大于100ppm。
应用聚碳酸酯标准通过GPC测量,改性聚碳酸酯的重均分子量优选为15,000-60,000道尔顿。
本发明人发现改性聚碳酸酯的熔体体积速率按ASTM D1238(300℃,1.2kg)测量可以比聚碳酸酯的熔体体积速率高至少10%。
本发明人还发现改性聚碳酸酯在300℃下再加热30分钟后,熔体粘度变化小于25%。
改性聚碳酸酯优选具有包括邻-对和对,对-双酚A的酚端基,其中所述对-对BPA的酚端基占主导地位,且总的酚端基大于100ppm。
所述改性聚碳酸酯优选具有一种或多种如下性能:
-至少80%的透射率,
-至多5.0%的雾度,
-至多20的黄度指数,
-至少400J/m的缺口Izod冲击强度,
其中透射率、雾度和黄度指数在3.2mm的注塑板上测量。为了避免疑义,应注意这些性能在刚生产的注塑板上测量,即在任何老化前测量。
所述透射率优选为至少85%,更优选为至少86%。
所述雾度优选为至多2.0%,更优选为至多1.0%。
所述黄度指数优选为至多10,优选为至多5.0,更优选为至多2.0。
所述缺口Izod冲击强度优选为400-800J/m或400-700J/m。
优选的是所述改性聚碳酸酯具有如下一种或多种、优选全部性能:
-至少87%的透射率,
-至多2.0%的雾度,
-至多5、优选至多3的黄度指数,
-400-800J/m的缺口Izod冲击强度,
透射率、雾度和黄度指数在3.2mm的注塑板上测量。同样,为了避免疑义,应注意这些性能在刚生产的注塑板上测量,即在任何老化前测量。
因此,本发明涉及生产具有如下一种或多种、优选全部性能的改性聚碳酸酯的方法:至少80%的透射率、至多5%的雾度、至多20的黄度指数和至少400J/m的缺口Izod冲击强度。
因此和优选地,本发明涉及生产具有如下一种或多种、优选全部性能的改性聚碳酸酯的方法:
-至少87%的透射率,
-至多2.0%的雾度,
-至多5、优选至多3的黄度指数,
-400-800J/m的缺口Izod冲击强度,
其中透射率、雾度和黄度指数在3.2mm的注塑板上测量。同样,为了避免疑义,应注意这些性能在刚生产的注塑板上测量,即在任何老化前测量。
缺口Izod冲击强度按ASTM D256-10在23℃在尺寸为64x13x3.2mm的注塑棒上进行测量。
本发明还涉及一种包含这里所公开的改性聚碳酸酯(即由这里所公开方法获得或可获得的改性聚碳酸酯)的组合物。
除了改性聚碳酸酯外,这种组合物还可以包含一种或多种本领域常用的添加剂,如抗氧化剂、UV稳定剂、红外线阻隔材料、填料、增强剂、抗冲改性剂、阻燃剂、抗滴落剂、热稳定剂、着色剂。
在这里公开的熔融改性方法中,优选使用亚磷酸酯、亚膦酸酯或它们的混合物作为稳定剂。所述稳定剂的量通常为0.01-1.0wt%。优选的含磷稳定剂为亚膦酸酯(phosphonite),其中一个P键直接连接于芳基基团。在US 4,075,163中给出了这类化合物的实例。也可以应用双官能含磷化合物。优选的亚磷酸酯或亚膦酸酯稳定剂选自:烷基取代的三芳基亚磷酸酯、四(2,4-二叔丁基苯基)4,4'-联苯二亚膦酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、三(壬基苯基)亚磷酸酯、双(2,4-二异丙苯)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基苯基-4-甲基季戊四醇)二亚磷酸酯、三苯基亚磷酸酯、三甲酚亚磷酸酯或它们的任意混合物。稳定剂的分子量可以大于或等于300g/mol。在一些实施方案中,分子量大于或等于500g/mol的含磷稳定剂是有用的。
方法
使聚碳酸酯改性以形成改性聚碳酸酯在温度至少230℃下在熔融状态下实施足够时间,以使伯酰胺与聚碳酸酯反应,已经发现所述时间至少为0.5分钟。所述温度可以为250-350℃,优选为270-320℃,反应时间为至少0.5分钟,如0.5-15分钟、0.5-10分钟、0.5-5分钟。所述反应时间可以为1-15、1-10、2-15、2-10分钟。最优条件取决于酰胺的类型、聚碳酸酯的MVR和改性温度等。聚碳酸酯的改性可以通过改性聚碳酸酯的粘度例如熔体体积速率来确认。相比于改性前的聚碳酸酯,改性聚碳酸酯的熔体体积速率更高。
改性期间应用的酰胺量为待改性聚碳酸酯重量的0.05-5.0wt%。所述量优选为0.1-1.0wt%。
固体形式的待改性的聚碳酸酯可以与伯酰胺预先混合,随后将所获得的混合物进料至熔融混合设备,具体为挤出机。替代地,可以以固体形式进料待改性的聚碳酸酯,例如以颗粒或粉末形式进料至挤出机的进料区,并使伯酰胺进料至相同挤出机的所述进料区的下游区域。在另一个替代方案中,将聚碳酸酯以熔融态进料至挤出机,并将伯酰胺一起进料至挤出机或所述挤出机进料区的下游区域。这种特定的实施方案是优选的,特别是对于通过熔融方法获得的聚碳酸酯来说,其中来自最后一个缩聚反应器的熔融物流直接进料至挤出机。通过利用伯胺“在线”处理,避免了聚碳酸酯的附加热循环,这对于产品质量、特别是颜色性能来说是有益的。
为了避免疑义,应注意这里公开的方法不包括应用溶剂,即所述方法是无溶剂方法。
所述方法可以在本领域中已知的聚合物熔融混合设备中实施,所述设备本身包括内部混合器,如Banbury混合器、单螺杆挤出机、同向旋转双螺杆挤出机和反向旋转双螺杆挤出机。
所述方法优选在挤出机如同向旋转双螺杆挤出机中实施。应用挤出机允许连续实施改性,从而提供具有稳定改性水平的聚碳酸酯。
所述方法优选包括应用在250-380℃下以200-1000rpm的螺杆速度操作的双螺杆挤出机。优选应用常压。可以应用真空排气处理添加剂和/或反应物。
在挤出机中实施改性后,优选使改性聚碳酸酯通过模具挤出为至少一股线材,随后将所述至少一股线材冷却为颗粒。然后可以应用所述颗粒进行制品的注塑、挤塑或低塑。
替代地,可以应用所获得的改性聚碳酸酯生产配混物或掺混物,例如聚碳酸酯-丙烯腈-丁二烯-苯乙烯共聚物掺混物(PC/ABS)或聚碳酸酯-聚酯掺混物,如聚碳酸酯与如下一种或多种的掺混物:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯和聚对苯二甲酸环己二亚甲基酯。随后可以应用这些掺混物生产注塑制品。
本发明涉及包含这里所公开的改性聚碳酸酯的制品。这种制品优选为注塑制品。在一个实施方案中,所述制品的壁厚为1.0-10.0mm。
本发明还涉及通式结构为R-CO-NH2的伯酰胺的用途,其中R为具有10-50个碳原子的有机基团,优选为脂族基团,用于在温度至少230℃下在熔融混合设备中使聚碳酸酯改性至少0.5分钟,以提高所述聚碳酸酯的熔体体积速率。
所述改性聚碳酸酯优选具有至少50ppm的酚端基含量。所述酚端基含量优选为80-200ppm。
下面基于如下非限定性实施例进一步描述本发明。
实施例
所有实施例均按如下所讨论的类似方式制备和测试。在油漆搅动器中翻动混合下面所示的实施例组分,随后在30mm的Werner Pfleiderer同向旋转双螺杆挤出机上挤出,所述挤出机带有常压排气混合螺杆,料桶和模头温度为250-300℃且螺杆速度为400rpm。将熔体作为线材挤出,所述线材通过水浴冷却,之后切割成颗粒。
颗粒在125℃下干燥至少2h,之后用于制备试样。
利用在50%RH下平衡至少2天的3.2mm的ASTM部件实施模塑部件测试。
缺口Izod按ASTM D256-10测量。
黄度指数(YI)、透射率(%T)和雾度(%H)按ASTM D1003-03在3.2mm的注塑板上测量,按刚模塑好(即不老化)和在130℃下在空气中老化7天后测量。
Tg按ASTM D3418-03在20℃/min的加热速率下测量。
分子量按ASTM D5296-05应用凝胶渗透色谱法(GPC)测量,聚碳酸酯(PC)应用PC标准,PBT Mw应用聚苯乙烯标准。
熔体粘度按ASTM D1238-13通过以cc/10min表达的熔体体积速率(MVR)测量,所述测量在温度300℃和重量1.2kg且经过6分钟或18分钟的平衡后实施。
按ASTM D4440-15在氮气气氛下在300℃下应用平行板/锥形板夹具流变仪以10弧度/秒的速率运行30分钟,测量粘度与时间的关系,也称作熔体停留或时间扫描。比较测试开始时(6分钟平衡后)和结束时(30分钟平衡后)的粘度,以表示熔融聚合物的相对稳定性。
酚端基含量由NMR确定。羟基端基含量可以例如按US 9,040,651(第13栏,第40-57行)所公开的方法测量。在该方法中,225毫克聚合物与4毫升0.5M具有已知内标浓度的乙酰丙酮铬的氯仿溶液混合。一旦聚合物溶解,则用过量1,2-亚苯基次氯酸化膦(phosphorochloridite)处理所得溶液,并将其立即转移至直径为5或10毫米的核磁共振(NMR)样品管中,并用35°的脉冲宽度、每次扫描32,000或64,000个数据点、1.8秒的延迟和1600-2500次扫描记录31P NMR位移。按下式计算羟基端基的重量ppm(ppm OH):
ppm OH=(标准的重量/标准的分子量)×(总OH/总标准)×17.01×(1/聚合物重量)×(4mL/100mL)×106。
在K.P.Chan,D.S.Argyropoulos,D.M.White,G.W.Yeager和A.S.Hay的“FacileQuantitative Analysis of Hydroxyl End Groups of Poly(2,6-dimethyl-1,4-phenylene oxide)s by 31P NMR Spectroscopy,”Macromolecules,1994,volume 27,pages 6371-6375中描述了测量芳族聚合物的羟基端基含量的类似方法。p-BPA的酚基(OH)端基信号在125.2ppm处,而o-BPA OH的信号在130.8ppm处。
实施例中所应用的材料在下表1中给出。
表1
酰胺1、2和3为伯酰胺。
基于这些材料,制备制备表2所所详细列出的组合物。材料以重量份表示,每种组合物的总量为100wt%。
表2
在表2中:
-Mw_颗粒代表被模塑为部件前颗粒形式的材料的重均分子量。
-Mw_部件代表模塑颗粒成为模塑部件后材料的重均分子量。
-Mw_下降代表由于材料改性和/或模塑造成的分子量下降百分比。
-MVR_6代表经过平衡时间6分钟后的熔体体积速率。
-MVR_18代表经过平衡时间18分钟后的熔体体积速率。
-ΔMVR代表MVR_18相对于MVR_6的差(以%表示)。
-NI代表在23℃下的缺口冲击强度(J/m)。
表2中的实施例表明用伯酰胺改性的聚碳酸酯的MVR有明显改进。同时其光学性能以及冲击性能维持在可接受水平。对于所有样品,分子量基本维持不变。
由表3可以看出,与PC对照(Ref)或用PETS改性的PC(CE1)和用仲酰胺改性的PC(CE2和CE3)相比,实施例1-4中化学改性的聚碳酸酯表现出酚端基增加。已经发现聚碳酸酯具有邻和对-酚端基两者。本发明方法的化学改性产生超过100ppm的对-酚链终端,而如果存在的话,只有很少的邻-酚含量变化。
表3
实施例 | Ref | CE1 | CE2 | CE3 | E1 | E2 | E3 | E4 |
PPM p-BPA-OH | 69 | 71 | 79 | 78 | 117 | 167 | 103 | 113 |
PPM o-BPA-OH | 74 | 83 | 74 | 76 | 68 | 75 | 81 | 84 |
该数据表明聚碳酸酯实际上已被本发明的方法改性。
表4给出了各实施例的熔体稳定性,其中用伯酰胺改性的聚碳酸酯表现出至少80%的初始粘度保留率。左列表示时间(秒),而数据代表在温度300℃下如上所述测量的粘度。
表4
实施利用伯酰胺AM_2(山嵛酰胺)的进一步实验,其中应用不同浓度的酰胺。过程设置与上述实施例1-4和CE1-CE3相同。
表5给出了这些附加实验的结果。
表5
实施例 | Ref | E5 | E6 | E7 | E8 |
PC | 99.92 | ||||
Am_2 | 0.05 | 0.10 | 0.15 | 0.30 | |
Stab. | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
Mw_颗粒 | 21520 | 21550 | 21440 | 21443 | 21419 |
Mn_颗粒 | 9402 | 9781 | 9759 | 9715 | 9656 |
MVR_6 | 27.1 | 31.5 | 33.1 | 37 | 44.6 |
由表5可知,相对少量的伯酰胺已经导致熔体体积速率的提高。
脱模性能
在杯形工具上注塑实施例2、3和4中用伯酰胺改性的PC树脂,以测量使聚碳酸酯部件从钢制工具中脱除所需的顶出力。使部件灵活脱除的较低压力是优选的。现有技术的对比技术应用非反应性脱模剂来克服PC树脂的固有粘性。这种非反应性的脱模剂通常为烷基酯如PETS(对比例1)。
杯形工具是用于将部件模塑成壁厚为3mm的圆筒状杯子的模具。
应用杯形工具由在125℃下干燥4小时的材料模塑杯子。在注塑设备中,螺杆温度为270-300℃,和循环时间为35秒,注射速率为每秒1.2英寸(3.05cm),注射压力为750psi(51.7bar),保持压力为500psi(34.5bar),模具温度为85℃和模具为0.24英寸(0.61cm)。顶出压力值用压力传感器测量(psi),该值是弃掉前5次测量值后20次测量的平均值。
表6
顶出力[psi] | |
CE1 | 360 |
CE3 | 340 |
E2 | 250 |
E3 | 230 |
E4 | 280 |
表6表明,对于用伯酰胺改性的聚碳酸酯来说,释放压力显著降低。相比于基于常用的PETS脱模剂的CE1,仲酰胺EBS(CE3)几乎没有改进。
Claims (17)
1.一种生产改性聚碳酸酯的方法,所述方法包括在温度至少230℃下在熔融混合设备中使聚碳酸酯与至少一种伯酰胺反应至少0.5分钟,其中所述改性聚碳酸酯按ASTM D1238在300℃和1.2kg测量的熔体体积速率比聚碳酸酯的熔体体积速率高至少10%,其中所述聚碳酸酯为双酚A聚碳酸酯,其由包括使双酚A与光气反应的界面方法、或由包括使双酚A与碳酸二苯酯以熔融态反应的直接酯交换方法获得。
2.权利要求1所述的方法,其中所述改性聚碳酸酯具有如下一种或多种:至少87%的透射率、至多2%的雾度、至多5的黄度指数和至少400J/m的缺口Izod冲击强度,其中黄度指数、透射率和雾度按ASTM D1003-03在3.2mm的注塑板上测量,按刚模塑好和在130℃下在空气中老化7天后测量,和缺口Izod冲击强度按ASTM D256-10在23℃在尺寸为64x 13x 3.2mm的注塑棒上进行测量。
3.权利要求1-2任一项所述的方法,其中所述改性聚碳酸酯应用聚碳酸酯标准通过GPC测量的重均分子量为15,000-60,000道尔顿,和酚端基的含量为至少80ppm。
4.权利要求1-2任一项所述的方法,其中所述伯酰胺的通式结构为R-CO-NH2,其中R为具有10-50个碳原子的有机基团。
5.权利要求4所述的方法,其中R为具有10-50个碳原子的饱和的有机基团。
6.权利要求4所述的方法,其中R为脂族基团。
7.权利要求1-2任一项所述的方法,其中所述伯酰胺选自丁酰胺、己酰胺、辛酰胺、柠檬酰胺、月桂酰胺、肉豆蔻酰胺、棕榈酰胺、硬脂酰胺、花生四烯酰胺、山嵛酰胺、蜡酸酰胺、褐煤蜡酰胺、蜂花酸酰胺、异癸酰胺、异十八碳酰胺、棕榈油酰胺、油酰胺、十八碳烯酰胺、芥酸酰胺、亚麻酸酰胺、亚油酰胺、鳕油酰胺及前述伯酰胺中两种或更多种的混合物。
8.权利要求1-2任一项所述的方法,其中所述聚碳酸酯包含消费后回收的聚碳酸酯或由消费后回收的聚碳酸酯组成。
9.权利要求1-2任一项所述的方法,其中所述方法为连续方法,其中熔融混合设备为挤出机,和其中所述挤出机在250-380℃的温度和200-1000rpm的螺杆速度下操作。
10.权利要求9所述的方法,其中所述挤出机为双螺杆挤出机。
11.权利要求1-2任一项所述的方法,还包括通过模具将改性聚碳酸酯挤出为至少一股线材,随后冷却所述至少一股线材为颗粒。
12.通过权利要求1-11任一项所述的方法获得的改性聚碳酸酯。
13.包含权利要求12所述的改性聚碳酸酯的组合物。
14.包含权利要求12所述的改性聚碳酸酯或权利要求13所述的组合物的制品。
15.权利要求14所述的制品,其中所述制品为注塑制品。
16.通式结构为R-CO-NH2的伯酰胺的用途,其中R为具有10-50个碳原子的有机基团,用于在至少230℃的温度下在熔融混合设备中使聚碳酸酯改性至少0.5分钟,以提高所述聚碳酸酯的熔体体积速率。
17.权利要求16所述的用途,其中R为具有10-50个碳原子的脂族基团。
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