CN112812287B - A kind of method that ionic liquid catalysis prepares polycarbonate - Google Patents
A kind of method that ionic liquid catalysis prepares polycarbonate Download PDFInfo
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- CN112812287B CN112812287B CN202110003421.XA CN202110003421A CN112812287B CN 112812287 B CN112812287 B CN 112812287B CN 202110003421 A CN202110003421 A CN 202110003421A CN 112812287 B CN112812287 B CN 112812287B
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- molecular weight
- fluorene
- polycarbonate
- ionic liquid
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 87
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 87
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 150000001408 amides Chemical class 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 150000005690 diesters Chemical class 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 38
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 31
- 238000005809 transesterification reaction Methods 0.000 claims description 31
- -1 butyl trihexyl phosphorus Chemical compound 0.000 claims description 25
- 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 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 12
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- CIFFBTOJCKSRJY-UHFFFAOYSA-N (cis)-3a,4,7,7a-Tetrahydro-1H-isoindole-1,3(2H)-dione Natural products C1C=CCC2C(=O)NC(=O)C21 CIFFBTOJCKSRJY-UHFFFAOYSA-N 0.000 claims description 7
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229960002317 succinimide Drugs 0.000 claims description 5
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 5
- HBTONAMIPDVQRI-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-phenylphenyl]fluoren-9-yl]-2-phenylphenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 HBTONAMIPDVQRI-UHFFFAOYSA-N 0.000 claims description 4
- NJCVPQRHRKYSAZ-UHFFFAOYSA-N 3-(4-Hydroxyphenyl)-1-propanol Chemical compound OCCCC1=CC=C(O)C=C1 NJCVPQRHRKYSAZ-UHFFFAOYSA-N 0.000 claims description 4
- WLDMPODMCFGWAA-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione Chemical compound C1CCCC2C(=O)NC(=O)C21 WLDMPODMCFGWAA-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 4
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 4
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 4
- FNIPRNMPSXNBDI-UHFFFAOYSA-N 3-azaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCCCC1 FNIPRNMPSXNBDI-UHFFFAOYSA-N 0.000 claims description 3
- FCEJCPKDDWSUIU-UHFFFAOYSA-N C(C)[P](CCCC)(CCCC)CCCC Chemical compound C(C)[P](CCCC)(CCCC)CCCC FCEJCPKDDWSUIU-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- HLSUQUJDDMLNMX-UHFFFAOYSA-N 1-(2-octadec-9-enoxyethoxy)octadec-9-ene Chemical class CCCCCCCCC=CCCCCCCCCOCCOCCCCCCCCC=CCCCCCCCC HLSUQUJDDMLNMX-UHFFFAOYSA-N 0.000 claims description 2
- BJWYRLOGOZMCPV-UHFFFAOYSA-N 1-[5-[9-[6-(2-hydroxypropoxy)naphthalen-1-yl]fluoren-9-yl]naphthalen-2-yl]oxypropan-2-ol Chemical compound CC(COC1=CC2=C(C=C1)C(=CC=C2)C3(C4=CC=CC=C4C5=CC=CC=C53)C6=CC=CC7=C6C=CC(=C7)OCC(C)O)O BJWYRLOGOZMCPV-UHFFFAOYSA-N 0.000 claims description 2
- GZZLQUBMUXEOBE-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diol Chemical compound OCCC(C)CC(C)(C)CO GZZLQUBMUXEOBE-UHFFFAOYSA-N 0.000 claims description 2
- QDPWYNRXOWBPMD-UHFFFAOYSA-N 2-[2-[5-[9-[5-[2-(2-hydroxyethoxy)ethoxy]naphthalen-1-yl]fluoren-9-yl]naphthalen-1-yl]oxyethoxy]ethanol Chemical compound OCCOCCOC1=C2C=CC=C(C2=CC=C1)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC=CC2=C(C=CC=C12)OCCOCCO QDPWYNRXOWBPMD-UHFFFAOYSA-N 0.000 claims description 2
- YBHWVDKCKDWQBX-UHFFFAOYSA-N 2-[2-cyclohexyl-4-[9-[3-cyclohexyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound OCCOC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C2CCCCC2)C=C1C1CCCCC1 YBHWVDKCKDWQBX-UHFFFAOYSA-N 0.000 claims description 2
- CUPZWXCTZHAVPP-UHFFFAOYSA-N 2-[2-tert-butyl-4-[9-[3-tert-butyl-4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=C(OCCO)C(C(C)(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(OCCO)=CC=2)C(C)(C)C)=C1 CUPZWXCTZHAVPP-UHFFFAOYSA-N 0.000 claims description 2
- JTLKXEMTIVAKJG-UHFFFAOYSA-N 2-[2-tert-butyl-4-[9-[5-tert-butyl-4-(2-hydroxyethoxy)-2-methylphenyl]fluoren-9-yl]-5-methylphenoxy]ethanol Chemical compound CC1=CC(OCCO)=C(C(C)(C)C)C=C1C1(C=2C(=CC(OCCO)=C(C=2)C(C)(C)C)C)C2=CC=CC=C2C2=CC=CC=C21 JTLKXEMTIVAKJG-UHFFFAOYSA-N 0.000 claims description 2
- LBZZJNPUANNABV-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)phenyl]ethanol Chemical compound OCCC1=CC=C(CCO)C=C1 LBZZJNPUANNABV-UHFFFAOYSA-N 0.000 claims description 2
- IRTFFZWZLVOXMG-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluoren-9-yl]-2,6-dimethylphenoxy]ethanol Chemical compound CC1=C(OCCO)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(OCCO)=C(C)C=2)=C1 IRTFFZWZLVOXMG-UHFFFAOYSA-N 0.000 claims description 2
- QRCCWWMVEGTUOR-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-(2-methylpropyl)phenyl]fluoren-9-yl]-2-(2-methylpropyl)phenoxy]ethanol Chemical compound C1=C(OCCO)C(CC(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CC(C)C)C(OCCO)=CC=2)=C1 QRCCWWMVEGTUOR-UHFFFAOYSA-N 0.000 claims description 2
- LUXQHIIWBDDUDE-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)-3-methylphenyl]fluoren-9-yl]-2-methylphenoxy]ethanol Chemical compound C1=C(OCCO)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(OCCO)=CC=2)=C1 LUXQHIIWBDDUDE-UHFFFAOYSA-N 0.000 claims description 2
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 claims description 2
- SWTUHYYCCASQOR-UHFFFAOYSA-N 2-[5-[9-[5-(2-hydroxyethoxy)naphthalen-1-yl]fluoren-9-yl]naphthalen-1-yl]oxyethanol Chemical compound OCCOC1=C2C=CC=C(C2=CC=C1)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC=CC2=C(C=CC=C12)OCCO SWTUHYYCCASQOR-UHFFFAOYSA-N 0.000 claims description 2
- AJKXDPSHWRTFOZ-UHFFFAOYSA-N 2-ethylhexane-1,6-diol Chemical compound CCC(CO)CCCCO AJKXDPSHWRTFOZ-UHFFFAOYSA-N 0.000 claims description 2
- LYZMKCWNBRTLTJ-UHFFFAOYSA-N 2-methylcyclohexane-1,4-diol Chemical compound CC1CC(O)CCC1O LYZMKCWNBRTLTJ-UHFFFAOYSA-N 0.000 claims description 2
- OBNBMKQOGZKSIM-UHFFFAOYSA-N 3-[4-[9-[4-(3-hydroxy-2,2-dimethylpropoxy)phenyl]fluoren-9-yl]phenoxy]-2,2-dimethylpropan-1-ol Chemical compound C1=CC(OCC(C)(CO)C)=CC=C1C1(C=2C=CC(OCC(C)(C)CO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 OBNBMKQOGZKSIM-UHFFFAOYSA-N 0.000 claims description 2
- URFNSYWAGGETFK-UHFFFAOYSA-N 4,4'-Dihydroxybibenzyl Chemical compound C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 2
- UABRZRLUXFHBDT-UHFFFAOYSA-N 5-[9-(5-hydroxynaphthalen-1-yl)fluoren-9-yl]naphthalen-1-ol Chemical compound OC1=C2C=CC=C(C2=CC=C1)C1(C2=CC=CC=C2C=2C=CC=CC1=2)C1=CC=CC2=C(C=CC=C12)O UABRZRLUXFHBDT-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- XZKVNMAFEWZICM-UHFFFAOYSA-N C(CCCCC)[P](CCCCCCCCCCCCCC)(CCCCCC)CCCCCC Chemical compound C(CCCCC)[P](CCCCCCCCCCCCCC)(CCCCCC)CCCCCC XZKVNMAFEWZICM-UHFFFAOYSA-N 0.000 claims description 2
- DSNWTXHQGMGXLR-UHFFFAOYSA-N CC(COC1=C(C2=CC=CC=C2C=C1)C3=C(C=CC4=CC=CC=C43)OCC(C)O)O Chemical group CC(COC1=C(C2=CC=CC=C2C=C1)C3=C(C=CC4=CC=CC=C43)OCC(C)O)O DSNWTXHQGMGXLR-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 2
- RABVYVVNRHVXPJ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-adamantyl]methanol Chemical compound C1C(C2)CC3CC1(CO)CC2(CO)C3 RABVYVVNRHVXPJ-UHFFFAOYSA-N 0.000 claims description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- RREXWZAEZVTJBF-UHFFFAOYSA-N 2-[2-(2-hydroxy-5-methylphenyl)propan-2-yl]-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C=2C(=CC=C(C)C=2)O)=C1 RREXWZAEZVTJBF-UHFFFAOYSA-N 0.000 claims 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 claims 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000003440 toxic substance Substances 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 98
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 30
- 229960002479 isosorbide Drugs 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000011987 methylation Effects 0.000 description 9
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- 238000005886 esterification reaction Methods 0.000 description 8
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- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 7
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- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 4
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000000178 monomer Substances 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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Abstract
Description
技术领域technical field
本发明属于聚合物制备技术领域，涉及一种离子液体催化制备聚碳酸酯的方法。The invention belongs to the technical field of polymer preparation, and relates to a method for preparing polycarbonate by catalyzing an ionic liquid.
背景技术Background technique
聚碳酸酯(PC)是一种分子链中含有碳酸酯基的高性能聚合物，由于其结构上的特殊性，使其具有良好的透明性、优异的尺寸稳定性和突出的抗冲击性，被广泛用于光学元件、电子电器、汽车零部件、建筑建材、航空航天等领域，是五大工程塑料中需求增速最快的热塑性工程塑料。但是，目前通常使用的聚碳酸酯不仅需使用石油化工产品双酚A和剧毒化学品光气来制备，而且由于其生产原料双酚A具有雌激素效应和慢性毒效应，限制了其在食品包装和医疗器械等领域的应用。此外，随着石油资源紧缺的问题日渐严峻和环境的日益恶化，源自短期可再生生物资源的聚合物的研发引起了人们的极大兴趣。因此，发展一种绿色可持续的聚碳酸酯制备方法是该领域研究的热点。Polycarbonate (PC) is a high-performance polymer containing carbonate groups in its molecular chain. Due to its special structure, it has good transparency, excellent dimensional stability and outstanding impact resistance. It is widely used in optical components, electronic appliances, auto parts, building materials, aerospace and other fields, and is the thermoplastic engineering plastic with the fastest growing demand among the five major engineering plastics. However, currently commonly used polycarbonate not only needs to be prepared by using petrochemical product bisphenol A and highly toxic chemical phosgene, but also because its production raw material bisphenol A has estrogen effect and chronic toxic effect, which limits its application in food. Applications in areas such as packaging and medical devices. In addition, with the increasing shortage of petroleum resources and the deteriorating environment, the development of polymers derived from short-term renewable biological resources has attracted great interest. Therefore, the development of a green and sustainable polycarbonate preparation method is a research hotspot in this field.
作为最丰富的生物原料之一，糖类可以通过多种方法得到制备高分子聚合物所需的生物基单体。1,4:3,6-二缩水己六醇是由糖类脱水制得，具有两个相邻的呋喃环，这种刚性结构赋予聚合物材料所需的热稳定性；此外，其手性结构使其有望合成具有特殊选择性的高分子；同时，它的无毒特性使其应用于食品包装和医学设备成为可能。因此，1,4:3,6-二缩水己六醇被认为是替代传统石油化工原料绿色制备聚碳酸酯的最有潜力的生物基单体。文献报道得1,4:3,6-二缩水己六醇(共)聚碳酸酯的研究大部分采用与碳酸二苯酯直接反应(Green Chemistry,2019,21,3891-3901；ACS Sustainable Chemistry&Engineering,2018,6,2684-2693；Polymer,2017,116,153-159)。虽然该方法获得了高分子量的聚碳酸酯，但所使用得碳酸二苯酯的纯度较高，价格昂贵，且反应的副产物苯酚须在高温高真空条件下进行分离，增加了能耗。另外，目前报道的用于制备1,4:3,6-二缩水己六醇(共)聚碳酸酯的催化剂大部分是金属催化剂，比如甲醇钠(Polymer,2019,179,1-6)、金属乙酰丙酮化合物(CN 102746504A)、金属氢氧化物(Industrial&Engineering Chemistry Research,2018,57,4824-4831)、金属碳酸盐(CN 104031249A)等。但是这些催化剂具有一定毒性，不仅可能造成环境污染，而且还残留于合成的聚碳酸酯产品中，限制了产品在婴儿用品、医用器材和食品包装等方面的应用。As one of the most abundant biological raw materials, sugars can be obtained by various methods to obtain bio-based monomers for the preparation of high molecular weight polymers. 1,4:3,6-Dihexanol is prepared by the dehydration of sugars and has two adjacent furan rings. This rigid structure endows the polymer material with the required thermal stability; in addition, its chirality The structure makes it possible to synthesize polymers with special selectivity; at the same time, its non-toxic properties make it possible to apply it to food packaging and medical equipment. Therefore, 1,4:3,6-dihexanol is considered to be the most potential bio-based monomer to replace traditional petrochemical raw materials for the green production of polycarbonate. Most of the researches on 1,4:3,6-dihexanol (co)polycarbonate reported in the literature use direct reaction with diphenyl carbonate (Green Chemistry, 2019, 21, 3891-3901; ACS Sustainable Chemistry & Engineering, 2018, 6, 2684-2693; Polymer, 2017, 116, 153-159). Although this method obtains high-molecular-weight polycarbonate, the purity of the diphenyl carbonate used is high and the price is expensive, and the by-product phenol of the reaction must be separated under high-temperature and high-vacuum conditions, which increases energy consumption. In addition, most of the catalysts currently reported for the preparation of 1,4:3,6-dihexanol (co)polycarbonate are metal catalysts, such as sodium methoxide (Polymer, 2019, 179, 1-6), Metal acetylacetonate (CN 102746504A), metal hydroxide (Industrial & Engineering Chemistry Research, 2018, 57, 4824-4831), metal carbonate (CN 104031249A), etc. However, these catalysts have certain toxicity, which may not only cause environmental pollution, but also remain in the synthetic polycarbonate products, which limits the application of the products in baby products, medical equipment and food packaging.
因此，开发一种环保、可持续的聚碳酸酯的高效制备方法是本领域的研究重点。Therefore, the development of an environmentally friendly and sustainable polycarbonate efficient preparation method is the focus of research in this field.
发明内容Contents of the invention
本发明的目的在于提供一种离子液体催化制备聚碳酸酯的方法，所述方法是开发酰胺类离子液体催化剂，用于高效催化碳酸二酯和二羟基化合物熔融缩聚生成聚碳酸酯；本发明所述方法采用的酰胺类离子液体催化剂以含酰胺基的化合物为阴离子，四烷基磷为阳离子，其具有结构可设计、催化位点多、活性高、选择性好和不影响聚碳酸酯的品质的优势，并且催化得到了分子量大、玻璃化转变温度高的聚碳酸酯。本发明所述方法的反应条件温和，原料选择范围广；反应过程不需要溶剂，不使用剧毒光气，不会造成环境污染；反应得到的产物无催化剂残留，不含有毒物质，是一种绿色环保的低成本聚碳酸酯制备工艺。The object of the present invention is to provide a kind of method that ionic liquid catalyzes and prepares polycarbonate, described method is to develop amides ionic liquid catalyst, is used for highly efficient catalyzing carbonic acid diester and dihydroxy compound fusion polycondensation and generates polycarbonate; The amide-based ionic liquid catalyst adopted in the method is an anion with an amide-containing compound, and tetraalkylphosphorus is a cation, which has designable structure, many catalytic sites, high activity, good selectivity and does not affect the quality of polycarbonate Advantages, and catalyzed polycarbonate with large molecular weight and high glass transition temperature. The method of the invention has mild reaction conditions and a wide selection of raw materials; the reaction process does not require solvents, does not use highly toxic phosgene, and will not cause environmental pollution; the product obtained by the reaction has no catalyst residue and no toxic substances, and is a kind of A green and environmentally friendly low-cost polycarbonate preparation process.
为达到此发明目的，本发明采用以下技术方案：To achieve this purpose of the invention, the present invention adopts the following technical solutions:
本发明提供了一种离子液体催化制备聚碳酸酯的方法，所述方法包括以下步骤：The invention provides a kind of method that ionic liquid catalysis prepares polycarbonate, described method comprises the following steps:
(1)酯交换阶段：在常压条件下，反应单体碳酸二酯和二羟基化合物发生酯交换反应，得到预聚物；(1) Transesterification stage: under normal pressure conditions, the reaction monomer carbonic acid diester and the dihydroxy compound undergo a transesterification reaction to obtain a prepolymer;
(2)缩聚阶段：在真空条件下，将步骤(1)得到的预聚物进行缩聚反应，得到聚碳酸酯；(2) polycondensation stage: under vacuum conditions, the prepolymer obtained in step (1) is subjected to polycondensation reaction to obtain polycarbonate;
所述离子液体催化剂为酰胺类离子液体，结构如下：Described ionic liquid catalyst is amide ionic liquid, and structure is as follows:
其中，阴离子X-为含酰胺基的化合物，离子液体阳离子中的R1，R2，R3和R4为C1-C20的烷基、C4-C20的环烷基和C6-C20的芳基中的任意一种。Wherein, the anion X - is a compound containing an amide group, R 1 , R 2 , R 3 and R 4 in the ionic liquid cation are C 1 -C 20 alkyl, C 4 -C 20 cycloalkyl and C 6 Any of -C 20 aryl groups.
本发明所述方法采用以含酰胺基的化合物为阴离子，四烷基磷为阳离子的酰胺类离子液体催化剂时，提高了催化剂的催化活性和选择性，加快了反应速率，大大减少了反应时间；且所述酰胺类离子液体催化剂的结构可设计，通过改变阴阳离子的结构或者阴阳离子的组合可以调控聚合物的分子量，得到具有不同分子量的聚碳酸酯产品；此外，所述酰胺类离子液体催化剂能同时活化二羟基化合物的羟基和碳酸二酯的羰基碳，促进二羟基化合物的羟基氧原子进攻碳酸二酯的羰基碳，从而抑制甲基化副反应的发生，促进酯交换反应和缩聚反应的正向进行；如图1所示，随着酰胺类离子液体含量增加时，异山梨醇的质子峰全部向高场移动，说明酰胺类离子液体可以高效活化异山梨醇，打破异山梨醇内氢键，提高异山梨醇内外羟基的活性；另外，所述酰胺类离子液体催化剂热稳定性佳，使其能保证在熔融聚合反应的酯交换阶段和缩聚阶段都保持良好的催化活性，又能够在反应最后阶段热分解，不残留于聚碳酸酯产品中，不影响产品的色泽，使制备得到的聚碳酸酯聚合物更加安全，应用更加广泛。When the method of the present invention adopts the amide-based ionic liquid catalyst with the amide group-containing compound as an anion and tetraalkylphosphorus as a cation, the catalytic activity and selectivity of the catalyst are improved, the reaction rate is accelerated, and the reaction time is greatly reduced; And the structure of the amide-based ionic liquid catalyst can be designed, and the molecular weight of the polymer can be regulated by changing the structure of anions and cations or the combination of anions and cations to obtain polycarbonate products with different molecular weights; in addition, the amide-based ionic liquid catalyst It can activate the hydroxyl group of the dihydroxy compound and the carbonyl carbon of the carbonic acid diester at the same time, and promote the hydroxyl oxygen atom of the dihydroxy compound to attack the carbonyl carbon of the carbonic acid diester, thereby inhibiting the occurrence of methylation side reactions and promoting the transesterification reaction and polycondensation reaction. Forward; as shown in Figure 1, as the content of amide ionic liquid increases, the proton peaks of isosorbide all move to the high field, indicating that amide ionic liquid can efficiently activate isosorbide and break the internal hydrogen of isosorbide. bond, improve the activity of the internal and external hydroxyl groups of isosorbide; in addition, the amide ionic liquid catalyst has good thermal stability, which can ensure good catalytic activity in the transesterification stage and polycondensation stage of the melt polymerization reaction. The final stage of the reaction is thermally decomposed, does not remain in the polycarbonate product, does not affect the color of the product, and makes the prepared polycarbonate polymer safer and more widely used.
本发明所述方法得到的聚碳酸酯中不含有毒物质，副产物易分离且可以回收利用。The polycarbonate obtained by the method of the invention does not contain toxic substances, and by-products are easy to separate and can be recycled.
优选地，所述酰胺类离子液体催化剂的阴离子包括N-甲基乙酰胺、N-乙基乙酰胺、乙酰苯胺、2-吡咯烷酮、2-氮己环酮、1,8-萘二甲酰亚胺、1,2-环戊二甲酰亚胺、3,3-戊亚甲基戊二酰亚胺、3,3-四亚甲基戊二酰亚胺、1,2,3,6-四氢邻苯二甲酰亚胺、六氢邻苯二甲酰亚胺、二乙酰胺、丁二酰亚胺、戊二酰亚胺、己二酰亚胺、马来酰亚胺、琥珀酰亚胺、邻苯二甲酰亚胺或双三氟乙酰胺中的任意一种。Preferably, the anion of the amide-based ionic liquid catalyst includes N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-azhecyclone, 1,8-naphthalene dicarboxylic acid Amine, 1,2-cyclopentadicarboximide, 3,3-pentamethylene glutarimide, 3,3-tetramethylene glutarimide, 1,2,3,6- Tetrahydrophthalimide, Hexahydrophthalimide, Diacetamide, Succinimide, Glutarimide, Adipimide, Maleimide, Succinyl Any one of imine, phthalimide or bistrifluoroacetamide.
优选地，所述酰胺类离子液体催化剂的阳离子包括十四烷基三己基磷、丁基三己基磷、丙基三己基磷、乙基三丁基磷、四甲基磷、四丙基磷或四丁基磷中的任意一种。Preferably, the cation of the amide-based ionic liquid catalyst includes tetradecyl trihexyl phosphorus, butyl trihexyl phosphorus, propyl trihexyl phosphorus, ethyl tributyl phosphorus, tetramethyl phosphorus, tetrapropyl phosphorus or Any one of tetrabutylphosphine.
优选地，所述酰胺类离子液体为如下化合物1～18中的任意一种：Preferably, the amide-based ionic liquid is any one of the following compounds 1-18:
本发明所述方法中酰胺类离子液体催化活性高，不仅能有效活化二羟基化合物的羟基，增加羟基的亲核性，提高羟基进攻碳酸二酯羰基的能力，而且能活化碳酸二酯的羰基碳，增加羰基碳的亲电性，使其更易受羟基进攻，在酯交换反应阶段提高了酯交换产物的选择性，抑制了甲基化副产物的生成。此外，上述酰胺类离子液体热稳定性佳，在缩聚反应阶段的高温高真空条件下依然能保持优异的催化性能，促进端基基团反应，加快分子链增长。同时，上述酰胺类离子液体可以通过改变酰胺阴离子的结构获得具有不同分子量的产物，实现了对聚合反应过程和产品结构的调控。另外，通过DFT模拟计算催化剂和反应单体的相互作用，再结合实验数据，发现上述酰胺类离子液体催化剂能同时活化二羟基化合物和碳酸二酯，不会造成特定一种官能团活性偏高而导致聚合反应受抑制的情况，促进了反应的正向进行，提高了催化效率和选择性，因此优于其他酰胺类离子液体催化剂，得到了具有更高分子量、窄分子量分布的聚碳酸酯。In the method of the present invention, the amide ionic liquid has high catalytic activity, not only can effectively activate the hydroxyl group of the dihydroxy compound, increase the nucleophilicity of the hydroxyl group, improve the ability of the hydroxyl group to attack the carbonyl group of the carbonic acid diester, but also activate the carbonyl carbon of the carbonic acid diester , increasing the electrophilicity of the carbonyl carbon, making it more susceptible to hydroxyl attack, improving the selectivity of transesterification products in the transesterification reaction stage, and inhibiting the formation of methylated by-products. In addition, the above-mentioned amide-based ionic liquid has good thermal stability, and can still maintain excellent catalytic performance under high temperature and high vacuum conditions in the polycondensation reaction stage, promote the reaction of terminal groups, and accelerate the growth of molecular chains. At the same time, the above-mentioned amide-based ionic liquid can obtain products with different molecular weights by changing the structure of the amide anion, which realizes the regulation of the polymerization process and product structure. In addition, the interaction between the catalyst and the reaction monomer was calculated by DFT simulation, combined with the experimental data, it was found that the above-mentioned amide-based ionic liquid catalyst can activate dihydroxy compounds and carbonic acid diesters at the same time, and will not cause a specific functional group to be highly active. The inhibited polymerization reaction promotes the positive progress of the reaction and improves the catalytic efficiency and selectivity. Therefore, it is better than other amide ionic liquid catalysts, and polycarbonate with higher molecular weight and narrow molecular weight distribution is obtained.
优选地，步骤(1)中二羟基化合物和碳酸二酯的摩尔比为1:(0.95-11)，例如1:0.95、1:1、1:2、1:3、1:5、1:7、1:9或1:11等。Preferably, the mol ratio of dihydroxy compound and carbonic acid diester in step (1) is 1:(0.95-11), such as 1:0.95, 1:1, 1:2, 1:3, 1:5, 1: 7. 1:9 or 1:11 etc.
优选地，步骤(1)所述酯交换反应的时间为1-7h，例如1h、2h、3h、4h、5h、6h或7h。Preferably, the time for the transesterification reaction in step (1) is 1-7h, such as 1h, 2h, 3h, 4h, 5h, 6h or 7h.
优选地，步骤(1)所述酯交换反应的温度为120-175℃，例如120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃或175℃等。Preferably, the temperature of the transesterification reaction in step (1) is 120-175°C, such as 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C , 170°C or 175°C, etc.
优选地，所述酰胺类离子液体催化剂的用量是1×10-6-1×10-2mol，例如1×10- 6mol、5×10-6mol、8×10-6mol、2×10-5mol、6×10-5mol、9×10-5mol、1×10-4mol、5×10-4mol、1×10-3mol、3×10-3mol、5×10-3mol、8×10-3mol或1×10-2mol等。Preferably, the amount of the amide-based ionic liquid catalyst is 1×10 -6 -1×10 -2 mol, such as 1×10 -6 mol, 5×10 -6 mol, 8×10 -6 mol, 2× 10 -5 mol, 6×10 -5 mol, 9×10 -5 mol, 1×10 -4 mol, 5×10 -4 mol, 1×10 -3 mol, 3× 10 -3 mol, 5×10 -3 mol, 8×10 -3 mol or 1×10 -2 mol, etc.
优选地，步骤(2)所述缩聚反应的真空度为50-1000Pa，例如50Pa、200Pa、350Pa、500Pa、600Pa、700Pa、800Pa、900Pa或1000Pa等。Preferably, the vacuum degree of the polycondensation reaction in step (2) is 50-1000Pa, such as 50Pa, 200Pa, 350Pa, 500Pa, 600Pa, 700Pa, 800Pa, 900Pa or 1000Pa.
优选地，步骤(2)所述缩聚反应的温度为220-290℃，例如220℃、230℃、240℃、250℃、260℃、270℃、280℃或290℃等。Preferably, the temperature of the polycondensation reaction in step (2) is 220-290°C, such as 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C or 290°C.
优选地，步骤(2)所述缩聚反应的时间为0.5-6.0h，例如0.5h、1.0h、1.5h、2.0h、2.5h、3.0h、3.5h、4.0h、4.5h、5.0h、5.5h或6.0h等。Preferably, the time of the polycondensation reaction in step (2) is 0.5-6.0h, such as 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h or 6.0h etc.
优选地，步骤(1)所述碳酸二酯包括碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二苯酯、碳酸二甲苯酯或碳酸二萘酯中的任意一种或至少两种的组合，所述组合示例性的包括碳酸二甲酯和碳酸二乙酯的组合、碳酸二丙酯和碳酸二丁酯的组合、碳酸二苯酯和碳酸二甲苯酯的组合或碳酸二萘酯和碳酸二甲酯的组合等。Preferably, the carbonic diester described in step (1) includes any of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, xylyl carbonate or dinaphthyl carbonate One or a combination of at least two, the combination illustratively includes a combination of dimethyl carbonate and diethyl carbonate, a combination of dipropyl carbonate and dibutyl carbonate, diphenyl carbonate and xylene carbonate A combination or a combination of dinaphthyl carbonate and dimethyl carbonate, etc.
优选地，步骤(1)所述二羟基化合物包括1,4:3,6-二缩水己六醇、脂肪族二羟基化合物或芳香族二羟基化合物中的任意一种或至少两种的组合，所述组合示例性的包括1,4:3,6-二缩水己六醇和脂肪族二羟基化合物的组合或芳香族二羟基化合物和脂肪族二羟基化合物的组合等。Preferably, the dihydroxy compound in step (1) includes any one or a combination of at least two of 1,4:3,6-dihexanol, aliphatic dihydroxy compound or aromatic dihydroxy compound, The combination exemplarily includes a combination of 1,4:3,6-dihexanol and an aliphatic dihydroxy compound, or a combination of an aromatic dihydroxy compound and an aliphatic dihydroxy compound, and the like.
优选地，所述二羟基化合物为1,4:3,6-二缩水己六醇和脂肪族二羟基化合物的混合物或1,4:3,6-二缩水己六醇和芳香族二羟基化合物的混合物。Preferably, the dihydroxy compound is a mixture of 1,4:3,6-dihexanol and an aliphatic dihydroxy compound or a mixture of 1,4:3,6-dihexanol and an aromatic dihydroxy compound .
优选地，所述1,4:3,6-二缩水己六醇和脂肪族二羟基化合物的混合物中1,4:3,6-二缩水己六醇和脂肪族二羟基化合物的摩尔比为(0.2-7):1，例如0.2:1、0.4:1、0.6:1、0.8:1、1:1、2:1、3:1、4:1、5:1、6:1或7:1等。Preferably, the molar ratio of 1,4:3,6-dihexanol and the aliphatic dihydroxy compound in the mixture of 1,4:3,6-dihexanol and the aliphatic dihydroxy compound is (0.2 -7):1, such as 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1 or 7:1 Wait.
优选地，所述1,4:3,6-二缩水己六醇和芳香族二羟基化合物的混合物中1,4:3,6-二缩水己六醇和芳香族二羟基化合物的摩尔比为(0.2-7):1，例如0.2:1、0.4:1、0.6:1、0.8:1、1:1、2:1、3:1、4:1、5:1、6:1或7:1等。Preferably, the molar ratio of 1,4:3,6-dihexanol and the aromatic dihydroxy compound in the mixture of 1,4:3,6-dihexanol and the aromatic dihydroxy compound is (0.2 -7):1, such as 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1 or 7:1 Wait.
本发明所述催化反应过程中采用上述二羟基化合物组合能明显提高产物聚碳酸酯的分子量。The use of the above-mentioned dihydroxy compound combination in the catalytic reaction process of the present invention can obviously increase the molecular weight of the product polycarbonate.
优选地，所述1,4:3,6-二缩水己六醇选自异山梨醇、异甘露醇或异艾杜醇中的任意一种或至少两种的组合，所述组合示例性的包括异山梨醇和异甘露醇的组合、异艾杜醇和异山梨醇的组合或异甘露醇和异艾杜醇的组合等。Preferably, the 1,4:3,6-dihexylhexyl alcohol is selected from any one or a combination of at least two of isosorbide, isomannide or isoidide, and the combination is exemplary Including a combination of isosorbide and isomannide, a combination of isoidide and isosorbide or a combination of isomannide and isoidide, and the like.
所述脂肪族二羟基化合物选自1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,10-癸二醇、1,2-环己二醇、1,3-环己二醇、1,4-环己二醇、1,2-环己烷二甲醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇、2-甲基-1,4-环己二醇、一缩二乙二醇、二缩三乙二醇、三缩四乙二醇、新戊二醇、氢化二油基二醇、氢化二亚油基二醇、2-乙基-1,6-己二醇、2,2,4-三甲基-1,6-己二醇、1,5-萘烷二甲醇、2,3-萘烷二甲醇、2,6-萘烷二甲醇、2,3-降冰片烷二甲醇、2,5-降冰片烷二甲醇、1,3-金刚烷二甲醇或4,8-双(羟甲基)三环癸烷中的任意一种或至少两种的组合；The aliphatic dihydroxy compound is selected from 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -octanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2-methyl-1,4-cyclohexanediol, diethylene glycol, diethylene glycol, triethylene glycol Tetraethylene glycol, neopentyl glycol, hydrogenated dioleyl glycol, hydrogenated dilinoleyl glycol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1, 6-Hexanediol, 1,5-Decalindimethanol, 2,3-Decalindimethanol, 2,6-Decalindimethanol, 2,3-Norbornanedimethanol, 2,5-Norbornanedimethanol Any one or a combination of at least two of dimethanol, 1,3-adamantanedimethanol or 4,8-bis(hydroxymethyl)tricyclodecane;
所述芳香族二羟基化合物选自对苯二酚、1,4-苯二甲醇、1,4-苯二乙醇、9,9-双[4-(2-羟基乙氧基)苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-甲基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-甲异丙基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-异丁基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-叔丁基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-环己基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-苯基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3,5-二甲基苯基]芴、9,9-双[4-(2-羟基乙氧基)-3-叔丁基-6-甲基苯基]芴、9,9-双[4-(3-羟基-2,2二甲基丙氧基)苯基]芴、9,9-双(3-苯基-4-(2-羟基乙氧基)苯基)芴、9,9-双(5-羟基-1-萘基)芴、9,9-双(5-(2-羟基乙氧基)-1-萘基)芴、9,9-双(6-(2-羟基丙氧基)萘基)芴、9,9-双(6-(2-(2-羟基乙氧基)乙氧基)萘基)芴、9,9-双(5-(2-(2-羟基乙氧基)乙氧基)-1-萘基)芴、4,4'-(1-苯乙基)双酚、2,2-二(4-羟苯基)丁烷、4,4'-亚乙基双苯酚、4,4'-二羟基二苯甲烷、1,3-双[2-(4-羟苯基)-2-丙基]苯、4,4'-二羟基四苯甲烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、2,2-双(4-羟基-3-甲苯基)丙烷、2,2-双(4-羟基苯基)丙烷、2,2'-双(2-羟基丙氧基)-1,1'-联萘、2,2'-双(2-(2-羟基乙氧基)乙氧基)-1,1'-联萘、2,2-二(4-羟基苯基)丁烷、2,2-二(4-羟基苯基)丙烷或3-(4-羟基苯基)-1-丙醇中的任意一种或至少两种的组合。The aromatic dihydroxy compound is selected from hydroquinone, 1,4-benzenedimethanol, 1,4-benzenediethanol, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene , 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylisopropyl Phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isobutylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3 -tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy )-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2 -Hydroxyethoxy)-3-tert-butyl-6-methylphenyl]fluorene, 9,9-bis[4-(3-hydroxy-2,2-dimethylpropoxy)phenyl]fluorene, 9,9-bis(3-phenyl-4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, 9,9-bis(5 -(2-hydroxyethoxy)-1-naphthyl)fluorene, 9,9-bis(6-(2-hydroxypropoxy)naphthyl)fluorene, 9,9-bis(6-(2-( 2-hydroxyethoxy)ethoxy)naphthyl)fluorene, 9,9-bis(5-(2-(2-hydroxyethoxy)ethoxy)-1-naphthyl)fluorene, 4,4 '-(1-phenylethyl)bisphenol, 2,2-bis(4-hydroxyphenyl)butane, 4,4'-ethylenebisphenol, 4,4'-dihydroxydiphenylmethane, 1 ,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-dihydroxytetraphenylmethane, 2,2-bis(4-hydroxy-3,5-dimethyl Phenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2'-bis(2-hydroxypropoxy) -1,1'-binaphthyl, 2,2'-bis(2-(2-hydroxyethoxy)ethoxy)-1,1'-binaphthyl, 2,2-bis(4-hydroxyphenyl ) butane, 2,2-bis(4-hydroxyphenyl)propane or 3-(4-hydroxyphenyl)-1-propanol or a combination of at least two.
优选地，所述催化制备聚碳酸酯的方法的反应通式为：Preferably, the general reaction formula of the method for preparing polycarbonate by catalysis is:
其中，R1为苯环或碳原子数为1～15，例如2、5、6、8、10、11、13或15等，的烷基；R1示例性地包括但不限于甲基、乙基、丙基、丁基或戊基中的任意一种。Wherein, R 1 is a benzene ring or an alkyl group with 1 to 15 carbon atoms, such as 2, 5, 6, 8, 10, 11, 13 or 15, etc.; R 1 exemplarily includes but is not limited to methyl, Any of ethyl, propyl, butyl or pentyl.
R2为取代或未取代的碳原子数为2～20，例如2、4、5、8、10、11、13、16、18或20等的直链或支链烷基、取代或未取代的碳原子数为3～20，例如3、5、7、10、12、14、15、17或20等的环烷基、取代或未取代的碳原子数为3～20，例如3、5、7、10、12、14、15、17或20等的杂环烷基、取代或未取代的碳原子数为6～24，例如6、10、13、15、16、18、20或24等的芳基中的任意一种或至少两种的组合；m、m'各自独立地为不小于0的整数，例如0、1、5、10、20、30、40、50、65、75、90、110、130或150等，且m、m'不同时为0。 R2 is a substituted or unsubstituted straight chain or branched alkyl group with 2 to 20 carbon atoms, such as 2, 4, 5, 8, 10, 11, 13, 16, 18 or 20, substituted or unsubstituted The number of carbon atoms is 3 to 20, such as 3, 5, 7, 10, 12, 14, 15, 17 or 20, etc. Cycloalkyl, substituted or unsubstituted carbon atoms are 3 to 20, such as 3, 5 , 7, 10, 12, 14, 15, 17 or 20 etc. heterocycloalkyl, substituted or unsubstituted carbon atoms number is 6-24, such as 6, 10, 13, 15, 16, 18, 20 or 24 Any one or a combination of at least two of the aryl groups; m and m' are each independently an integer not less than 0, such as 0, 1, 5, 10, 20, 30, 40, 50, 65, 75 , 90, 110, 130 or 150, etc., and m and m' are not 0 at the same time.
当m为0时，m'用n表示，所述催化制备聚碳酸酯的方法的反应通式为：When m is 0, m' is represented by n, and the general reaction formula of the method for preparing polycarbonate by catalysis is:
其中，R1为苯环或碳原子数为1～15，例如2、5、6、8、10、11、13或15等，的烷基；R1示例性地包括但不限于甲基、乙基、丙基、丁基或戊基中的任意一种。Wherein, R 1 is a benzene ring or an alkyl group with 1 to 15 carbon atoms, such as 2, 5, 6, 8, 10, 11, 13 or 15, etc.; R 1 exemplarily includes but is not limited to methyl, Any of ethyl, propyl, butyl or pentyl.
R2为取代或未取代的碳原子数为2～20，例如2、4、5、8、10、11、13、16、18或20等的直链或支链烷基、取代或未取代的碳原子数为3～20，例如3、5、7、10、12、14、15、17或20等的环烷基、取代或未取代的碳原子数为3～20，例如3、5、7、10、12、14、15、17或20等的杂环烷基、取代或未取代的碳原子数为6～24，例如6、10、13、15、16、18、20或24等的芳基中的任意一种或至少两种的组合，n为大于0的整数，例如10、30、50、70、90、150、170或200等。 R2 is a substituted or unsubstituted straight chain or branched alkyl group with 2 to 20 carbon atoms, such as 2, 4, 5, 8, 10, 11, 13, 16, 18 or 20, substituted or unsubstituted The number of carbon atoms is 3 to 20, such as 3, 5, 7, 10, 12, 14, 15, 17 or 20, etc. Cycloalkyl, substituted or unsubstituted carbon atoms are 3 to 20, such as 3, 5 , 7, 10, 12, 14, 15, 17 or 20 etc. heterocycloalkyl, substituted or unsubstituted carbon atoms number is 6-24, such as 6, 10, 13, 15, 16, 18, 20 or 24 Any one or a combination of at least two of the aryl groups, etc., n is an integer greater than 0, such as 10, 30, 50, 70, 90, 150, 170 or 200, etc.
上述杂环烷基中的杂原子为O、S、P或N中的任意一种或至少两种的组合，所述组合示例性的包括O和S的组合或P和N的组合等。The heteroatom in the above heterocycloalkyl group is any one or a combination of at least two of O, S, P or N, and the combination exemplarily includes a combination of O and S or a combination of P and N.
作为本发明优选的技术方案，所述方法包括以下步骤：As a preferred technical solution of the present invention, the method comprises the following steps:
(1)酯交换阶段：在常压条件下，碳酸二酯和二羟基化合物发生酯交换反应，得到预聚物，所述酯交换反应采用的催化剂为酰胺类离子液体；所述酯交换反应的时间为1-7h，所述酯交换反应的温度为120-175℃；所述酰胺类离子液体催化剂的阴离子包括N-甲基乙酰胺、N-乙基乙酰胺、乙酰苯胺、2-吡咯烷酮、2-氮己环酮、1,8-萘二甲酰亚胺、1,2-环戊二甲酰亚胺、3,3-戊亚甲基戊二酰亚胺、3,3-四亚甲基戊二酰亚胺、1,2,3,6-四氢邻苯二甲酰亚胺、六氢邻苯二甲酰亚胺、二乙酰胺、丁二酰亚胺、戊二酰亚胺、己二酰亚胺、马来酰亚胺、琥珀酰亚胺、邻苯二甲酰亚胺或双三氟乙酰胺中的任意一种；所述酰胺类离子液体催化剂的阳离子包括十四烷基三己基磷、丁基三己基磷、丙基三己基磷、乙基三丁基磷、四甲基磷、四丙基磷或四丁基磷中的任意一种；(1) transesterification stage: under normal pressure conditions, carbonic acid diester and dihydroxy compound transesterify, obtain prepolymer, the catalyst that described transesterification adopts is amide ionic liquid; The time is 1-7h, the temperature of the transesterification reaction is 120-175°C; the anion of the amide ionic liquid catalyst includes N-methylacetamide, N-ethylacetamide, acetanilide, 2-pyrrolidone, 2-Azicyclone, 1,8-naphthalimide, 1,2-cyclopentadicarboximide, 3,3-pentamethyleneglutarimide, 3,3-tetramethylene Methylglutarimide, 1,2,3,6-tetrahydrophthalimide, hexahydrophthalimide, diacetamide, succinimide, glutarimide Any one of amine, adipimide, maleimide, succinimide, phthalimide or bistrifluoroacetamide; the cation of the amide ionic liquid catalyst includes fourteen Any one of alkyl trihexyl phosphorus, butyl trihexyl phosphorus, propyl trihexyl phosphorus, ethyl tributyl phosphorus, tetramethyl phosphorus, tetrapropyl phosphorus or tetrabutyl phosphorus;
(2)缩聚阶段：在真空条件下，将步骤(1)得到的预聚物进行缩聚反应，得到聚碳酸酯；所述缩聚反应的真空度为50-1000Pa，所述缩聚反应的温度为220-290℃，所述缩聚反应的时间为0.5-6.0h。(2) Polycondensation stage: Under vacuum conditions, the prepolymer obtained in step (1) is subjected to polycondensation reaction to obtain polycarbonate; the vacuum degree of the polycondensation reaction is 50-1000Pa, and the temperature of the polycondensation reaction is 220 -290°C, the time for the polycondensation reaction is 0.5-6.0h.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明所述方法以酰胺类离子液体作为催化剂，利用酰胺类离子液体的高催化活性和选择性，不仅打破二羟基化合物的分子间氢键，提高了二羟基化合物的羟基活性，而且激活了碳酸二酯的羰基，使碳酸二酯的羰基易受二羟基化合物的羟基进攻，从而抑制了甲基化副产物的生成，提高了酯交换产物的选择性，促进二羟基化合物和碳酸二酯的反应向正向进行；(1) The method of the present invention uses amide ionic liquid as catalyst, utilizes high catalytic activity and selectivity of amide ionic liquid, not only breaks the intermolecular hydrogen bond of dihydroxy compound, improves the hydroxyl activity of dihydroxy compound, and Activates the carbonyl group of the carbonic acid diester, making the carbonyl group of the carbonic acid diester susceptible to the attack of the hydroxyl group of the dihydroxy compound, thereby inhibiting the formation of methylated by-products, improving the selectivity of the transesterification product, and promoting the formation of the dihydroxy compound and the carbonic acid dihydroxy compound. The reaction of the ester proceeds forward;
(2)本发明所述方法采用的酰胺类离子液体催化剂结构可设计，通过改变阴阳离子的结构和阴阳离子的组合，可以调节酰胺类离子液体催化剂的催化活性和选择性，获得具有不同分子量的聚碳酸酯产物，实现对聚合反应过程和产品的定向调控；此外，通过优化酰胺类离子液体催化剂的阴阳离子结构和组合，解决了传统催化剂对不同种类醇羟基活化作用普适性差的问题，成功实现一锅法制备共聚聚碳酸酯，简化了反应步骤，减少了反应流程，提高了合成效率；(2) The structure of the amide ionic liquid catalyst adopted in the method of the present invention can be designed, and by changing the structure of anions and cations and the combination of anions and cations, the catalytic activity and selectivity of the amide ionic liquid catalyst can be adjusted to obtain compounds with different molecular weights. Polycarbonate products, to achieve directional control of the polymerization process and products; in addition, by optimizing the structure and combination of anions and cations of amide-based ionic liquid catalysts, the problem of poor universality of traditional catalysts for the activation of hydroxyl groups of different alcohols has been solved. Realize the preparation of copolycarbonate by one-pot method, which simplifies the reaction steps, reduces the reaction process and improves the synthesis efficiency;
(3)本发明所述方法采用的酰胺类离子液体催化剂不仅绿色环保，用量少，使获得的聚合物更加安全，应用更加广泛，而且具有优异的热稳定性，使其能在酯交换阶段和缩聚阶段均保持良好的催化活性，加快了反应速率；(3) The amide ionic liquid catalyst adopted in the method of the present invention is not only green and environmentally friendly, but also in a small amount, which makes the obtained polymer safer and more widely used, and has excellent thermal stability, so that it can be used in the transesterification stage. It maintains good catalytic activity in both the polycondensation stage and the polycondensation stage, which accelerates the reaction rate;
(4)本发明所述方法采用熔融聚合工艺，反应条件温和，反应过程不产生有机废水和固体废弃物，制备得到了分子量大、分子量分布窄、玻璃化转变温度高的聚碳酸酯，且产物不含有毒物质，应用更加广泛。(4) The method of the present invention adopts a melt polymerization process, the reaction conditions are mild, no organic waste water and solid waste are produced in the reaction process, and polycarbonate with large molecular weight, narrow molecular weight distribution and high glass transition temperature is prepared, and the product It does not contain toxic substances and is more widely used.
附图说明Description of drawings
图1是酰胺类离子液体活化异山梨醇的1H NMR图谱。Fig. 1 is the 1 H NMR spectrum of isosorbide activated by amide ionic liquid.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.
本发明所用的酰胺类离子液体合成范例如下：The synthesis example of the amide ionic liquid used in the present invention is as follows:
(1)合成
将四丁基氢氧化磷水溶液(0.01mol，6.9g)和邻苯二甲酰亚胺(0.01mol,1.47g)加入到装有磁子的50mL单口圆底烧瓶中，将烧瓶置于水浴中，使反应混合物在室温下搅拌24h，反应结束后于70℃减压旋蒸4h，再在60℃真空干燥12h，最终得到产物3.85g，产率95％。Add tetrabutylphosphorus hydroxide aqueous solution (0.01mol, 6.9g) and phthalimide (0.01mol, 1.47g) into a 50mL single-necked round bottom flask equipped with a magnet, place the flask in a water bath, and The reaction mixture was stirred at room temperature for 24 hours. After the reaction was completed, it was rotary evaporated at 70° C. for 4 hours under reduced pressure, and then vacuum-dried at 60° C. for 12 hours. Finally, 3.85 g of the product was obtained with a yield of 95%.
(2)合成
将四丁基氢氧化磷水溶液(0.01mol，6.9g)和戊二酰亚胺(0.01mol,1.13g)加入到装有磁子的50mL单口圆底烧瓶中，将烧瓶置于水浴中，使反应混合物在室温下搅拌24h，反应结束后于70℃减压旋蒸4h，再在60℃真空干燥12h，最终得到产物3.34g，产率90％。Tetrabutylphosphorus hydroxide aqueous solution (0.01mol, 6.9g) and glutarimide (0.01mol, 1.13g) were added to a 50mL single-necked round bottom flask equipped with a magnet, and the flask was placed in a water bath to make the reaction mixture Stirring at room temperature for 24 hours, rotary evaporation at 70° C. for 4 hours under reduced pressure after the reaction, and vacuum drying at 60° C. for 12 hours to finally obtain 3.34 g of the product with a yield of 90%.
(3)合成
将四丁基氢氧化磷水溶液(0.01mol，6.9g)和六氢邻苯二甲酰亚胺(0.01mol,1.53g)加入到装有磁子的50mL单口圆底烧瓶中，将烧瓶置于水浴中，使反应混合物在室温下搅拌24h，反应结束后于70℃减压旋蒸4h，再在60℃真空干燥12h，最终得到产物3.95g，产率96％。Tetrabutylphosphorus hydroxide aqueous solution (0.01mol, 6.9g) and hexahydrophthalimide (0.01mol, 1.53g) were added to a 50mL single-necked round bottom flask equipped with a magnet, and the flask was placed in a water bath , the reaction mixture was stirred at room temperature for 24 h, and after the reaction was completed, it was rotary evaporated at 70° C. for 4 h under reduced pressure, and then vacuum-dried at 60° C. for 12 h to finally obtain 3.95 g of the product with a yield of 96%.
实施例1Example 1
本实施例中以异山梨醇、碳酸二甲酯为原料，在酰胺类离子液体催化下制备一种聚碳酸酯，反应式如下：In this example, isosorbide and dimethyl carbonate are used as raw materials to prepare a polycarbonate under the catalysis of amide ionic liquid, and the reaction formula is as follows:
制备方法包括以下步骤：The preparation method comprises the following steps:
(1)酯交换阶段：在氮气气氛和常压下，向反应瓶中加入7.3g(0.05mol)异山梨醇，22.5g(0.25mol)碳酸二甲酯和四丁基磷邻苯二甲酰亚胺(0.0005mol，0.2025g)，使反应混合物在160℃反应2h，接着温度缓慢升到180℃，反应0.5h，使未反应的碳酸二甲酯和低沸点产物甲醇挥发，得到预聚物；(1) Transesterification stage: under nitrogen atmosphere and normal pressure, add 7.3g (0.05mol) isosorbide, 22.5g (0.25mol) dimethyl carbonate and tetrabutylphosphorus phthaloyl to the reaction flask Imine (0.0005mol, 0.2025g), react the reaction mixture at 160°C for 2h, then slowly raise the temperature to 180°C, react for 0.5h, volatilize the unreacted dimethyl carbonate and low boiling point product methanol, and obtain the prepolymer ;
(2)缩聚阶段：将步骤(1)中的温度从180℃升到250℃，真空度缓缓降到50Pa，进行1.5h的反应得到产物异山梨醇型聚碳酸酯；(2) Polycondensation stage: the temperature in step (1) is raised from 180°C to 250°C, the vacuum is slowly reduced to 50Pa, and the reaction is carried out for 1.5h to obtain the product isosorbide polycarbonate;
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为25000g/mol，重均分子量Mw为41000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 25000g/mol and a weight average molecular weight Mw of 41000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为165℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 165°C.
核磁测试：甲基化选择性0.4％，甲酯化选择性99.6％。NMR test: methylation selectivity 0.4%, methyl esterification selectivity 99.6%.
实施例2Example 2
本实施例与实施例1的区别在于，所用的催化剂为四丁基磷戊二酰亚胺(0.0005mol，0.1855g)，其他条件与实施例1相比完全相同。The difference between this example and example 1 is that the catalyst used is tetrabutylphosphoglutarimide (0.0005mol, 0.1855g), and other conditions are exactly the same as those of example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为22000g/mol，重均分子量Mw为37000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 22000g/mol and a weight average molecular weight Mw of 37000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为163℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 163°C.
核磁测试：甲基化选择性0.7％，甲酯化选择性99.3％。NMR test: methylation selectivity 0.7%, methyl esterification selectivity 99.3%.
实施例3Example 3
本实施例与实施例1的区别在于，所用的催化剂为四丁基磷六氢邻苯二甲酰亚胺(0.0005mol，0.2055g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is tetrabutylphosphine hexahydrophthalimide (0.0005mol, 0.2055g), and other conditions are exactly the same as those of Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为20000g/mol，重均分子量Mw为33000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 20000g/mol and a weight average molecular weight Mw of 33000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为160℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 160°C.
核磁测试：甲基化选择性1.3％，甲酯化选择性98.7％。NMR test: methylation selectivity 1.3%, methyl esterification selectivity 98.7%.
实施例4Example 4
本实施例与实施例1的区别在于，所用的催化剂为四丁基磷1,8-萘二甲酰亚胺(0.0005mol，0.2275g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为17000g/mol，重均分子量Mw为29000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 17000g/mol and a weight average molecular weight Mw of 29000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为159℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 159°C.
核磁测试：甲基化选择性1.8％，甲酯化选择性98.2％。NMR test: methylation selectivity 1.8%, methyl esterification selectivity 98.2%.
实施例5Example 5
本实施例与实施例1的区别在于，所用的催化剂为四丁基磷琥珀酰亚胺(0.0005mol，0.1785g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is tetrabutylphosphorusuccinimide (0.0005mol, 0.1785g), and other conditions are exactly the same as those of Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为15000g/mol，重均分子量Mw为25000g/mol。Molecular weight test: GPC test results of the product show that the polycarbonate has a number average molecular weight M n of 15000 g/mol and a weight average molecular weight M w of 25000 g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为155℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 155°C.
核磁测试：甲基化选择性2.0％，甲酯化选择性98.0％。NMR test: methylation selectivity 2.0%, methyl esterification selectivity 98.0%.
实施例6Example 6
本实施例与实施例1的区别在于，所用的催化剂为四丁基磷1,2-环戊二甲酰亚胺(0.0005mol，0.1985g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为13000g/mol，重均分子量Mw为20000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 13000g/mol and a weight average molecular weight Mw of 20000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为150℃。Thermal performance test: The DSC test result of the product shows that the polycarbonate has a glass transition temperature Tg of 150°C.
核磁测试：甲基化选择性3.7％，甲酯化选择性96.3％。NMR test: methylation selectivity 3.7%, methyl esterification selectivity 96.3%.
实施例7Example 7
本实施例与实施例1的区别在于，所用的催化剂为丙基三己基磷邻苯二甲酰亚胺(0.0005mol，0.2375g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is propyltrihexylphosphorus phthalimide (0.0005mol, 0.2375g), and other conditions are exactly the same as those in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为11000g/mol，重均分子量Mw为18000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 11000g/mol and a weight average molecular weight Mw of 18000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为148℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 148°C.
核磁测试：甲基化选择性4.7％，甲酯化选择性95.3％。NMR test: methylation selectivity 4.7%, methyl esterification selectivity 95.3%.
实施例8Example 8
本实施例与实施例1的区别在于，所用的催化剂为十四烷基三己基磷3,3-四亚甲基戊二酰亚胺(0.0005mol，0.3245g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the catalyst used is
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为10000g/mol，重均分子量Mw为16000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 10000g/mol and a weight average molecular weight Mw of 16000g/mol.
热性能测试：产物的DSC测试结果表明，聚碳酸酯的玻璃化转变温度Tg为146℃。Thermal performance test: The DSC test result of the product shows that the glass transition temperature T g of polycarbonate is 146°C.
核磁测试：甲基化选择性5.1％，甲酯化选择性94.9％。NMR test: methylation selectivity 5.1%, methyl esterification selectivity 94.9%.
实施例9Example 9
本实施例与实施例1的区别在于，将碳酸二甲酯的质量由22.5g替换为4.275g(0.0475mol)，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the quality of dimethyl carbonate is replaced by 22.5g to 4.275g (0.0475mol), and other conditions are exactly the same as in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为5000g/mol，重均分子量Mw为5400g/mol。Molecular weight test: GPC test results of the product show that the polycarbonate has a number average molecular weight M n of 5000 g/mol and a weight average molecular weight M w of 5400 g/mol.
实施例10Example 10
本实施例与实施例1的区别在于，将碳酸二甲酯的质量由22.5g替换为40.5g(0.45mol)，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the quality of dimethyl carbonate is replaced by 22.5g to 40.5g (0.45mol), and other conditions are completely the same as in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为31000g/mol，重均分子量Mw为50000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 31000g/mol and a weight average molecular weight Mw of 50000g/mol.
实施例11Example 11
本实施例与实施例1的区别在于，将碳酸二甲酯的质量由22.5g替换为49.5g(0.55mol)，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the quality of dimethyl carbonate is replaced by 22.5g to 49.5g (0.55mol), and other conditions are completely the same as in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为24000g/mol，重均分子量Mw为40000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 24000g/mol and a weight average molecular weight Mw of 40000g/mol.
对比实施例1、9-11可以看出，当二羟基化合物和碳酸二酯的摩尔比为1:(5-9)时，催化制备得到的聚碳酸酯的数均分子量和重均分子量较大。Comparative examples 1,9-11 can find out, when the mol ratio of dihydroxy compound and carbonic acid diester is 1:(5-9), the number-average molecular weight and the weight-average molecular weight of the polycarbonate that catalysis prepares are bigger .
实施例12Example 12
本实施例与实施例1的区别在于，酯交换反应时间由2h替换为1h，其他条件与实施例1相比完全相同。The difference between this example and example 1 is that the transesterification reaction time is replaced by 2h to 1h, and other conditions are exactly the same as those of example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为20000g/mol，重均分子量Mw为33000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 20000g/mol and a weight average molecular weight Mw of 33000g/mol.
实施例13Example 13
本实施例与实施例1的区别在于，酯交换反应时间由2h替换为3h，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the transesterification reaction time is replaced by 2h to 3h, and other conditions are completely the same as those in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为33000g/mol，重均分子量Mw为55000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 33000g/mol and a weight average molecular weight Mw of 55000g/mol.
实施例14Example 14
本实施例与实施例1的区别在于，酯交换反应时间由2h替换为5h，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the transesterification reaction time is replaced by 2h to 5h, and other conditions are completely the same as those of Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为30000g/mol，重均分子量Mw为49000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 30000g/mol and a weight average molecular weight Mw of 49000g/mol.
实施例15Example 15
本实施例与实施例1的区别在于，酯交换反应时间由2h替换为7h，其他条件与实施例1相比完全相同。The difference between this example and example 1 is that the transesterification reaction time is replaced by 2h to 7h, and other conditions are completely the same as those of example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为21000g/mol，重均分子量Mw为34000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 21000g/mol and a weight average molecular weight Mw of 34000g/mol.
对比实施例1、12-15可以看出，当酯交换反应时间为3-5h时，催化制备得到的聚碳酸酯的数均分子量和重均分子量较大。Comparing Examples 1 and 12-15, it can be seen that when the transesterification reaction time is 3-5h, the number-average molecular weight and weight-average molecular weight of the polycarbonate prepared by catalysis are relatively large.
实施例16Example 16
本实施例与实施例1的区别在于，将酯交换反应的起始反应温度由160℃替换为120℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the initial reaction temperature of the transesterification reaction is replaced by 120° C. from 160° C., and other conditions are completely the same as those of Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为19000g/mol，重均分子量Mw为32000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 19000g/mol and a weight average molecular weight Mw of 32000g/mol.
实施例17Example 17
本实施例与实施例1的区别在于，将酯交换反应的起始反应温度由160℃替换为175℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the initial reaction temperature of the transesterification reaction is replaced by 175° C. from 160° C., and other conditions are completely the same as those of Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为21000g/mol，重均分子量Mw为34000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 21000g/mol and a weight average molecular weight Mw of 34000g/mol.
实施例18Example 18
本实施例与实施例1的区别在于，将催化剂用量由5×10-4mol替换为1×10-6mol，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of catalyst used is replaced by 5×10 -4 mol to 1×10 -6 mol, and other conditions are completely the same as those in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为18000g/mol，重均分子量Mw为30000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 18000g/mol and a weight average molecular weight Mw of 30000g/mol.
实施例19Example 19
本实施例与实施例1的区别在于，将催化剂用量由5×10-4mol替换为1×10-2mol，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of catalyst used is replaced by 5×10 -4 mol to 1×10 -2 mol, and other conditions are completely the same as those in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为22000g/mol，重均分子量Mw为37000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 22000g/mol and a weight average molecular weight Mw of 37000g/mol.
实施例20Example 20
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，将步骤(2)中缩聚反应的真空度替换为1000Pa，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), and the vacuum degree of the polycondensation reaction in step (2) is replaced by 1000Pa, and other conditions are compared with Example 1 exactly the same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为4700g/mol，重均分子量Mw为5600g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 4700g/mol and a weight average molecular weight Mw of 5600g/mol.
实施例21Example 21
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，将步骤(2)中缩聚反应的真空度替换为100Pa，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), and the vacuum degree of the polycondensation reaction in step (2) is replaced by 100Pa, and other conditions are compared with Example 1 exactly the same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为21000g/mol，重均分子量Mw为34000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 21000g/mol and a weight average molecular weight Mw of 34000g/mol.
实施例22Example 22
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的温度替换为220℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the temperature of the polycondensation reaction in step (2) is replaced by 220°C, and other conditions are completely different from those in Example 1. same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为28000g/mol，重均分子量Mw为46000g/mol。Molecular weight test: GPC test results of the product show that the polycarbonate has a number average molecular weight M n of 28000 g/mol and a weight average molecular weight M w of 46000 g/mol.
实施例23Example 23
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的温度替换为240℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the temperature of the polycondensation reaction in step (2) is replaced by 240°C, and other conditions are completely compared with Example 1. same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为34000g/mol，重均分子量Mw为57000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 34000g/mol and a weight average molecular weight Mw of 57000g/mol.
实施例24Example 24
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的温度替换为270℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the temperature of the polycondensation reaction in step (2) is replaced by 270°C, and other conditions are completely compared with Example 1. same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为30000g/mol，重均分子量Mw为49000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 30000g/mol and a weight average molecular weight Mw of 49000g/mol.
实施例25Example 25
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的温度替换为290℃，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the temperature of the polycondensation reaction in step (2) is replaced by 290°C, and other conditions are completely different from those in Example 1. same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为27000g/mol，重均分子量Mw为46000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 27000g/mol and a weight average molecular weight Mw of 46000g/mol.
对比实施例1、22-25可以看出，当控制缩聚阶段反应的温度为240-270℃时，催化制备得到的聚碳酸酯的数均分子量和重均分子量较大。Comparing Examples 1 and 22-25, it can be seen that when the reaction temperature in the polycondensation stage is controlled to be 240-270° C., the number average molecular weight and weight average molecular weight of the polycarbonate prepared by catalysis are relatively large.
实施例26Example 26
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的时间替换为0.5h，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the time of polycondensation reaction in step (2) is replaced by 0.5h, and other conditions are compared with Example 1 completely same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为16000g/mol，重均分子量Mw为26000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 16000g/mol and a weight average molecular weight Mw of 26000g/mol.
实施例27Example 27
本实施例与实施例1的区别在于，将碳酸二甲酯的用量调整为40.5g(0.45mol)，步骤(2)中缩聚反应的时间替换为6.0h，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that the amount of dimethyl carbonate is adjusted to 40.5g (0.45mol), the time of polycondensation reaction in step (2) is replaced by 6.0h, and other conditions are completely compared with Example 1 same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为28000g/mol，重均分子量Mw为46000g/mol。Molecular weight test: GPC test results of the product show that the polycarbonate has a number average molecular weight M n of 28000 g/mol and a weight average molecular weight M w of 46000 g/mol.
实施例28Example 28
本实施例与实施例1中的区别在于，将碳酸二甲酯替换为等摩尔的碳酸二苯酯，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that dimethyl carbonate is replaced by equimolar diphenyl carbonate, and other conditions are completely the same as in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为45000g/mol，重均分子量Mw为75000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 45000g/mol and a weight average molecular weight Mw of 75000g/mol.
实施例29Example 29
本实施例与实施例1的区别在于，将碳酸二甲酯替换为等摩尔的碳酸二苯酯，所用的催化剂为四丁基磷戊二酰亚胺(0.0005mol，0.1855g)，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that dimethyl carbonate is replaced by equimolar diphenyl carbonate, the catalyst used is tetrabutylphosphoglutarimide (0.0005mol, 0.1855g), and other conditions are the same as Example 1 is exactly the same.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为44000g/mol，重均分子量Mw为71000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 44000g/mol and a weight average molecular weight Mw of 71000g/mol.
实施例30Example 30
本实施例与实施例1的区别在于，将碳酸二甲酯替换为等摩尔的碳酸二苯酯，所用的催化剂为四丁基磷六氢邻苯二甲酰亚胺(0.0005mol，0.2055g)，其他条件与实施例1相比完全相同。The difference between this embodiment and Example 1 is that dimethyl carbonate is replaced by equimolar diphenyl carbonate, and the catalyst used is tetrabutylphosphine hexahydrophthalimide (0.0005mol, 0.2055g) , other conditions compared with
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为40000g/mol，重均分子量Mw为66000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 40000g/mol and a weight average molecular weight Mw of 66000g/mol.
实施例31Example 31
本实施例与实施例1中的区别在于，将异山梨醇替换为等摩尔的异甘露醇，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that isosorbide is replaced by equimolar isomannide, and other conditions are exactly the same as those in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为17000g/mol，重均分子量Mw为28000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 17000g/mol and a weight average molecular weight Mw of 28000g/mol.
实施例32Example 32
本实施例与实施例1的区别在于，将异山梨醇替换为等摩尔的双酚A，碳酸二甲酯替换为等摩尔的碳酸二苯酯，所用的催化剂为四丁基磷1,8-萘二甲酰亚胺(0.0005mol，0.2275g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that isosorbide is replaced by equimolar bisphenol A, dimethyl carbonate is replaced by equimolar diphenyl carbonate, and the catalyst used is
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为41000g/mol，重均分子量Mw为67000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 41000g/mol and a weight average molecular weight Mw of 67000g/mol.
实施例33Example 33
本实施例与实施例1的区别在于，将异山梨醇替换为等摩尔的双酚A，碳酸二甲酯替换为等摩尔的碳酸二苯酯，所用的催化剂为四丁基磷琥珀酰亚胺(0.0005mol，0.1785g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that isosorbide is replaced by equimolar bisphenol A, dimethyl carbonate is replaced by equimolar diphenyl carbonate, and the catalyst used is tetrabutylphosphorusuccinimide (0.0005mol, 0.1785g), other conditions are exactly the same as in Example 1.
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为42000g/mol，重均分子量Mw为69000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 42000g/mol and a weight average molecular weight Mw of 69000g/mol.
实施例34Example 34
本实施例与实施例1的区别在于，将异山梨醇替换为等摩尔的双酚A，碳酸二甲酯替换为等摩尔的碳酸二苯酯，所用的催化剂为四丁基磷1,2-环戊二甲酰亚胺(0.0005mol，0.1985g)，其他条件与实施例1相比完全相同。The difference between this example and Example 1 is that isosorbide is replaced by equimolar bisphenol A, dimethyl carbonate is replaced by equimolar diphenyl carbonate, and the catalyst used is
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为38000g/mol，重均分子量Mw为63000g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight Mn of 38000g/mol and a weight average molecular weight Mw of 63000g/mol.
实施例35Example 35
本实施例中以异山梨醇、碳酸二甲酯、1,4-苯二甲醇为原料，在四丁基磷邻苯二甲酰亚胺催化下制备一种聚碳酸酯，反应式如下：In this example, isosorbide, dimethyl carbonate, and 1,4-benzenedimethanol are used as raw materials to prepare a polycarbonate under the catalysis of tetrabutylphosphorus phthalimide. The reaction formula is as follows:
制备方法包括以下步骤：The preparation method comprises the following steps:
(1)酯交换阶段：在氮气气氛和常压下，在反应瓶中加入5.84g(0.04mol)异山梨醇、40.5g(0.45mol)碳酸二甲酯、1.38g(0.01mol)1,4-苯二甲醇和0.2025g(0.0005mol)四丁基磷邻苯二甲酰亚胺，使反应混合物在160℃反应2h，接着温度缓慢升到180℃，反应0.5h，使未反应的碳酸二甲酯和低沸点产物甲醇挥发，得到预聚物；(1) Transesterification stage: under nitrogen atmosphere and normal pressure, add 5.84g (0.04mol) isosorbide, 40.5g (0.45mol) dimethyl carbonate, 1.38g (0.01mol) 1,4 - Benzene dimethanol and 0.2025g (0.0005mol) tetrabutylphosphorus phthalimide, the reaction mixture was reacted at 160°C for 2h, then the temperature was slowly raised to 180°C, and reacted for 0.5h to make the unreacted carbonic acid di Methyl ester and low boiling product methanol are volatilized to obtain prepolymer;
(2)缩聚阶段：将步骤(1)中的温度从180℃升到250℃，真空度缓缓降到50Pa，进行1.5h的反应得到产物异山梨醇型共聚碳酸酯；(2) Polycondensation stage: the temperature in step (1) is raised from 180°C to 250°C, the vacuum is slowly reduced to 50Pa, and the reaction is carried out for 1.5h to obtain the product isosorbide-type copolycarbonate;
分子量测试：产物的GPC测试结果表明，异山梨醇型共聚碳酸酯的数均分子量Mn为37000g/mol，重均分子量Mw为61000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of the isosorbide copolycarbonate is 37000g/mol, and the weight average molecular weight Mw is 61000g/mol.
实施例36Example 36
本实施例与实施例35的区别在于，步骤(1)中反应开始前，加入1.06g(0.01mol)一缩二乙二醇，其他条件与实施例35完全相同。The difference between this example and Example 35 is that 1.06 g (0.01 mol) of diethylene glycol was added before the reaction in step (1), and other conditions were exactly the same as in Example 35.
分子量测试：产物的GPC测试结果表明，异山梨醇型共聚碳酸酯的数均分子量Mn为36000g/mol，重均分子量Mw为59000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of the isosorbide copolycarbonate is 36000g/mol, and the weight average molecular weight Mw is 59000g/mol.
实施例37Example 37
本实施例与实施例35的区别在于，步骤(1)中反应开始前，加入1.44g(0.01mol)1,4-环己二甲醇，其他条件与实施例35完全相同。The difference between this example and Example 35 is that 1.44 g (0.01 mol) of 1,4-cyclohexanedimethanol was added before the reaction in step (1), and other conditions were exactly the same as in Example 35.
分子量测试：产物的GPC测试结果表明，异山梨醇型共聚碳酸酯的数均分子量Mn为34000g/mol，重均分子量Mw为57000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of the isosorbide copolycarbonate is 34000g/mol, and the weight average molecular weight Mw is 57000g/mol.
实施例38Example 38
本实施例与实施例35的区别在于，步骤(1)中反应开始前，加入1.18g(0.01mol)1,6-己二醇，其他条件与实施例35完全相同。The difference between this example and Example 35 is that 1.18 g (0.01 mol) of 1,6-hexanediol was added before the reaction in step (1), and other conditions were exactly the same as in Example 35.
分子量测试：产物的GPC测试结果表明，异山梨醇型共聚碳酸酯的数均分子量Mn为33000g/mol，重均分子量Mw为54000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of the isosorbide copolycarbonate is 33000g/mol, and the weight average molecular weight Mw is 54000g/mol.
实施例39Example 39
本实施例与实施例35的区别在于，将碳酸二甲酯替换为等摩尔的碳酸二苯酯，其他条件与实施例35完全相同。The difference between this example and Example 35 is that dimethyl carbonate is replaced by equimolar diphenyl carbonate, and other conditions are exactly the same as in Example 35.
分子量测试：产物的GPC测试结果表明，异山梨醇型共聚碳酸酯的数均分子量Mn为49000g/mol，重均分子量Mw为81000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of the isosorbide copolycarbonate is 49000g/mol, and the weight average molecular weight Mw is 81000g/mol.
实施例40Example 40
本实施例与实施例35的区别在于，将异山梨醇替换为等摩尔的双酚A，其他条件与实施例35完全相同。The difference between this example and Example 35 is that isosorbide is replaced by equimolar bisphenol A, and other conditions are exactly the same as in Example 35.
分子量测试：产物的GPC测试结果表明，双酚A型共聚碳酸酯的数均分子量Mn为47000g/mol，重均分子量Mw为78000g/mol。Molecular weight test: The GPC test result of the product shows that the number average molecular weight Mn of bisphenol A copolycarbonate is 47000g/mol, and the weight average molecular weight Mw is 78000g/mol.
对比例1Comparative example 1
本对比例中以异山梨醇和碳酸二甲酯为原料，在乙酰丙酮钠催化剂的催化作用下制备一种聚碳酸酯；In this comparative example, with isosorbide and dimethyl carbonate as raw materials, a kind of polycarbonate is prepared under the catalysis of sodium acetylacetonate catalyst;
具体制备方法包括以下步骤：Concrete preparation method comprises the following steps:
(1)酯交换阶段：在氮气气氛和常压下，在反应瓶中加入36.5g(0.25mol)异山梨醇、168.75g(1.875mol)碳酸二甲酯、36.5mg乙酰丙酮钠催化剂，于98℃反应6h，接着温度缓慢升到180℃，反应1h，使未反应的碳酸二甲酯和低沸点产物甲醇挥发，得到预聚物；(1) Transesterification stage: under nitrogen atmosphere and normal pressure, add 36.5g (0.25mol) isosorbide, 168.75g (1.875mol) dimethyl carbonate, 36.5mg sodium acetylacetonate catalyst in reaction flask, in 98 ℃ for 6 hours, then slowly increase the temperature to 180 ℃, and react for 1 hour to volatilize the unreacted dimethyl carbonate and low-boiling product methanol to obtain a prepolymer;
(2)缩聚阶段：将步骤(1)中的温度从180℃升到240℃，并在此温度下进行5h的反应得到产物异山梨醇型聚碳酸酯；(2) Polycondensation stage: the temperature in step (1) is raised from 180°C to 240°C, and the reaction is carried out at this temperature for 5h to obtain the product isosorbide polycarbonate;
分子量测试：产物的GPC测试结果表明，聚碳酸酯的数均分子量Mn为15300g/mol，重均分子量Mw为25400g/mol。Molecular weight test: The GPC test result of the product shows that the polycarbonate has a number average molecular weight M n of 15300 g/mol and a weight average molecular weight M w of 25400 g/mol.
采用酰胺类离子液体活化异山梨醇的1H NMR图谱如图1所示，由图1可以看出，随着酰胺类离子液体的摩尔比从0:3升到2:3，异山梨醇3、4、2、5和1’位氢的质子峰明显移向高场。异山梨醇的质子峰向右发生位移，说明了酰胺类离子液体能高效活化异山梨醇。The 1 H NMR spectrum of isosorbide activated by amide ionic liquid is shown in Figure 1, as can be seen from Figure 1, along with the mol ratio of amide ionic liquid rises to 2:3 from 0:3,
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and those skilled in the art should understand that any person skilled in the art should be aware of any disclosure in the present invention Within the technical scope, easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.
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