CN115232102A - Preparation method and production device of lactide - Google Patents
Preparation method and production device of lactide Download PDFInfo
- Publication number
- CN115232102A CN115232102A CN202211083222.5A CN202211083222A CN115232102A CN 115232102 A CN115232102 A CN 115232102A CN 202211083222 A CN202211083222 A CN 202211083222A CN 115232102 A CN115232102 A CN 115232102A
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- CN
- China
- Prior art keywords
- sulfonic acid
- lactide
- acid
- lactic acid
- reaction
- Prior art date
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 65
- 239000004310 lactic acid Substances 0.000 claims abstract description 64
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 22
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 31
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 3
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- IQOJIHIRSVQTJJ-UHFFFAOYSA-N 3-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Cl)=C1 IQOJIHIRSVQTJJ-UHFFFAOYSA-N 0.000 claims description 3
- KWXICGTUELOLSQ-UHFFFAOYSA-N 4-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-N 0.000 claims description 3
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- LEDKKDPOPIKMSZ-UHFFFAOYSA-N 2,4,5-trichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl LEDKKDPOPIKMSZ-UHFFFAOYSA-N 0.000 claims description 2
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 claims description 2
- GWGBNENHEGYJSN-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GWGBNENHEGYJSN-UHFFFAOYSA-N 0.000 claims description 2
- LFXZSGVZSSMCMB-UHFFFAOYSA-N 2,5-dichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(Cl)=CC=C1Cl LFXZSGVZSSMCMB-UHFFFAOYSA-N 0.000 claims description 2
- IRLYGRLEBKCYPY-UHFFFAOYSA-N 2,5-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(C)C(S(O)(=O)=O)=C1 IRLYGRLEBKCYPY-UHFFFAOYSA-N 0.000 claims description 2
- JDZQIEWYWDTUEW-UHFFFAOYSA-N 2,6-dichloro-3-nitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C(Cl)C=CC([N+]([O-])=O)=C1Cl JDZQIEWYWDTUEW-UHFFFAOYSA-N 0.000 claims description 2
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 claims description 2
- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 claims description 2
- FKBTZADMCXPVSF-UHFFFAOYSA-N 4-chloro-3-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C(C=O)=C1 FKBTZADMCXPVSF-UHFFFAOYSA-N 0.000 claims description 2
- RPKWNMFDAOACCX-UHFFFAOYSA-N 4-chloro-3-nitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 RPKWNMFDAOACCX-UHFFFAOYSA-N 0.000 claims description 2
- WVSYONICNIDYBE-UHFFFAOYSA-N 4-fluorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(F)C=C1 WVSYONICNIDYBE-UHFFFAOYSA-N 0.000 claims description 2
- XSAOGXMGZVFIIE-UHFFFAOYSA-N 4-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=O)C=C1 XSAOGXMGZVFIIE-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical class [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229960000448 lactic acid Drugs 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000008054 sulfonate salts Chemical class 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 69
- 238000012360 testing method Methods 0.000 description 46
- 238000000605 extraction Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 16
- 230000003068 static effect Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 15
- -1 antimony dodecyl benzene sulfonate Chemical compound 0.000 description 15
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000004626 polylactic acid Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 229920000747 poly(lactic acid) Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 229940101629 l- methyl lactate Drugs 0.000 description 5
- 229910001510 metal chloride Inorganic materials 0.000 description 5
- LPEKGGXMPWTOCB-VKHMYHEASA-N methyl (S)-lactate Chemical compound COC(=O)[C@H](C)O LPEKGGXMPWTOCB-VKHMYHEASA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- LZCLXQDLBQLTDK-BYPYZUCNSA-N ethyl (2S)-lactate Chemical compound CCOC(=O)[C@H](C)O LZCLXQDLBQLTDK-BYPYZUCNSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- DFGPKYJVFROPJB-UHFFFAOYSA-L zinc;3-nitrobenzenesulfonate Chemical compound [Zn+2].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1.[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 DFGPKYJVFROPJB-UHFFFAOYSA-L 0.000 description 3
- KWXICGTUELOLSQ-UHFFFAOYSA-M 4-dodecylbenzenesulfonate Chemical compound CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- JNJXZCHAIDWRLM-UHFFFAOYSA-N 2-methylbenzenesulfonic acid;zinc Chemical compound [Zn].CC1=CC=CC=C1S(O)(=O)=O JNJXZCHAIDWRLM-UHFFFAOYSA-N 0.000 description 1
- ALVPDCHBQRCKRQ-UHFFFAOYSA-N 4-chloro-3,5-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 ALVPDCHBQRCKRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RQPOKPOLPFYXHS-UHFFFAOYSA-N toluene;zinc Chemical compound [Zn].CC1=CC=CC=C1 RQPOKPOLPFYXHS-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- DUTBLPJAUDMXQT-UHFFFAOYSA-L zinc;2-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=CC=C1S([O-])(=O)=O.CC1=CC=CC=C1S([O-])(=O)=O DUTBLPJAUDMXQT-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of material synthesis, and particularly provides a preparation method and a production device of lactide, wherein the preparation method of the lactide comprises the following steps: (1) Performing polycondensation reaction on lactic acid monomers under the action of a catalyst to obtain oligomeric lactic acid; (2) Carrying out depolymerization reaction on the low-polymer lactic acid to obtain lactide; the catalyst is sulfonate. Compared with the prior art, the preparation method of the lactide provided by the invention adopts the sulfonate as the catalyst, has high reaction speed, avoids the product purification problem brought to subsequent products by introducing other additives compared with the conventional method of cracking by adopting a solvent, reduces the production cost, improves the yield of the lactide, and can be used for industrial production of the lactide.
Description
Technical Field
The invention relates to the technical field of material synthesis, in particular to a preparation method and a production device of lactide.
Background
Polylactic acid (PLA) is based on biomass resources and can degrade green high polymer materials, and has the advantages of good biocompatibility, bioabsorbability and the like. PLA has excellent biodegradability, and can be completely degraded by microorganisms in soil after being discarded to generate CO 2 And water, and no pollution is caused to the environment. PLA also has the characteristic of saving resources, and can reduce solid waste pollutionAnd (4) conversion, reclamation and harmlessness. PLA mechanical property is excellent, and simultaneously the performances of permeability resistance, glossiness, transmittance, processing and the like of the PLA are similar to those of polystyrene, and various disposable products can be prepared by adopting the processes of injection molding, plastic suction molding, melt spinning and the like to replace the existing non-degradable plastic or fiber products.
PLA can be synthesized by direct polycondensation of lactic acid or by ring-opening polymerization of lactide. The direct polycondensation method is to directly polycondense lactic acid into PLA under the action of a catalyst. The method is simple, but the polymerization reaction temperature is high, the molecular weight of the polymerization product is low, the color of the product is dark, and the mechanical property of the product is poor. The ring-opening polymerization method is also called as a two-step method, firstly lactic acid is dehydrated under the action of a catalyst to generate oligomeric lactic acid, then the oligomeric lactic acid is cracked at high temperature to generate lactide, and the lactide is subjected to ring-opening polymerization under the action of the catalyst to generate PLA.
Patent application CN102675277A proposes a preparation method of lactide, in which a surfactant is added into lactic acid to perform dehydration reaction to obtain lactic acid oligomer, and then the lactic acid oligomer is depolymerized at high temperature and distilled under vacuum condition to obtain the lactide. However, this solution does not solve the problem of coking and carbonization during the cracking of the oligolactic acid.
Disclosure of Invention
In view of the above, the present invention provides a method and an apparatus for preparing lactide, which can reduce the residence time of lactic acid oligomer at high temperature, solve the problems of coking and carbonization of the low-poly lactic acid during the preparation of lactide, improve the purity of lactide, and simultaneously improve the production efficiency of lactide, thereby reducing the production cost of lactide and promoting the industrialization process of the product.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing lactide, comprising:
(1) Performing polycondensation reaction on lactic acid monomers under the action of a catalyst to obtain oligomeric lactic acid;
(2) Carrying out depolymerization reaction on the low-polymer lactic acid to obtain lactide;
the catalyst is sulfonate.
In the invention, lactic acid monomers are subjected to polycondensation reaction under the action of a catalyst to obtain oligomeric lactic acid; the mass ratio of the catalyst to the lactic acid monomer is (0.01-10): 100, more preferably (0.5 to 6): 100, respectively;
the lactic acid monomer used in the invention is one or more of lactic acid, methyl lactate and ethyl lactate, and is more preferably L-lactic acid, L-methyl lactate or L-ethyl lactate; the purity of the lactic acid monomer used in the invention is 80-100%, and more preferably 85-100%;
the catalyst used in the invention is sulfonate; the sulfonate is preferably a substituted benzene sulfonate, and more preferably a substituted or unsubstituted alkyl sulfonate or a substituted or unsubstituted aryl sulfonate;
the sulfonic acid in the sulfonate is selected from p-toluenesulfonic acid, 2-methylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, dodecylbenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,6-trinitrobenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 4-chloro-3-formylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 4-ethylbenzenesulfonic acid, 4-fluoro-benzenesulfonic acid, 4-isopropylbenzenesulfonic acid, 2,6-dichloro-3-nitrobenzenesulfonic acid, 4-formylbenzenesulfonic acid, 4-bromobenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid and 4-chloro-3,5-dinitrobenzenesulfonic acid, and further preferably at least one of 2-methylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-nitrobenzenesulfonic acid, dodecylbenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, 4-ethylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid and p-toluenesulfonic acid;
the metal ion in the sulfonate is at least one selected from tin, zinc, antimony and lanthanum.
The sulfonate of the invention is preferably one or more of zinc 2-methyl benzene sulfonate, stannous 2-nitrobenzene sulfonate, zinc 3-nitrobenzene sulfonate, antimony dodecyl benzene sulfonate, lanthanum 4-nitrobenzene sulfonate, antimony 3-chlorobenzene sulfonate, stannous 4-dodecyl benzene sulfonate, lanthanum 4-ethyl benzene sulfonate, antimony 2,4-dimethyl benzene sulfonate and stannous p-toluene sulfonate.
In the context of the present invention, the term "substituted" means that one or more (for example 1, 2, 3 or 4) atoms (for example hydrogen atoms) or radicals (for example triflate groups) on the indicated radical are replaced by other atoms or radicals, provided that the indicated radical in the present case satisfies the valence requirements and forms a stable compound after substitution. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds. If a substituent is described as "optionally substituted with …," that substituent may be unsubstituted or substituted. If a first substituent is described as being optionally substituted with one or more of the list of second substituents, one or more hydrogen atoms in the first substituent may be replaced by one or more of the list of second substituents, either individually (indevidually) or each independently (independently), or not.
In the present invention, the term "alkylsulfonate" refers to a group of organic compounds in which a sulfo group is linked to a hydrocarbon group, wherein alkyl refers to a straight-chain or branched aliphatic hydrocarbon group, and alkyl includes (but is not limited to) methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and the like. The alkyl sulfonates in the present invention are optionally substituted with one or more substituents (e.g., halogen).
In the present invention, the term "arylsulfonate" refers to an organic compound in which a sulfo group is connected to an aryl group, wherein the aryl group refers to a monocyclic or fused polycyclic aromatic hydrocarbon group having a conjugated pi-electron system, and the aryl group specifically includes (but is not limited to) phenyl, naphthyl, anthryl, phenanthryl, acenaphthenyl, azulenyl, fluorenyl, indenyl, pyrenyl, and the like. The arylsulfonate salts of the invention are optionally substituted with one or more substituents such as halogen, hydroxy, cyano, nitro, C1-6 alkyl, and the like.
The source of the sulfonate is not particularly limited in the present invention and may be commercially available or prepared according to methods well known to those skilled in the art.
In the present invention, the method for preparing the sulfonate preferably comprises: reacting the metal hydroxide with a sulfonic acid monomer to obtain a sulfonic acid metal salt; the reaction temperature is 25-100 ℃, and the reaction time is 1-20 h; the metal hydroxide is prepared by reacting metal chloride with alkali; the base is preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia; the ratio of metal chloride to base is 1:2 to 1:5, the ratio of the metal hydroxide to the benzene sulfonic acid monomer is 1:2 to 1:5.
in the invention, the reaction of the metal chloride and the alkali is carried out in an aqueous solution, the concentration of the metal chloride in water is 5-30%, the reaction temperature of the metal chloride and the alkali is 20-70 ℃, and the reaction time is 10-300 min.
The preparation method of the sulfonate specifically comprises the following steps: mixing stannous chloride, sodium hydroxide and water, reacting for 1h at 25 ℃, then adding a sulfonic acid monomer, heating to 30 ℃ for continuous reaction, cooling to room temperature after 6h, separating solid from liquid of reaction liquid, and drying the solid to obtain sulfonate;
the solid-liquid separation is preferably filtration or centrifugation; the method for filtering and drying is not particularly limited in the invention, and the technical scheme of filtering and drying known to those skilled in the art can be adopted; in the present invention, the drying is preferably carried out by heating under vacuum, the drying time is preferably 12 to 48 hours, most preferably 24 hours, and the drying temperature is preferably 50 to 80 ℃, most preferably 70 ℃.
In the invention, the temperature of the polycondensation reaction is 100-220 ℃, and the polycondensation reaction preferably carries out normal-pressure polycondensation on the raw materials and then carries out reduced-pressure polycondensation; the time of normal pressure polycondensation is 1-15 h, the temperature is 100-220 ℃, and the pressure is 1-5000 Pa; the time of decompression polycondensation is 1-15 h, the temperature is 140-220 ℃, and the pressure is 1-1000 Pa; the polycondensation reaction is preferably carried out under vacuum conditions; the polycondensation reaction is preferably carried out under stirring, and the stirring is not particularly limited in the present invention, and a stirring method known to those skilled in the art may be employed.
The polycondensation reaction preferably comprises: mixing lactic acid monomers and a catalyst, heating to 160-200 ℃, stirring simultaneously, performing normal-pressure polycondensation, vacuumizing for performing polycondensation reaction, heating to 180-220 ℃ after P = 3000-5000Pa and 1h, simultaneously increasing the vacuum degree to 700-1000 Pa, and continuously performing polycondensation reaction to obtain oligolactic acid; the time for normal pressure polycondensation is preferably 2h to 4h, and the time for reduced pressure polycondensation is preferably 6h to 13h.
The invention carries out depolymerization reaction on the low-polymer lactic acid to obtain lactide; the molecular weight of the oligolactic acid is 400-10000, preferably 3000-5000, and the melting point of the oligolactic acid is 120-175 ℃, preferably 150-170 ℃.
In the invention, the temperature of the depolymerization reaction is 150-250 ℃, preferably 190-210 ℃, the time is 30-120 min, and the pressure is 1-1000 Pa, preferably 300Pa; the depolymerization reaction is preferably carried out under vacuum conditions.
The lactide prepared by the invention is preferably L-lactide, and the acid value of the L-lactide is 14-46 ppm.
In one embodiment of the present invention, the mass ratio of the catalyst to the lactic acid monomer is (1-6): 100, respectively; lactic acid monomer is lactic acid or methyl lactate, catalyst is stannous p-toluenesulfonate, 4-nitrobenzene lanthanum sulfonate or 3-chlorobenzene antimony sulfonate, polycondensation reaction temperature is 140-160 ℃, time is 10-17 h, pressure is 700-3000 Pa; the molecular weight of the low-polymer lactic acid is 3100-3500; the depolymerization reaction temperature is 190-210 ℃, the time is 1-2 h, and the pressure is 300Pa.
The invention also provides a lactide production device, which comprises:
a first reaction kettle;
the inlet of the second reaction kettle is connected with the outlet of the first reaction kettle;
the injection device is arranged in the second reaction kettle; and the injection device is connected with an inlet of the second reaction kettle.
In the invention, the first reaction kettle is used for carrying out polycondensation reaction on lactic acid monomers and a catalyst;
the inlet of the second reaction kettle is connected with the outlet of the first reaction kettle, and the second reaction kettle is used for depolymerization reaction of the lactic acid oligomer;
the injection device is connected with the inlet of the second reaction kettle, and the injection device is preferably an injector; the sprayer comprises a spraying main body and a spraying head, the spraying head is connected with the spraying main body through a bearing, and the spraying main body is connected with an inlet of the second reaction kettle. The injector head continuously rotates to inject through the bearing, so that uniform injection is realized; the rotating speed of the spray head is 1-100 r/min, preferably 30-80 r/min, and the spray pressure is 0.01-10 MPa, preferably 0.05-0.3 MPa; the thickness of the oligolactic acid sprayed to the wall of the second reaction kettle is 2-30 mm, preferably 4-15 mm.
In the invention, the outlet of the first reaction kettle is communicated with the inlet of the second reaction kettle through a pipeline, so that the product of the low-polymer lactic acid of the first reaction kettle enters the second reaction kettle through the pipeline.
In the invention, the lactide production device also comprises a first extraction kettle arranged in the first reaction kettle and a second extraction kettle arranged in the second reaction kettle; the inlet of the first extraction kettle is connected with the outlet of the first reaction kettle, and the first extraction kettle is used for collecting byproducts generated by the reaction of the lactic acid monomers and the catalyst; the inlet of the second extraction kettle is connected with the outlet of the second reaction kettle, and the second extraction kettle is used for collecting lactide generated by depolymerization of the lactic acid oligomer.
In the invention, the lactide production device also comprises a first heat exchanger arranged between the first reaction kettle and the first extraction kettle, a second heat exchanger arranged between the first reaction kettle and the second reaction kettle, and a third heat exchanger arranged between the second reaction kettle and the second extraction kettle; the first heat exchanger is used for cooling by-products generated by the polycondensation reaction of lactic acid monomers and catalysts, the second heat exchanger is used for heating the oligomeric lactic acid, and the third heat exchanger is used for cooling and depolymerizing the obtained lactide.
In the invention, the lactide production device also comprises a first vacuum system arranged in the first extraction kettle and a second vacuum system arranged in the second extraction kettle; an inlet of the first vacuum system is connected with an outlet of the first extraction kettle, and the first vacuum system can vacuumize the first reaction kettle and the first extraction kettle; the inlet of the second vacuum system is connected with the outlet of the second extraction kettle, and the second vacuum system can vacuumize the second reaction kettle and the second extraction kettle.
In the invention, the lactide production device also comprises a power transmission device arranged between the first reaction kettle and the second reaction kettle, and the power transmission device is preferably a melt pump; the power transmission device can convey the product of the first reaction kettle, namely the low-polymer lactic acid, to the second reaction kettle.
In the invention, the lactide production device further comprises a mixer arranged at the inlet of the first reaction kettle, and the mixer is preferably a static mixer; the mixer is used for fully mixing the lactic acid monomers and the catalyst.
In one embodiment of the present invention, the apparatus for producing lactide is specifically shown in fig. 1, wherein M1 is a static mixer, R1 is a first reaction vessel, HE1 is a first heat exchanger, E1 is a first extraction vessel, V1 is a first vacuum system, P1 is a melt pump, HE2 is a second heat exchanger, B1 is a bearing, BH1 is an ejector, R2 is a second reaction vessel, HE3 is a third heat exchanger, E2 is a second extraction vessel, and V2 is a second vacuum system.
The method comprises the steps of carrying out polycondensation reaction on lactic acid monomers under the action of a sulfonate catalyst to obtain oligomeric lactic acid, and carrying out depolymerization reaction on the oligomeric lactic acid to obtain lactide; the method adopts sulfonate as a catalyst, has high reaction speed, avoids the product purification problem brought to subsequent products by introducing other additives compared with the conventional method of cracking by adopting a solvent, reduces the production cost, improves the yield of the lactide, and can be used for industrial production of the lactide.
The invention realizes the rapid cracking of the low-polymer lactic acid in the cracking working section by a rotary jetting mode, shortens the material retention time compared with the conventional cracking method, and solves the problems of coking and carbonization caused by overlong high-temperature retention time in the cracking process of the lactic acid oligomer.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for synthesizing lactide according to an embodiment of the present invention;
FIG. 2 is a gas chromatogram of lactide produced in example 11 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To further illustrate the present invention, the following examples are provided for illustration. The starting materials used in the following examples of the present invention are all commercially available products.
The preparation method of the stannous p-toluenesulfonate catalyst in the embodiment 11 of the invention comprises the following steps:
189g of stannous chloride, 90g of sodium hydroxide and 2000mL of water are added into a 5000mL round-bottom flask, the mixture reacts for 1h at 25 ℃, then 360g of p-toluenesulfonic acid is added, the temperature is increased to 30 ℃ to start the reaction, the reaction solution is cooled to room temperature after 6h, the reaction solution is filtered to obtain a solid, and the solid is dried in a 70 ℃ vacuum drying oven for 24h to obtain the stannous p-toluenesulfonate.
The zinc 2-methylbenzenesulfonate, stannous 2-nitrobenzenesulfonate, zinc 3-nitrobenzenesulfonate, antimony dodecylbenzenesulfonate, lanthanum 4-nitrobenzenesulfonate, antimony 3-chlorobenzenesulfonate, stannous 4-dodecylbenzenesulfonate, lanthanum 4-ethylbenzenesulfonate and antimony 2,4-dimethylbenzenesulfonate in examples 2 to 10 of the present invention can be prepared by the above methods, and other benzenesulfonic acid metal salts can be prepared by the above methods.
Example 1
The structure schematic diagram of the lactide synthesis device is shown in fig. 1, wherein M1 is a static mixer, R1 is a first reaction vessel, R1 comprises a gas phase outlet and a liquid phase outlet, an inlet of R1 is connected with an outlet of M1 through a pipeline, HE1 is a first heat exchanger, an inlet of HE1 is connected with a gas phase outlet of R1 through a pipeline, E1 is a first extraction vessel, an inlet of E1 is connected with an outlet of HE1 through a pipeline, V1 is a first vacuum system, an inlet of V1 is connected with an outlet of E1 through a pipeline, P1 is a melt pump, an inlet of P1 is connected with a liquid phase outlet of R1 through a pipeline, HE2 is a second heat exchanger, an inlet of HE2 is connected with an outlet of P1 through a pipeline, B1 is a bearing, BH1 is an injector head, BH1 is connected with outlets of B1 and HE2, R2 is a second reaction vessel, an inlet of R2 is directly connected with B1, HE3 is a third heat exchanger, an inlet of HE3 is connected with an outlet of R2 through a pipeline, E2 is connected with an outlet of the second reaction vessel, and an outlet of the second reaction vessel is connected with an inlet of the vacuum system through a pipeline, and an inlet of the HE2 is connected with an inlet of the HE2 through a vacuum system.
Process for the preparation of lactide using the above described device:
1) Conveying a lactic acid monomer and a catalyst into a first reaction kettle R1 through a static mixer M1, cooling a byproduct generated in the polycondensation reaction of the lactic acid monomer and the catalyst in the R1 by using a first heat exchanger HE1, carrying out normal-pressure polycondensation on the lactic acid monomer and the catalyst in the R1, vacuumizing the R1 through a first vacuum system V1, carrying out reduced-pressure polycondensation reaction to obtain oligomeric lactic acid, and collecting the byproduct of the polycondensation reaction in a first extraction kettle E1;
2) The method comprises the steps of conveying the low-polymer lactic acid to an injection head BH1 through a melt pump P1 and a second heat exchanger HE2, wherein the injection head BH1 is connected to a bearing B1, the low-polymer lactic acid is uniformly dispersed in a second reaction kettle R2 through the injection head BH1, lactide depolymerized out from the interior of the R2 is cooled through a third heat exchanger HE3, the R2 is vacuumized through a second vacuum system V2, the low-polymer lactic acid is depolymerized in the interior of the R2, and a product lactide is collected in a second extraction kettle E2.
Example 2
2.1 conveying 900g of 100% L-lactic acid and 18g of 2-methylbenzenesulfonic acid zinc catalyst into R1 through a static mixer M1, heating to 150 ℃, starting stirring, carrying out normal-pressure polycondensation, setting the HE1 temperature to be 20 ℃, stopping distilling liquid after 3 hours, starting vacuumizing to carry out polycondensation reaction, after P =3000Pa and 1h, heating to 160 ℃, simultaneously increasing the vacuum degree to P =700Pa, and continuing the polycondensation reaction for 7 hours to obtain 711g of oligomeric lactic acid, wherein the melting point is 158 ℃.
And (3) measuring the molecular weight of the obtained polylactic acid by a potentiometric titrator according to the test conditions, and measuring the number average molecular weight of the polylactic acid to be 3900.
2.2 the oligolactic acid of example 2.1 was transferred to BH1 by HE2 at HE2 temperature of 200 ℃, and uniformly dispersed in R2 by BH1 to carry out depolymerization reaction with jet head rotation speed of 40 rpm, jet pressure of 0.1MPa, oligolactic acid covering thickness of 0.8 cm on the wall of R2 kettle, cracking vacuum degree P =300pa, he3 temperature of 65 ℃, material residence time of 1.5h, to obtain 705g of lactide with yield of 97.9%.
The gas chromatography test was performed on the lactide prepared in example 2 of the present invention, and the test results were: the L-lactide content was 96.8%.
The lactide prepared in the embodiment 2 of the invention is tested for acidity according to the method, and the test result is as follows: the acid value of lactide was 37ppm.
Example 3
3.1 conveying 900g of 100% L-lactic acid and 5g of 2-nitrobenzenesulfonic acid stannous catalyst into R1 through a static mixer M1, heating to 160 ℃, starting stirring, carrying out normal-pressure polycondensation, keeping the HE1 temperature at 20 ℃, stopping distilling the liquid after 2 hours, starting vacuumizing to carry out polycondensation reaction, increasing the vacuum degree to P =700Pa after P =3000Pa and 1h, and continuing the polycondensation reaction for 8 hours to obtain 709g of oligomeric lactic acid, wherein the melting point is 160 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator according to the above test conditions, and the number average molecular weight of the oligolactic acid was 4500.
3.2 the oligolactic acid of example 3.1 was transferred to BH1 by HE2, the temperature of HE2 was 210 ℃, the oligolactic acid was uniformly dispersed in R2 by BH1, depolymerization reaction was carried out, the rotational speed of the jet head was 30 rpm, the jet pressure was 0.2MPa, the thickness of the covering of the oligolactic acid on the wall of the R2 pot was 1 cm, the degree of vacuum of cracking P =300pa, the temperature of HE3 was 70 ℃, the residence time of the material was 0.5h, 702g of lactide was obtained, and the yield was 97.5%.
The gas chromatography test was performed on the lactide prepared in example 3 of the present invention, and the test results were: the L-lactide content was 96.3%.
The lactide prepared in example 3 of the present invention was tested for acidity according to the method described above, and the test results were: the acid value of lactide was 32ppm.
Example 4
4.1 conveying 900g of 100% L-lactic acid and 27g of zinc 3-nitrobenzenesulfonate catalyst into R1 through a static mixer M1, heating to 160 ℃, starting stirring, carrying out normal-pressure polycondensation, keeping the HE1 temperature at 20 ℃, stopping distilling the liquid after 2 hours, starting vacuumizing to carry out polycondensation reaction, heating to 170 ℃ after P =3000Pa and 1h, simultaneously increasing the vacuum degree to P =700Pa, and continuing the polycondensation reaction for 10 hours to obtain 705g of oligomeric lactic acid, wherein the melting point is 156 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator under the above-mentioned conditions, and the number average molecular weight of the oligolactic acid was 3700.
4.2 the oligolactic acid of example 4.1 was transferred to BH1 by HE2 at HE2 temperature of 190 ℃, evenly dispersed in R2 by BH1 for depolymerization reaction at jet head rotation speed of 80 rpm with jet pressure of 0.05MPa, covering the wall of R2 with oligolactic acid thickness of 0.4 cm, cracking vacuum degree P =300pa, he3 temperature of 75 ℃ and material residence time of 2h to obtain 698g of lactide with yield of 96.9%.
The gas chromatography test was performed on the lactide prepared in example 4 of the present invention, and the test results were: the L-lactide content was 97.1%.
The lactide prepared in the embodiment 4 of the present invention was tested for acidity according to the method described above, and the test results were: the acid value of lactide was 34ppm.
Example 5
5.1, 1040g of 100% L-methyl lactate and 40g of antimony dodecyl benzene sulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 170 ℃, stirring is started, normal-pressure polycondensation is carried out, the temperature of HE1 is 20 ℃, after 2 hours, liquid is not distilled, vacuumizing is started to carry out polycondensation, after P =3000Pa and 1h, the vacuum degree is increased to P =700Pa, the polycondensation is continued for 8 hours, and 702g of oligolactic acid is obtained, wherein the melting point is 161 ℃.
The molecular weight of the obtained polylactic acid is measured by a potentiometric titrator according to the test conditions, and the number average molecular weight of the polylactic acid is 4600.
5.2 the oligolactic acid of example 5.1 was transferred to BH1 by HE2, the temperature of HE2 was 200 ℃, the oligolactic acid was uniformly dispersed in R2 by BH1 for depolymerization reaction, the rotational speed of the injector head was 40 rpm, the injection pressure was 0.1MPa, the thickness of the oligolactic acid coating on the wall of the R2 pot was 0.8 cm, the cracking vacuum degree P =300Pa, the HE3 temperature was 80 ℃, the residence time of the material was 1h, 696g of lactide was obtained, and the yield was 96.7%.
The gas chromatography test was performed on the lactide prepared in example 5 of the present invention, and the test results were: the L-lactide content was 97.5%.
The lactide prepared in the embodiment 5 of the invention is tested for acidity according to the method, and the test result is as follows: the acid value of lactide was 24ppm.
Example 6
6.1, 1040g of 100% L-methyl lactate and 50g of 4-lanthanum nitrobenzenesulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 140 ℃, stirring is started, normal-pressure polycondensation is carried out, the temperature of HE1 is 20 ℃, after 4 hours, liquid is not distilled, vacuumizing is started to carry out polycondensation, after P =3000Pa and 1h, the temperature is increased to 150 ℃, the vacuum degree is increased to P =700Pa, and the polycondensation reaction is continued for 12 hours, so that 712g of oligolactic acid is obtained, and the melting point is 152 ℃.
The molecular weight of the obtained oligolactic acid is measured by a potentiometric titrator according to the test conditions, and the number average molecular weight of the oligolactic acid is 3300.
6.2 the oligolactic acid of example 6.1 was transferred to BH1 by HE2 at a temperature of 210 ℃ and homogeneously dispersed in R2 by BH1 for depolymerization reaction at a jet head rotation speed of 20 rpm at a jet pressure of 0.3MPa, the oligolactic acid covered on the wall of R2 with a thickness of 1.5 cm, a cracking vacuum P =300Pa, an HE3 temperature of 85 ℃ and a material residence time of 1h to give 707g of lactide at a yield of 98.2%.
The gas chromatography test was performed on the lactide prepared in example 6 of the present invention, and the test results were: the L-lactide content was 96.7%.
The lactide prepared in example 6 of the present invention was tested for acidity according to the method described above, and the test results were: the acid value of lactide was 46ppm.
Example 7
7.1, 1040g of 100% L-methyl lactate and 60g of 3-chlorobenzene antimony sulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 150 ℃, stirring is started, normal-pressure polycondensation is carried out, the temperature of HE1 is 20 ℃, after 3 hours, liquid is not distilled, vacuumizing is started to carry out polycondensation, after P =3000Pa and 1h, the temperature is increased to 160 ℃, the vacuum degree is increased to P =700Pa, the polycondensation reaction is continued for 10 hours, 711g of oligomeric lactic acid is obtained, and the melting point is 153 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator according to the above test conditions, and the number average molecular weight of the oligolactic acid was 3500.
7.2 the oligolactic acid of example 7.1 was transferred to BH1 via HE2 at an HE2 temperature of 190 ℃, homogeneously dispersed in R2 via BH1 for depolymerization reaction at an injector head rotation speed of 60 rpm with an injection pressure of 0.1MPa, covering the wall of the R2 pot with oligolactic acid of 0.5 cm thickness, cracking vacuum P =300pa, an he3 temperature of 90 ℃, and a material retention time of 2h, to obtain 706g of lactide with a yield of 98.1%.
The gas chromatography test was performed on the lactide prepared in example 7 of the present invention, and the test results were: the L-lactide content was 96.2%.
The lactide prepared in example 7 of the present invention was tested for acidity according to the method described above, and the test results were: the acid value of lactide was 39ppm.
Example 8
8.1, 1040g of 100% L-methyl lactate and 20g of 4-dodecylbenzene stannous sulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 150 ℃, stirring is started, the temperature of HE1 is 20 ℃, polycondensation is carried out at normal pressure, after 3 hours, liquid is not distilled, vacuumizing is started to carry out polycondensation reaction, after P =3000Pa and after 1h, the temperature is increased to 170 ℃, meanwhile, the vacuum degree is increased to P =700Pa, the polycondensation reaction is continued for 8 hours, and 710g of oligomeric lactic acid is obtained, wherein the melting point is 164 ℃.
The molecular weight of the obtained oligolactic acid is measured by a potentiometric titrator according to the test conditions, and the number average molecular weight of the oligolactic acid is 4900.
8.2 the oligolactic acid of example 8.1 was transferred to BH1 by HE2 at HE2 temperature of 200 ℃, evenly dispersed in R2 by BH1 for depolymerization reaction at jet head rotation speed of 60 rpm with jet pressure of 0.1MPa, covering the wall of R2 with oligolactic acid thickness of 0.5 cm, cracking vacuum degree P =300pa, he3 temperature of 95 ℃, material residence time of 1h, to give 705g of lactide with yield of 97.9%.
The gas chromatography test was performed on the lactide prepared in example 8 of the present invention, and the test results were: the L-lactide content was 97.8%.
The lactide prepared in the embodiment 8 of the invention is subjected to acidity test according to the method, and the test result is as follows; the acid value of lactide was 17ppm.
Example 9
9.1, 1180g of 100% L-ethyl lactate and 70g of lanthanum 4-ethyl benzene sulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 160 ℃, stirring is started, normal-pressure polycondensation is carried out, the temperature of HE1 is 20 ℃, after 2 hours, liquid is not distilled, vacuumizing is started to carry out polycondensation, after P =3000Pa and 1h, the temperature is increased to 170 ℃, the vacuum degree is increased to P =700Pa, and the polycondensation is continued for 6 hours, so that 709g of oligomeric lactic acid is obtained, and the melting point is 160 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator under the above-mentioned conditions, and the number average molecular weight of the oligolactic acid was 4100.
9.2 the oligolactic acid of example 9.1 was transferred to BH1 via HE2 at HE2 temperature of 210 ℃, evenly dispersed in R2 via BH1 for depolymerization reaction at jet head rotation speed of 30 rpm with jet pressure of 0.2MPa, covering thickness of 1 cm on R2 kettle wall with oligolactic acid, cracking vacuum P =300pa, he3 temperature of 100 ℃, material residence time of 1.5h, resulting in 703g of lactide with yield of 97.6%.
The gas chromatography test was performed on the lactide prepared in example 9 of the present invention, and the test results were: the L-lactide content was 97.3%.
The lactide prepared in example 9 of the present invention was tested for acidity according to the method described above, and the test results were: the acid value of lactide was 28ppm.
Example 10
10.1, 1180g of 100% L-ethyl lactate and 35g of 2, 4-dimethyl antimony benzenesulfonate catalyst are conveyed into R1 through a static mixer M1, the temperature is increased to 160 ℃, stirring is started, normal-pressure polycondensation is carried out, the temperature of HE1 is 20 ℃, liquid is not distilled after 2 hours, vacuum pumping is started to carry out polycondensation reaction, after P =3000Pa and 1h, the temperature is increased to 180 ℃, the vacuum degree is increased to P =700Pa, the polycondensation reaction is continued for 5 hours, 706g of oligolactic acid is obtained, and the melting point is 163 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator according to the above test conditions, and the number average molecular weight of the oligolactic acid was 4800.
10.2 the oligolactic acid of example 10.1 was transferred to BH1 by HE2 at HE2 temperature of 200 ℃, homogeneously dispersed in R2 by BH1 for depolymerization reaction at jet head rotation speed of 60 rpm and jet pressure of 0.1MPa, covering the wall of R2 with oligolactic acid of 0.5 cm thickness, cracking vacuum P =300pa, he3 temperature of 105 ℃ and material residence time of 2h to give 699g of lactide with a yield of 97.0%.
The gas chromatography test was performed on the lactide prepared in example 10 of the present invention, and the test results were: the L-lactide content was 97.6%.
The lactide prepared in the embodiment 10 of the present invention was tested for acidity according to the above method, and the test results were: the acid value of lactide was 14ppm.
Example 11
11.1 conveying 900g of 100% L-lactic acid and 9g of stannous P-toluenesulfonate catalyst into R1 through a static mixer M1, heating to 140 ℃, starting stirring, carrying out polycondensation at normal pressure, keeping the HE1 temperature at 20 ℃, stopping distilling the liquid after 4 hours, starting vacuumizing to carry out polycondensation reaction, heating to 160 ℃ after P =3000Pa and 1h, simultaneously increasing the vacuum degree to P =700Pa, and continuing the polycondensation reaction for 6 hours to obtain 713g of oligomeric lactic acid, wherein the melting point is 150 ℃.
The molecular weight of the obtained oligolactic acid was measured by a potentiometric titrator under the above-mentioned conditions, and the number average molecular weight of the oligolactic acid was found to be 3100.
11.2 the oligolactic acid of example 11.1 was transferred to BH1 by HE2 at HE2 temperature of 190 ℃, homogeneously dispersed in R2 by BH1 for depolymerization reaction at jet head rotation speed of 60 rpm and jet pressure of 0.1MPa, covering the wall of R2 with oligolactic acid of 0.5 cm thickness, cracking vacuum degree P =300pa, he3 temperature of 60 ℃ and material residence time of 1h to obtain 706g of lactide with yield of 98.1%.
The lactide prepared in example 11 of the present invention was subjected to gas chromatography tests, and the test results are shown in table 1 and fig. 2: the L-lactide content was 96.6%.
Table 1 gas chromatography data for lactide as provided in example 11 of the present invention
| Retention time (minutes) | Area of | % area | ||
| 1 | Lactic acid | 2.95 | 491 | 0.68 |
| 2 | Racemic lactide | 4.756 | 1281 | 1.77 |
| 3 | L-lactide | 5.643 | 69852 | 96.67 |
| 4 | - | 6.271 | 157 | 0.22 |
| 5 | - | 6.484 | 160 | 0.22 |
| 6 | - | 7.439 | 185 | 0.26 |
| 7 | - | 10.337 | 130 | 0.18 |
The lactide prepared in example 11 of the present invention was subjected to an acidity test, and the acid value of the lactide was measured to be 43ppm.
Comparative example 1
1.1 conveying 900g of 100% L-lactic acid and 9g of P-toluenesulfonic acid catalyst into R1 through a static mixer M1, heating to 140 ℃, starting stirring, carrying out polycondensation at normal pressure, setting the HE1 temperature at 20 ℃, starting vacuumizing for polycondensation after 4 hours, heating to 160 ℃ after P =3000Pa and 1h, simultaneously increasing the vacuum degree to P =700Pa, and continuing the polycondensation for 6 hours to obtain 715g of oligolactic acid with the melting point of 135 ℃.
And (3) measuring the molecular weight of the obtained oligomeric lactic acid by a potentiometric titrator according to the test conditions, and measuring the number average molecular weight of the oligomeric lactic acid to be 1600.
1.2 the oligolactic acid of comparative example 1.1 was transferred to BH1 by HE2, the temperature of HE2 was 190 ℃, the oligolactic acid was uniformly dispersed in R2 by BH1, depolymerization reaction was carried out, the rotational speed of the jet head was 60 rpm, the jet pressure was 0.1MPa, the thickness of the oligolactic acid covering the wall of the R2 pot was 0.5 cm, the degree of vacuum for cracking P =300pa, the temperature of HE3 was 60 ℃, the material residence time was 1h, 452g of lactide was obtained, the yield was 59.0%.
The gas chromatography test was performed on the lactide prepared in comparative example 1 of the present invention, and the test results were: the L-lactide content was 86.2%.
The lactide prepared in comparative example 1 of the present invention was subjected to an acidity test, and the acid value of the lactide was measured to be 330ppm.
Comparative example 2
2.1 conveying 900g of 100% L-lactic acid and 9g of stannous chloride catalyst into R1 through a static mixer M1, heating to 140 ℃, starting stirring, carrying out polycondensation at normal pressure, setting the HE1 temperature at 20 ℃, starting vacuumizing for polycondensation after 4 hours, heating to 160 ℃ after P =3000Pa and 1h, simultaneously increasing the vacuum degree to P =700Pa, and continuing the polycondensation for 6 hours to obtain 714g of oligolactic acid with a melting point of 148 ℃.
The molecular weight of the obtained oligolactic acid is measured by a potentiometric titrator according to the test conditions, and the number average molecular weight of the oligolactic acid is 2500.
2.2 the oligolactic acid of comparative example 2.1 was transferred to BH1 by HE2, the temperature of HE2 was 190 ℃, the oligolactic acid was uniformly dispersed in R2 by BH1, depolymerization reaction was carried out, the rotational speed of the jet head was 60 rpm, the jet pressure was 0.1MPa, the thickness of the oligolactic acid covering the wall of the R2 pot was 0.5 cm, the degree of vacuum of cracking P =300pa, the temperature of HE3 was 60 ℃, the residence time of the material was 1h, 662g of lactide was obtained, and the yield was 91.9%.
The gas chromatography test was performed on the lactide prepared in comparative example 2 of the present invention, and the test results were: the L-lactide content was 90.1%.
The lactide prepared in comparative example 2 of the present invention was subjected to an acidity test, and the acid value of the lactide was measured to be 210ppm.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for producing lactide, comprising:
(1) Performing polycondensation reaction on lactic acid monomers under the action of a catalyst to obtain oligomeric lactic acid;
(2) Carrying out depolymerization reaction on the low-polymer lactic acid to obtain lactide;
the catalyst is sulfonate.
2. The method for producing lactide according to claim 1, wherein the mass ratio of the catalyst to the lactic acid monomer is (0.01 to 10): 100.
3. the method for producing lactide according to claim 1, wherein the sulfonate is a substituted or unsubstituted alkylsulfonate or a substituted or unsubstituted arylsulfonate.
4. The method for producing lactide according to claim 3, wherein the sulfonate is a substituted benzene sulfonate.
5. The method of claim 4, wherein the sulfonic acid in the sulfonate salt is selected from at least one of p-toluene sulfonic acid, 2-methyl benzene sulfonic acid, 2-nitrobenzene sulfonic acid, 3-nitrobenzene sulfonic acid, dodecylbenzene sulfonic acid, 4-nitrobenzene sulfonic acid, 3-chlorobenzene sulfonic acid, 2,5-dichlorobenzene sulfonic acid, 2,4,6-trinitrobenzene sulfonic acid, 4-dodecylbenzene sulfonic acid, 4-chloro-3-nitrobenzene sulfonic acid, 2,4,5-trichlorobenzene sulfonic acid, 2,4-dinitrobenzene sulfonic acid, 4-chloro-3-formylbenzene sulfonic acid, 2,5-dimethyl benzene sulfonic acid, 4-ethyl benzene sulfonic acid, 4-fluoro-benzene sulfonic acid, 4-isopropyl benzene sulfonic acid, 2,6-dichloro-3-nitrobenzene sulfonic acid, 4-formylbenzene sulfonic acid, 4-bromobenzene sulfonic acid, 2,4-dimethyl benzene sulfonic acid, and 4-chloro-3432 zxft.
6. The method according to claim 1 or 3, wherein the metal ion in the sulfonate is at least one selected from tin, zinc, antimony, and lanthanum.
7. The method for producing lactide according to claim 1, wherein the molecular weight of the lactic acid oligomer is 400 to 10000.
8. The method for producing lactide according to claim 1, wherein the lactic acid monomer is one or more of lactic acid, methyl lactate and ethyl lactate.
9. The method for producing lactide according to claim 1, wherein the temperature of the polycondensation reaction is 100 to 220 ℃; the temperature of the depolymerization reaction is 150-250 ℃.
10. A lactide production apparatus, comprising:
a first reaction kettle;
the inlet of the second reaction kettle is connected with the outlet of the first reaction kettle;
the injection device is arranged in the second reaction kettle; and the injection device is connected with an inlet of the second reaction kettle.
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