CN105111418A - Method for preparing sterically regular polylactic acid on mild conditions - Google Patents
Method for preparing sterically regular polylactic acid on mild conditions Download PDFInfo
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- CN105111418A CN105111418A CN201510589810.XA CN201510589810A CN105111418A CN 105111418 A CN105111418 A CN 105111418A CN 201510589810 A CN201510589810 A CN 201510589810A CN 105111418 A CN105111418 A CN 105111418A
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- Prior art keywords
- epoxy compounds
- lactic acid
- add
- poly
- lactide
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- Granted
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000004626 polylactic acid Substances 0.000 title abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 49
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- -1 poly(lactic acid) Polymers 0.000 claims description 88
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 46
- 239000004593 Epoxy Substances 0.000 claims description 24
- 229910052804 chromium Inorganic materials 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 4
- UEMBNLWZFIWQFL-UHFFFAOYSA-N 3,5-dinitrophenol Chemical compound OC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UEMBNLWZFIWQFL-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WNBXIASKQKTACF-UHFFFAOYSA-N [O].[N+](=O)([O-])C1=C(C(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-])O Chemical compound [O].[N+](=O)([O-])C1=C(C(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-])O WNBXIASKQKTACF-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 238000001291 vacuum drying Methods 0.000 description 33
- 150000004032 porphyrins Chemical group 0.000 description 25
- 238000003756 stirring Methods 0.000 description 23
- 239000011651 chromium Substances 0.000 description 21
- 238000005406 washing Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 150000003233 pyrroles Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229940109126 chromous chloride Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 5
- 229940097267 cobaltous chloride Drugs 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- 238000000825 ultraviolet detection Methods 0.000 description 5
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical group OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YSOSYULWEYFKPL-UHFFFAOYSA-N OOCCF Chemical compound OOCCF YSOSYULWEYFKPL-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000003935 benzaldehydes Chemical class 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 101100207328 Arabidopsis thaliana TPPH gene Proteins 0.000 description 2
- MBVMOYGQFQTRCK-UHFFFAOYSA-N C1=CC(OC)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(OC)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 MBVMOYGQFQTRCK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- DRYBGKILXZPPQT-UHFFFAOYSA-N 5-bromo-2-butoxybenzaldehyde Chemical group CCCCOC1=CC=C(Br)C=C1C=O DRYBGKILXZPPQT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- HSVYWESBZIWXMS-DAXSKMNVSA-N CC/N=C\[IH]C=[IH] Chemical compound CC/N=C\[IH]C=[IH] HSVYWESBZIWXMS-DAXSKMNVSA-N 0.000 description 1
- AWKYGMBEDHZAEZ-UHFFFAOYSA-N CCCCOC1=CC=C(CCl)C=C1C=O Chemical group CCCCOC1=CC=C(CCl)C=C1C=O AWKYGMBEDHZAEZ-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- OQPITTIUWGQWER-UHFFFAOYSA-K [Al+3].[Cl-].[Cl-].[Cl-].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 OQPITTIUWGQWER-UHFFFAOYSA-K 0.000 description 1
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 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
- 230000007704 transition Effects 0.000 description 1
- 229950002929 trinitrophenol Drugs 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a method for preparing sterically regular polylactic acid. The method comprises the following steps of adding a composite catalyst and racemic lactide into a reaction vessel, adding an appropriate amount of solvent to perform dissolution, causing an obtained reaction solution to react for 20 min to 4 h at 0-25 DEG C; after the reaction is finished, adding a hydrochloric acid methanol solution to terminate the reaction, and using methanol to wash and precipitate the obtained product to obtain the sterically regular polylactic acid. According to the method, the ring opening polymerization of the racemic lactide is catalyzed on the mild conditions, the monomer conversion rate is over 90%, the polylactic acid obtained according to the preparation method is of a sterically regular structure, and the isotactic content is over 70%.
Description
Technical field
The present invention relates to technical field of macromolecules, be specifically related to a kind of method being prepared stereoregular poly(lactic acid) by rac-lactide polymerization.
Background technology
Poly(lactic acid) is a kind of polymer with good biodegradability properties, raw material sources are in biomass resources such as corns, energy-conserving and environment-protective, polyethylene can be replaced, polyvinyl chloride is applied to agricultural film, wrapping material etc., " white pollution " problem of solution, also can be applied to biological medicine aspect, as Absorbable rod surgical sewing thread, degradable material implanted and propping material, slow releasing carrier of medication etc., cause the broad interest of people.Have chiral carbon in poly(lactic acid) structural unit, the arrangement of chiral carbon can generate various stereoisomerism, comprise unformed, Quan Tong, assorted with, equal, the difference of three-dimensional arrangement directly can affect its performance.Undefined structure poly(lactic acid) second-order transition temperature is low, is 50-60 DEG C, poor mechanical property, easy degraded, stereoregular poly(lactic acid) (PLLA or poly-D-rac-Lactide) can form crystalline texture, Tc high (being greater than 170 DEG C), mechanical property is good, and degradation cycle is long.And when PLLA and poly-D-rac-Lactide form three-dimensional mixture (stereo-complex), Tc is higher, can reach 220 DEG C.Document has reported various Schiff's base alkyl/metal alkoxides catalyzer can the ring-opening polymerization of catalysis rac-lactide, prepare the poly(lactic acid) of high tacticity, but General reactions temperature high (being greater than 70 DEG C), long reaction time (a few hours), CN104211929A reports a kind of organozinc catalyst the ring-opening polymerization of catalysis rac-lactide can prepare poly(lactic acid), this catalyzer at room temperature has higher entirely with the feature of selectivity and greater activity, but catalyst preparing is loaded down with trivial details, also very harsh to the requirement of polymerizing condition, require anhydrous and oxygen-free.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, provides a kind of method utilizing rac-lactide to prepare stereoregular poly(lactic acid) in a mild condition, and in gained stereoregular poly(lactic acid), isotaxy content is more than 70%.
For solving the problems of the technologies described above, technical scheme provided by the invention is:
The preparation method of stereoregular poly(lactic acid) under a kind of mild conditions is provided, its step is as follows: add in reaction vessel by composite catalyst, rac-lactide, add dissolution with solvents, gained reaction solution is in 0-25 DEG C of reaction 20min-4 hour, add hydrochloric acid methanol termination reaction after reaction terminates, products therefrom methanol wash precipitation obtains stereoregulated poly(lactic acid);
Described composite catalyst is made up of Primary Catalysts and promotor, the mol ratio of Primary Catalysts and promotor is 1:0.5-2, wherein Primary Catalysts is metal salung M (III)-salen (M=Cr, or metalloporphyrin M (III)-porphyrin (M=Al Co), Cr, Co), promotor is the one in two-(dihalotriphenylphosphoranes base) ammonia chloride (PPNCl), dimethyl aminopyridine (DMAP), 2,6-lutidine;
The structural formula of described metal salung M (III)-salen (M=Cr, Co) is:
M=Cr or Co; R
1=o-C
6h
4, 1,2-cyclohexenyl ,-CH
2cH
2-or-CH (CH
3) CH
2-; R
2, R
3separately be selected from the aliphatic group that hydrogen, chlorine, bromine, chlorine replacement or bromine replace; X is-Cl ,-Br, CCl
3cOO-, CF
3one in COO-, 2,4-DNP oxygen base, 3,5-dinitrophenol(DNP) oxygen bases, 2，4，6-trinitrophenol oxygen base;
The structural formula of described metalloporphyrin M (III)-porphyrin (M=Al, Cr, Co) is:
M=Cr or Co or Al, R
2, R
3, R
4separately be selected from the aliphatic group that hydrogen, fluorine, chlorine, bromine, chlorine replacement or bromine replace; X is-Cl ,-OCH
2cH
3,-OCH (CH
3)
2,-Br, CCl
3cOO-, CF
3one in COO-, 2,4-DNP oxygen base, 3,5-dinitrophenol(DNP) oxygen bases, 2，4，6-trinitrophenol oxygen base;
Described solvent is epoxy compounds or the mixed solvent containing epoxy compounds, the described mixed solvent containing epoxy compounds is the mixture of epoxy compounds and tetrahydrofuran (THF) (THF), or the mixture of epoxy compounds and methylene dichloride, or the mixture of epoxy compounds and toluene, or the mixture of epoxy compounds and dioxane, account for volume ratio >=10% of mixed solvent containing epoxy compounds in the mixed solvent of epoxy compounds.
Preferably, the mol ratio of described Primary Catalysts and promotor is 1:1.
Preferably, described promotor is dimethyl aminopyridine (PPNCl).
By such scheme, described Primary Catalysts and rac-lactide mol ratio are 1:100-500.
By such scheme, described epoxy compounds is the one in propylene oxide, oxyethane, epoxy cyclohexane.
By such scheme, described rac-lactide is 0.01-0.1g/mL at described epoxy compounds or containing the mass body volume concentrations in the mixed solvent of epoxy compounds.
By such scheme, transformation efficiency >=90% of described rac-lactide.
The present invention also provides the stereoregular prepared according to aforesaid method poly(lactic acid), and described stereoregular poly(lactic acid) number-average molecular weight is 2500-10000, and molecular weight distribution is 1.1-1.5, and in poly(lactic acid), isotaxy content is 70-85%.
The synthesis route of metal salung M (III)-salen (M=Co, Cr) of the present invention is as follows:
I+MY
2+O
2→M(III)-salen-Y
Its preparation method is:
Prepare metal salung M (III)-salen (M=Cr, Co): substituted salicylic aldehydes and diamine monomer are dissolved in ethanol that (volumetric molar concentration of substituted salicylic aldehydes is 0.01-0.03M, substituted salicylic aldehydes and diamine monomer mol ratio are 2:1), add 2-3 and drip formic acid, in room temperature or back flow reaction 24h, sedimentation filtration must precipitate, precipitation uses water and washing with alcohol successively, vacuum-drying obtains salung part, then salung part is dissolved in methylene dichloride, (volumetric molar concentration of salung part is 0.05-0.1M to add the sub-cobalt of metal-salt acetic acid or chromous chloride, the mol ratio of salung part and metal-salt is 1:1.5), first room temperature reaction 24h in a nitrogen atmosphere, add halo metal-salt or replace organic acid or fortified phenol (salung part: halo metal-salt or replace organic acid or fortified phenol=1:1.5 (mol ratio)), react 24h in air atmosphere, except desolventizing, recycling water or washing with alcohol vacuum-drying obtains metal salung (SalenM, M=Cr, Co) catalyzer.
The synthesis route of metalloporphyrin M (III)-porphyrin (M=Al, Cr, Co) of the present invention is:
II+MY
2+O
2→Metal-porphyrin-YM＝Cr,Co
II+AlEt
2Cl→Al-porphyrin-Cl
II+AlMe
3→Al-porphyrin-Me
Al-porphyrin-Me+Y-H→Al-porphyrin-Y
Its preparation method is:
Phenyl aldehyde or substituted benzaldehyde and pyrroles are added in propionic acid solvent (volumetric molar concentration of phenyl aldehyde or substituted benzaldehyde is 0.4-0.5M, the mol ratio of pyrroles and phenyl aldehyde or substituted benzaldehyde is 1:1.2), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, then adds the methyl alcohol of equal volume amounts, in 0 DEG C of standing 24h after mixing, suction filtration, vacuum-drying, column purification prepares porphyrin part, then adopts following a or b step to obtain catalysis of metalloporphyrin agent:
A. metalloporphyrin (PorphyrinM, M=Cr, Co) preparation of catalyzer: porphyrin part and chromous chloride or cobaltous chloride are added in solvent dimethylformamide that (volumetric molar concentration of porphyrin part is 0.01-0.02M, the mol ratio of chromous chloride or cobaltous chloride and porphyrin part is 1.5:1), in 150-170 DEG C of reaction, took a morsel after 2 hours reaction solution, utilize ultraviolet detection, if porphyrin part unreacted is complete, add metal-salt chromous chloride or cobaltous chloride, the mol ratio of the chromous chloride added or cobaltous chloride and porphyrin part is 1.5:1, until porphyrin part all transforms, be cooled to room temperature subsequently, add hydrochloric acid, add a large amount of frozen water again, 0 DEG C of sedimentation 24 hours, filter, water or washing with alcohol, vacuum-drying, through column chromatography for separation, obtain metalloporphyrin (PorphyrinM, M=Cr, Co) catalyzer,
B. metalloporphyrin (PorphyrinM, M=Al) preparation of catalyzer: under nitrogen atmosphere, porphyrin part is dissolved in dichloromethane solvent (volumetric molar concentration is 0.05-0.1M), add the hexane solution (volumetric molar concentration is 1-2M) of diethyl aluminum chloride or trimethyl aluminium, the mol ratio of porphyrin part and diethyl aluminum chloride or trimethyl aluminium is 1:1.5, room temperature reaction 24h, decompression removing methylene dichloride, Skellysolve A is utilized to wash 3 times, vacuum-drying obtains porphyrin aluminum chloride catalyst PorphyrinAlCl or porphyrin and to methylate aluminium PorphyrinAlMe, porphyrin methylate aluminium PorphyrinAlMe dichloromethane solution in add alcohols or replace organic acid or fortified phenol that (volumetric molar concentration of PorphyrinAlMe is 0.05-0.1M, PorphyrinAlMe and alcohols or the mol ratio replacing organic acid or fortified phenol are 1:1.5), back flow reaction 24h, washing with alcohol, vacuum-drying obtains other metalloporphyrin aluminium (PorphyrinM, M=Al) catalyzer.
Beneficial effect of the present invention is: 1, the ring-opening polymerization of the present invention's (under air conditions, 0-25 DEG C) catalysis rac-lactide under relatively mild condition, and reacting 20min-4 hour monomer conversion can be greater than 90%; 2, the poly(lactic acid) that preparation in accordance with the present invention obtains has stereoregular structure, and isotactic structure content is greater than 70%.
Accompanying drawing explanation
The homogeneous phase uncoupling of the poly(lactic acid) of Fig. 1 prepared by embodiment 1
1hNMR collection of illustrative plates (structural unit-CH (the CH of polylactic acid PLA
3)-CH-part in COO-).
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
The present invention's rac-Lactide used is rac-lactide.
Embodiment 1
Prepare Primary Catalysts: in a nitrogen atmosphere, 7.7g phenyl aldehyde (72.6mmol) is dissolved in 180mL propionic acid solvent with 4.2g pyrroles (62.6mmol), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, add the methyl alcohol of equal volume amounts again, in 0 DEG C of standing 24h after mixing, suction filtration, vacuum-drying, column purification obtains tetraphenylporphyrin TPPH
2.1g tetraphenylporphyrin (1.6mmol) is dissolved in 20mL dichloromethane solvent, add the hexane solution (2.4mmol) that 2.4mL concentration is the diethyl aluminum chloride of 1M, stirring at room temperature reaction 24h, removal of solvent under reduced pressure, Skellysolve A washs 3 times, take solvent away, vacuum-drying obtains tetraphenylporphyrin aluminum chloride catalyst TPPAlCl, and structural formula is as follows:
Above-mentioned TPPAlCl catalyzer 23.6mg (0.035mmol), promotor PPNCl20mg (0.035mmol), rac-Lactide 0.504g, propylene oxide 5mL, dioxane 5mL are added (TPPAlCl catalyzer: promotor: rac-Lactide=1:1:100 (mol ratio)) in vial respectively, room temperature 25 DEG C of stirring reaction 1h, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) to stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Transformation efficiency>=90% of rac-lactide, the number-average molecular weight 2 of poly(lactic acid), 500, molecular weight distribution 1.3, in product, (wherein parameter Pm is the probability of a formation isotactic placement to isotaxy content Pm=0.78, namely-RRRRRRR-key or-SSSSSS-key connect probability, after title complex causes the open loop of a L-LA (or D-LA), continue to aggregate into the probability that has identical configuration monomer, Pr represents the assorted probability connected with vertical structure key, namely form RRSSRRSS type to connect, m represents complete in connecting, r represents assorted with connecting, in rac-lactide ring-opening polymerization resulting polymers, four-tuple also has five kinds of mode of connection, be respectively rmr, rmm, mmr, mmm and mrm, they are in homogeneous phase uncoupling
1also there will be five groups of peaks in HNMR spectrogram, chemical displacement value is respectively at 5.22,5.20,5.17,5.16,5.15ppm, integral area and Markov Equation for Calculating according to each group of peak: [mmm]=P
2 m+ (1-Pm) Pm/2, [mmr]=[rmm]=(1-Pm) Pm/2, [rmr]=[(1-Pm)
2]/2, [mrm]=[(1-Pm)
2+ Pm (1-Pm)]/2 can calculate Pm, figure mono-is the homogeneous phase uncoupling that this routine catalyst rac-lactide is polymerized the poly(lactic acid) obtained
1hNMR collection of illustrative plates (structural unit-CH (the CH of polylactic acid PLA
3)-CH-part in COO-, the distribution of [mmm], [rmm], [rmr] is see Fig. 1).
Embodiment 2
Prepare Primary Catalysts: in a nitrogen atmosphere, 9.87g aubepine (72.6mmol) is dissolved in 180mL propionic acid solvent with 4.2g pyrroles (62.6mmol), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, add the methyl alcohol of equal volume amounts again, in 0 DEG C of standing 24h after mixing, suction filtration, vacuum-drying, column purification obtains four (p-methoxy-phenyl) porphyrin.Under nitrogen atmosphere, gained four (p-methoxy-phenyl) porphyrin 1g (1.36mmol) is dissolved in 20mL dichloromethane solvent, add the hexane solution 1mL (2mmol) that concentration is the trimethyl aluminium of 2M, stirring at room temperature 24h, removal of solvent under reduced pressure, add 50mL Skellysolve A and wash 3 times, except desolventizing, add 20mL methylene dichloride and dissolve, add 2,2, 4-dinitrophenol 0.37g (72.6mmol), backflow 24h, decompression takes solvent away, washing with alcohol 3 times, take solvent away, vacuum-drying obtains porphyrin aluminium PorphyrinAl (O (C
6h
3(NO
2)
2) catalyzer, structural formula is as follows:
By above-mentioned PorphyrinAl (O (C
6h
3(NO
2)
2) catalyzer 26.6mg (0.035mmol), promotor DMAP8.54mg (0.07mmol), oxyethane 50mL and rac-Lactide 2.52g add (PorphyrinAl (O (C in vial respectively
6h
3(NO
2)
2) catalyzer: promotor: rac-Lactide=1:2:500 (mol ratio)), room temperature 25 DEG C of stirring reaction 4h, add 50mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) and stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 1,0000 of poly(lactic acid), molecular weight distribution 1.5, product P m=0.7 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 3
Prepare Primary Catalysts: in a nitrogen atmosphere, 14.23g pentafluorobenzaldehyde (72.6mmol) is dissolved in 180mL propionic acid solvent with 4.2g pyrroles (62.6mmol), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, add the methyl alcohol of equal volume amounts again, in 0 DEG C of standing 24h after mixing, suction filtration, column purification, vacuum-drying obtains four (pentafluorophenyl group) porphyrin.Gained four (pentafluorophenyl group) porphyrin ligand 1 g (1.03mmol) is dissolved in 100mLDMF solvent, add the sub-chromium (1.54mmol) of 0.189g anhydrous chlorides of rase, 150-170 DEG C of back flow reaction 2 hours, whether ultraviolet detection four (pentafluorophenyl group) porphyrin reacts completely, if do not had, add chromous chloride 0.189g (1.54mmol), till ultraviolet detection is without four (pentafluorophenyl group) porphyrin, be cooled to room temperature, add 50mL hydrochloric acid, add 300mL frozen water again, 0 DEG C of sedimentation 24 hours, wash by massive laundering after filtration, dry, alumina column chromatography separation and purification is utilized to obtain porphyrin chromium PorphyrinCrCl catalyzer, structural formula is as follows:
By above-mentioned PorphyrinCrCl catalyzer 37.6mg (0.035mmol), promotor 2,6-lutidine 3.75mg (0.035mmol), propylene oxide 5mL, rac-Lactide 0.504g, solvent dioxane 45mL adds (PorphyrinCrCl catalyzer: promotor: rac-Lactide=1:1:100 (mol ratio)) in vial respectively, room temperature 25 DEG C of stirring reaction 4h, add 20mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) to stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 5,500 of poly(lactic acid), molecular weight distribution 1.4, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 4
Prepare Primary Catalysts: prepare four (pentafluorophenyl group) porphyrin part by method described in embodiment 3.Gained four (pentafluorophenyl group) porphyrin ligand 1 g (1.03mmol) is dissolved in 100mLDMF solvent, add the sub-cobalt (1.54mmol) of 0.19g anhydrous chlorides of rase, 150-170 DEG C of back flow reaction 2 hours, whether ultraviolet detection four (pentafluorophenyl group) porphyrin reacts completely, if do not had, add cobaltous chloride 0.19g (1.54mmol), till ultraviolet detection is without four (pentafluorophenyl group) porphyrin, be cooled to room temperature, add 50mL hydrochloric acid, add 300mL frozen water again, 0 DEG C of sedimentation 24 hours, wash by massive laundering after filtration, dry, silica gel column chromatography separating purification is utilized to obtain Cobalt Porphyrin PorphyrinCoCl catalyzer, structural formula is as follows:
Above-mentioned PorphyrinCoCl catalyzer 37.3mg (0.035mmol), promotor PPNCl40mg (0.07mmol), oxyethane 10mL, rac-Lactide 0.504g (3.5mmol) are added (PorphyrinCoCl catalyzer: promotor: rac-Lactide=1:2:100 (mol ratio)) in vial respectively, room temperature 25 DEG C of stirring reaction 4h, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) to stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 4,500 of poly(lactic acid), molecular weight distribution 1.3, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 5
Prepare Primary Catalysts: in a nitrogen atmosphere, 13.43g p-bromobenzaldehyde (72.6mmol) is dissolved in 180mL propionic acid solvent with 4.2g pyrroles (62.6mmol), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, add the methyl alcohol of equal volume amounts again, in 0 DEG C of standing 24h after mixing, suction filtration, vacuum-drying obtains four (to bromophenyl) porphyrin.Under nitrogen atmosphere, gained four (to bromophenyl) porphyrin 1g (1.07mmol) is dissolved in 20mL dichloromethane solvent, add the hexane solution 0.8mL (1.6mmol) that concentration is the trimethyl aluminium of 2M, stirring at room temperature reaction 24h, removal of solvent under reduced pressure, add 50mL Skellysolve A and wash 3 times, except desolventizing, add 20mL methylene dichloride to dissolve, add trichoroacetic acid(TCA) 0.26g (1.6mmol), backflow 24h, solvent is taken in decompression away, washing with alcohol 3 times, except desolventizing, vacuum-drying obtains porphyrin aluminium PorphyrinAl (OOCCCl
3) catalyzer, structural formula is as follows:
By above-mentioned PorphyrinAl (OOCCCl
3) catalyzer 39mg (0.035mmol), promotor PPNCl20mg (0.035mmol), rac-Lactide 0.504g (3.5mmol), epoxy cyclohexane 2mL, methylene dichloride 18mL add (PorphyrinAl (OOCCCl in vial respectively
3) catalyzer: promotor: rac-Lactide=1:1:100 (mol ratio)), room temperature 25 DEG C of stirring reaction 4h, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) and stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 7,500 of poly(lactic acid), molecular weight distribution 1.2, product P m=0.85 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 6
Prepare Primary Catalysts: in a nitrogen atmosphere, 7.7g phenyl aldehyde (72.6mmol) is dissolved in 180mL propionic acid solvent with 4.2g pyrroles (62.6mmol), back flow reaction 24h, after back flow reaction terminates, solution is concentrated into the half of original volume, add the methyl alcohol of equal volume amounts again, in 0 DEG C of standing 24h after mixing, suction filtration, vacuum-drying, column purification obtains tetraphenylporphyrin TPPH
2.1g tetraphenylporphyrin (1.6mmol) is dissolved in 20mL dichloromethane solvent, adds the hexane solution (2.4mmol) that 1.2mL concentration is the trimethyl aluminium of 2M, stirring at room temperature reaction 24h, removal of solvent under reduced pressure, Skellysolve A washs 3 times, takes solvent away, adds 20mL methylene dichloride, add ethanol 0.11g, back flow reaction 24h, takes solvent away, washing with alcohol 3 times, vacuum-drying obtains porphyrin aluminium PorphyrinAl (OEt) catalyzer, and structural formula is as follows:
Above-mentioned PorphyrinAl (OEt) catalyzer 23.9mg (0.035mmol), promotor PPNCl10mg (0.0175mmol), rac-Lactide 0.504g (3.5mmol), propylene oxide 15mL, toluene 5mL are added (PorphyrinAl (OEt) catalyzer: promotor: rac-Lactide=1:0.5:100 (mol ratio)) in vial respectively, room temperature 25 DEG C of stirring reaction 2h, add 20mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) to stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 8,500 of poly(lactic acid), molecular weight distribution 1.1, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 7
Prepare Primary Catalysts: by 2g3, 5-dimethyl salicylic aldehyde (13.3mmol) is dissolved in 50mL ethanol, be added dropwise to 0.44mL1, 2-quadrol (6.65mmol), add 2-3 and drip formic acid, room temperature reaction 24h, 0 DEG C of sedimentation 24h, filter, then 3 times are washed successively with water, washing with alcohol 3 times, vacuum-drying prepares 3, 5-dimethyl salicylyl contracting quadrol (Salen part), get 1g3, 5-dimethyl salicylyl contracting ethylene diamine ligand (3mmol) is dissolved in 30mL dichloromethane solvent, add the sub-chromium (4.5mmol) of 0.57g anhydrous chlorides of rase, first stirring at room temperature reacts 24h in a nitrogen atmosphere, add 1.03g2, 4, 6-trinitrophenol (4.5mmol), blowing air, stirring at room temperature 24 hours, take solvent away, add 100mL water washing, filter, wash 3 times, washing with alcohol 3 times, vacuum-drying obtains salung chromium SalenCr (OC
6h
2(NO
2)
3) catalyzer, structural formula is as follows:
By above-mentioned SalenCr (OC
6h
2(NO
2)
3) catalyzer 21mg (0.035mmol), promotor PPNCl20mg (0.035mmol), oxyethane 10mL and rac-Lactide 0.504g (3.5mmol), solvent THF10mL add (SalenCr (OC in vial respectively
6h
2(NO
2)
3) catalyzer: promotor: rac-Lactide=1:1:100 (mol ratio)), room temperature 25 DEG C of stirring reaction 2h, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) and stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 5,500 of poly(lactic acid), molecular weight distribution 1.3, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 8
Prepare Primary Catalysts: be dissolved in 50mL ethanol by the 2g3-tertiary butyl-5-chloromethyl salicylaldehyde (8.8mmol), be added dropwise to 0.38mL1, 2-propylene diamine (4.4mmol), add 2-3 and drip formic acid, room temperature reaction 24h, 0 DEG C of sedimentation 24h, filter, then 3 times are washed successively with water, washing with alcohol 3 times, the 3-tertiary butyl-5-chloromethyl salicylyl contracting propylene diamine (Salen part) is prepared in vacuum-drying, get the 1g3-tertiary butyl-5-chloromethyl salicylyl contracting propylene diamine part (2mmol) and be dissolved in 30mL dichloromethane solvent, add the sub-chromium (3mmol) of 0.375g anhydrous chlorides of rase, first stirring at room temperature 24h in a nitrogen atmosphere, add 0.3mL trifluoroacetic acid (3mmol), blowing air, stirring at room temperature 24 hours, take solvent away, add 100mL water washing, filter, wash 3 times, ethanol washes 3 times, vacuum-drying obtains salung chromium SalenCr (OOCCF
3) catalyzer, structural formula is as follows:
By above-mentioned SalenCr (OOCCF
3) catalyzer 23mg (0.035mmol), two-(dihalotriphenylphosphoranes base) ammonium chloride PPNCl40mg (0.07mmol), oxyethane 10mL, rac-Lactide 0.504g (3.5mmol) add (SalenCr (OOCCF in vial respectively
3) catalyzer: promotor: rac-Lactide=1:2:100 (mol ratio)), room temperature 0 DEG C of stirring reaction 4h, adds 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) and stops, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 5,500 of poly(lactic acid), molecular weight distribution 1.3, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 9
Prepare Primary Catalysts: be dissolved in 50mL ethanol by the 2g3-tertiary butyl-5-bromosalicylaldehyde (7.8mmol), add 0.425g O-Phenylene Diamine (3.9mmol), add 2-3 and drip formic acid, back flow reaction 24h, 0 DEG C of sedimentation 24h, filter, then 3 times are washed successively with water, washing with alcohol 3 times, the 3-tertiary butyl-5-bromine salicylyl contracting O-Phenylene Diamine (Salen part) is prepared in vacuum-drying, get the 1g3-tertiary butyl-5-bromine salicylyl contracting O-Phenylene Diamine part (1.7mmol) and be dissolved in 30mL dichloromethane solvent, add the sub-cobalt of 0.637g tetra-hydration acetic acid, first stirring at room temperature 24h in a nitrogen atmosphere, add 0.468g2, 2, 4-dinitrophenol, blowing air, stirring at room temperature 24 hours, take solvent away, add 100mL water washing, filter, wash 3 times, washing with alcohol 3 times, vacuum-drying obtains salung cobalt SalenCo (OC
6h
3(NO
2)
2) catalyzer, structural formula is as follows:
By above-mentioned SalenCo (OC
6h
3(NO
2)
2) catalyzer 29mg (0.035mmol), promotor 2,6-lutidine 7.58mg (0.07mmol), oxyethane 10mL, rac-Lactide 0.504g (3.5mmol) add (SalenCo (OC in vial respectively
6h
3(NO
2)
2) catalyzer: promotor: rac-Lactide=1:2:100 (mol ratio)), room temperature 25 DEG C of stirring reaction 4h, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) and stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 4,500 of poly(lactic acid), molecular weight distribution 1.3, product P m=0.8 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
Embodiment 10
Prepare Primary Catalysts: by 2g3, 5-di-tert-butyl salicylaldehyde (8.5mmol) is dissolved in 50mL ethanol, add 0.52mL1, 2-cyclohexanediamine (4.25mmol), add 2-3 and drip formic acid, stirring at room temperature 24h, 0 DEG C of sedimentation 24h, filter, then 3 times are washed successively with water, washing with alcohol 3 times, vacuum-drying prepares 3, 5-di-t-butyl salicylyl contracting cyclohexanediamine (Salen part), get 1g (1.8mmol) 3, 5-di-t-butyl salicylyl contracting cyclohexanediamine part is dissolved in 30mL dichloromethane solvent, add the sub-chromium (2.7mmol) of 0.34g anhydrous chlorides of rase, first stirring at room temperature reacts 24h in a nitrogen atmosphere, add 0.11gLiCl, blowing air, stirring at room temperature 24 hours, take solvent away, add 100mL water washing, filter, ethanol washes 3 times, vacuum-drying obtains salung chromium SalenCrCl catalyzer, structural formula is as follows:
Above-mentioned SalenCrCl catalyzer 22.7mg (0.036mmol), promotor PPNCl20mg (0.036mmol), rac-Lactide 0.518g, propylene oxide 10mL are added (SalenCrCl catalyzer: promotor: rac-Lactide=1:1:100 (mol ratio)) in vial respectively, 25 DEG C of stirring reaction 20min, add 10mL hydrochloric acid methanol (mass percentage concentration of HCl is 1%) to stop, removal of solvent under reduced pressure.The a large amount of methanol wash of polymkeric substance, vacuum-drying obtains white adipose adoption ester PLA.Polymerization yield is greater than 90%, the number-average molecular weight 4,500 of poly(lactic acid), molecular weight distribution 1.2, product P m=0.75 (Pm method of calculation are shown in embodiment 1, and distribution and the Fig. 1 of [mmm] are similar, and figure slightly).
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (6)
1. the preparation method of stereoregular poly(lactic acid) under a mild conditions, it is characterized in that step is as follows: add in reaction vessel by composite catalyst, rac-lactide, add dissolution with solvents, gained reaction solution is in 0-25 DEG C of reaction 20min-4 hour, add hydrochloric acid methanol termination reaction after reaction terminates, products therefrom methanol wash precipitation obtains stereoregulated poly(lactic acid);
Described composite catalyst is made up of Primary Catalysts and promotor, the mol ratio of Primary Catalysts and promotor is 1:0.5-2, wherein Primary Catalysts is metal salung M (III)-salen (M=Cr, or metalloporphyrin M (III)-porphyrin (M=Al Co), Cr, Co), promotor is the one in two-(dihalotriphenylphosphoranes base) ammonia chloride, dimethyl aminopyridine, 2,6-lutidine;
The structural formula of described metal salung M (III)-salen (M=Cr, Co) is:
M=Cr or Co; R
1=o-C
6h
4, 1,2-cyclohexenyl ,-CH
2cH
2-or-CH (CH
3) CH
2-; R
2, R
3separately be selected from the aliphatic group that hydrogen, chlorine, bromine, chlorine replacement or bromine replace; X is-Cl ,-Br, CCl
3cOO-, CF
3one in COO-, 2,4-DNP oxygen base, 3,5-dinitrophenol(DNP) oxygen bases, 2，4，6-trinitrophenol oxygen base;
The structural formula of described metalloporphyrin M (III)-porphyrin (M=Al, Cr, Co) is:
M=Cr or Co or Al, R
2, R
3, R
4separately be selected from the aliphatic group that hydrogen, fluorine, chlorine, bromine, chlorine replacement or bromine replace; X is-Cl ,-OCH
2cH
3,-OCH (CH
3)
2,-Br, CCl
3cOO-, CF
3one in COO-, 2,4-DNP oxygen base, 3,5-dinitrophenol(DNP) oxygen bases, 2，4，6-trinitrophenol oxygen base;
Described solvent is epoxy compounds or the mixed solvent containing epoxy compounds, the described mixed solvent containing epoxy compounds is the mixture of epoxy compounds and tetrahydrofuran (THF), or the mixture of epoxy compounds and methylene dichloride, or the mixture of epoxy compounds and toluene, or the mixture of epoxy compounds and dioxane, account for volume ratio >=10% of mixed solvent containing epoxy compounds in the mixed solvent of epoxy compounds.
2. the preparation method of stereoregular poly(lactic acid) according to claim 1, is characterized in that described Primary Catalysts and rac-lactide mol ratio are 1:100-500.
3. the preparation method of stereoregular poly(lactic acid) according to claim 1, is characterized in that described epoxy compounds is the one in propylene oxide, oxyethane, epoxy cyclohexane.
4. the preparation method of stereoregular poly(lactic acid) according to claim 1, is characterized in that described rac-lactide is 0.01-0.1g/mL at described epoxy compounds or containing the mass body volume concentrations in the mixed solvent of epoxy compounds.
5. the preparation method of stereoregular poly(lactic acid) according to claim 1, is characterized in that transformation efficiency >=90% of described rac-lactide.
6. the stereoregular poly(lactic acid) prepared according to the arbitrary described method of claim 1-5, it is characterized in that, described stereoregular poly(lactic acid) number-average molecular weight is 2500-10000, and molecular weight distribution is 1.1-1.5, and in poly(lactic acid), isotaxy content is 70-85%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105949449A (en) * | 2016-05-15 | 2016-09-21 | 武汉理工大学 | Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst |
| CN111363127A (en) * | 2020-04-02 | 2020-07-03 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
| CN116217902A (en) * | 2023-03-24 | 2023-06-06 | 吉林大学 | Preparation method of high-stereoregularity polylactide |
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| Title |
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| RYOHEI ISHII ET AL: ""Stereoselective Bulk Polymerization of Racemic Lactide for Stereoblock Poly(racemic lactide) Using an Achiral Aluminum Complex"", 《POLYMER JOURNAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949449A (en) * | 2016-05-15 | 2016-09-21 | 武汉理工大学 | Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst |
| CN105949449B (en) * | 2016-05-15 | 2019-07-23 | 武汉理工大学 | It is used to prepare polyethers-polylactide-fatty poly-ester carbonate ternary block polymer composite catalyst and its application |
| CN111363127A (en) * | 2020-04-02 | 2020-07-03 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
| CN111363127B (en) * | 2020-04-02 | 2021-05-14 | 山西大学 | Method for catalyzing ring opening polymerization of cyclic ester by nitrogen heteroaromatic ring |
| CN116217902A (en) * | 2023-03-24 | 2023-06-06 | 吉林大学 | Preparation method of high-stereoregularity polylactide |
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