WO2023222042A1 - Procédé de fabrication d'acide polylactique de poids moléculaire élevé - Google Patents
Procédé de fabrication d'acide polylactique de poids moléculaire élevé Download PDFInfo
- Publication number
- WO2023222042A1 WO2023222042A1 PCT/CN2023/094816 CN2023094816W WO2023222042A1 WO 2023222042 A1 WO2023222042 A1 WO 2023222042A1 CN 2023094816 W CN2023094816 W CN 2023094816W WO 2023222042 A1 WO2023222042 A1 WO 2023222042A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- hours
- polylactic acid
- molecular weight
- lactate
- Prior art date
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 113
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 44
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000004310 lactic acid Substances 0.000 claims abstract description 19
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 150000003903 lactic acid esters Chemical class 0.000 claims description 32
- 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 30
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical group C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 30
- 229940057867 methyl lactate Drugs 0.000 claims description 30
- 239000004970 Chain extender Substances 0.000 claims description 18
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 18
- 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 claims description 16
- 239000001119 stannous chloride Substances 0.000 claims description 16
- 235000011150 stannous chloride Nutrition 0.000 claims description 16
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- -1 cyano, carbonyl Chemical group 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229940116333 ethyl lactate Drugs 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Chemical class 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 3
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- DGHQMSLDUXOQEO-GDVGLLTNSA-N butan-2-yl (2s)-2-hydroxypropanoate Chemical compound CCC(C)OC(=O)[C@H](C)O DGHQMSLDUXOQEO-GDVGLLTNSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 claims description 3
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 claims description 3
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- BQKCABNKOFEHEG-UHFFFAOYSA-N 5H-dioxazole Chemical compound O1ON=CC1 BQKCABNKOFEHEG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- 239000002841 Lewis acid Chemical class 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001462 antimony Chemical class 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002290 germanium Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 2
- IXXMVXXFAJGOQO-UHFFFAOYSA-N tert-butyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC(C)(C)C IXXMVXXFAJGOQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 238000012643 polycondensation polymerization Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- 238000010992 reflux Methods 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 9
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- HTSABYAWKQAHBT-UHFFFAOYSA-N 3-methylcyclohexanol Chemical compound CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- ISTJMQSHILQAEC-UHFFFAOYSA-N 2-methyl-3-pentanol Chemical compound CCC(O)C(C)C ISTJMQSHILQAEC-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- NDVWOBYBJYUSMF-UHFFFAOYSA-N 2-methylcyclohexan-1-ol Chemical compound CC1CCCCC1O NDVWOBYBJYUSMF-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- XKIRHOWVQWCYBT-UHFFFAOYSA-N 3-ethylpentan-3-ol Chemical compound CCC(O)(CC)CC XKIRHOWVQWCYBT-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- UPSFTMARMOEBKQ-UHFFFAOYSA-N 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane;isocyanic acid Chemical compound N=C=O.CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 UPSFTMARMOEBKQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009655 industrial fermentation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DNFWGKJSJIGGRJ-UHFFFAOYSA-N pentan-1-ol;propan-2-ol Chemical compound CC(C)O.CCCCCO DNFWGKJSJIGGRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940065514 poly(lactide) Drugs 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
Definitions
- This application relates to the technical field of degradable material synthesis. Specifically, this application relates to a new method for manufacturing polylactic acid, especially a method for preparing polylactic acid from the polycondensation reaction of lactic acid ester monomers. In addition, the present application also relates to polylactic acid produced by this method, especially high molecular weight polylactic acid.
- Polylactic acid is a polymer with excellent biodegradability and compatibility.
- the main raw material for industrial synthesis of polylactic acid is lactic acid, and lactic acid can be obtained directly from nature (such as grain fermentation).
- the degradation products of polylactic acid are pollution-free carbon dioxide and water, which can be realized in nature through plant photosynthesis. Green cycle.
- polylactic acid has almost no pollution to the environment. It is mainly used as medical drugs, environmentally friendly materials, plastic daily necessities, textile and clothing fabrics, agricultural mulch films, decorations and fitness equipment. In an environment where environmental protection, green, harmonious and sustainable development are the direction of today's economic and social development, this non-toxic, harmless and non-irritating polymer material emerged as the times require.
- the direct polymerization method mainly involves the dehydration polymerization of lactic acid to obtain polylactic acid, but deep dehydration is difficult to carry out.
- high boiling point solvents such as dimethyl ether, toluene, xylene, etc.
- This solvent can dissolve the polymer but does not participate in the reaction.
- the by-product lactide is brought back to the reaction system through solvent reflux to avoid the decomposition of PLA and obtain PLA with low water content and high relative molecular weight.
- this method is also called azeotropic distillation method. Due to the insoluble nature of polymers, solution polymerization requires a large amount of solvent. agents and can easily cause pollution to the environment. At the same time, the use of high boiling point organic solvents will complicate the process and increase the cost of equipment. Moreover, it is relatively difficult to purify polymers, and the resulting products usually contain residual organic solvents that are difficult to remove. The molecular weight of polylactic acid produced by this direct polymerization method is often low.
- melt polycondensation method Another type of direct polymerization of lactic acid is the melt polycondensation method, which means that after the oligomers formed by melt polycondensation are granulated, crystallized and dried, the oligomers are further polymerized under appropriate temperature conditions to form small Polylactic acid chains are linked together.
- melt-solid phase polycondensation method can improve the crystallinity and relative molecular weight of PLA, this method and equipment requirements are relatively high. Generally, the reaction must be carried out under a high degree of vacuum to obtain high molecular weight PLA. In industry It is still very difficult to popularize it.
- Lactide ring-opening polymerization is a method most studied by researchers.
- the general steps of the ring-opening polymerization method are: synthesize lactide using lactic acid as raw material, and then ring-opening polymerize lactide under different conditions to form poly(lactide). Lactic acid, the specific process flow has three steps, which are: preparation, purification and ring-opening of lactide.
- the indirect polymerization method using lactide as raw material can produce high molecular weight polylactic acid products, the steps are relatively complicated and the cost is too high.
- this application provides a manufacturing method with low cost, simple process and capable of obtaining high molecular weight polylactic acid.
- this application first provides a new method for manufacturing polylactic acid in one aspect, in which a polylactic acid ester monomer is subjected to a polycondensation reaction to obtain polylactic acid.
- a method for manufacturing polylactic acid includes:
- the polylactic acid prepolymer is subjected to a transesterification reaction with an exchange reagent selected from diols and dicarboxylic acids or their anhydrides, thereby forming an intermediate in which both end groups are hydroxyl or carboxyl groups.
- an exchange reagent selected from diols and dicarboxylic acids or their anhydrides, thereby forming an intermediate in which both end groups are hydroxyl or carboxyl groups.
- the lactic acid ester monomer in the polycondensation reaction has the following structural formula:
- R represents a substituted or unsubstituted C 1 -C 20 hydrocarbyl group or a substituted or unsubstituted C 1 -C 20 heterohydrocarbyl group.
- the polycondensation reaction of lactic acid ester can be carried out under the action of catalyst.
- the catalyst used in the polycondensation reaction is a suitable acidic or alkaline substance, and the amount is 0.01wt%-50wt% based on the amount of lactic acid ester.
- the polycondensation reaction can be at a temperature of 0°C to 350°C, preferably 50°C to 300°C, more preferably 100°C to 250°C, most preferably 100°C to 200°C, and/or at a temperature of 1Pa to 20MPa, preferably 10Pa to 10MPa, even more preferably It is carried out under an absolute pressure of 0.1 kPa to 1 MPa for 0.001 hours to 500 hours, for example, 1 hour to 200 hours.
- the polycondensation reaction can be carried out in steps, such as in two steps, three steps or four steps, wherein the absolute pressure in the first step is greater than or equal to atmospheric pressure, for example from 0.1MPa to 20MPa, in the second step and optionally
- the absolute pressure in the subsequent steps is less than atmospheric pressure, for example from 0.1 kPa to less than 0.1 MPa, and/or the temperature in the second step and optional subsequent steps is greater than or equal to the temperature in the first step.
- the polycondensation reaction is carried out in three steps, wherein the absolute pressure of the third step is less than or equal to, preferably less than the absolute pressure of the second step, and/or the temperature in the third step is greater than or equal to, preferably greater than the temperature in the second step. .
- the transesterification reaction is carried out at a temperature of greater than 0°C to 300°C, such as 100°C to 200°C, for 0.01 hours to 500 hours, such as 1 hour to 100 hours.
- the chain extension reaction is carried out at a temperature of greater than 0 to 300°C, such as 100°C to 200°C, for greater than 0.01 hours to 500 hours, such as 1 to 100 hours.
- the chain extender is one or more alcohols or amine compounds with low molecular weight polyfunctional groups containing hydroxyl or amino groups, for example, selected from diisocyanate, dioxazoline and epoxy resin, such as diphenyl Methane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate (IPDI), epoxy resin, preferably diphenyl Methane diisocyanate.
- MDI diphenyl Methane diisocyanate
- TDI toluene diisocyanate
- HDI hexamethylene diisocyanate
- HMDI dicyclohexyl
- the present application also provides polylactic acid produced by the above method.
- the polylactic acid has a weight average molecular weight greater than 500; or a weight average molecular weight greater than or equal to 1,000; or a weight average molecular weight greater than 2,000; or a weight average molecular weight greater than 5,000; or a weight average molecular weight greater than 10,000.
- the weight average molecular weight of polylactic acid can be greater than 50,000, or even greater than 100,000.
- This method uses lactic acid ester as the monomer raw material, and directly polycondensates under the action of a catalyst to synthesize high molecular weight polylactic acid products, and the reaction efficiency is much higher than that of the conventional lactic acid dehydration preparation process, greatly improving the polymerization progress of the reaction. degree, increase molecular weight and yield, thereby improving the quality of the final polylactic acid product and overall production efficiency.
- This application effectively increases the molecular weight of polylactic acid synthesis while reducing costs.
- the polymerization efficiency of PLA prepared from lactic acid ester is higher than that of traditional lactic acid dehydration polymerization. This can not only improve the reaction efficiency but also significantly reduce the production cost of polylactic acid. It is a new industrial production process route with very important significance and broad development prospects.
- Hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups, such as alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (such as phenyl or benzyl groups), and the like.
- C x means that there are X carbon atoms in the modified group.
- Heterohydrocarbyl refers to a hydrocarbyl group in which at least one carbon, but not all carbons, is replaced by a heteroatom.
- heteroatoms may be selected from halogen atoms (fluorine, chlorine, bromine, iodine), phosphorus, nitrogen, sulfur, oxygen, etc.
- the "atmospheric pressure” used in this article refers to 1 standard atmospheric pressure, which is approximately 0.1MPa.
- polylactic acid refers to a polyester polymer having a main chain of repeating units with the structure shown below.
- the (weight average) molecular weight of polylactic acid is at least 500 (g/mol), and generally can reach more than 1000, that is, the number n of repeating units can be at least 7, and generally can be more than 15. It can be understood that there will be a very small amount of other end groups or linking groups in polylactic acid due to the specific process used, but this does not affect the representation of the main chain structure of polylactic acid.
- polylactic acid can generally be prepared by direct polycondensation of lactic acid and ring-opening polycondensation of lactide.
- polylactic acid obtained by the direct (dehydration) condensation polymerization method of lactic acid usually has the disadvantages of low molecular weight and very difficult further dehydration.
- Lactic acid esters are important intermediates in the process of obtaining lactic acid through traditional industrial fermentation.
- lactate ester is also widely used, such as in medicine, resin coatings, adhesives, cleaning agents, dry cleaning fluids, printing inks and other fields.
- the inventor of the present application unexpectedly discovered for the first time that polylactic acid with high molecular weight and high yield can be easily obtained when lactic acid ester is used as a monomer for polycondensation reaction and dealcoholization condensation.
- a method for manufacturing polylactic acid which includes subjecting lactic acid ester monomer to a polycondensation reaction to obtain polylactic acid.
- lactic acid ester has the following structural formula:
- R represents a substituted or unsubstituted C 1 -C 20 hydrocarbyl group or a substituted or unsubstituted C 1 -C 20 heterohydrocarbyl group.
- R is selected from linear or branched C 1 -C 20 alkyl, linear or branched C 2 -C 20 alkenyl, linear or branched C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 3 -C 20 cycloalkenyl, C 6 -C 20 aryl, C 3 -C 20 heteroaryl, C 3 -C 20 heterocycloalkyl, C 3 -C 20 hetero A group of one of cycloalkenyl and C 4 -C 20 heteroaralkyl, wherein the group is unsubstituted or selected from C 1 -C 10 Substituents in alkyl, C 1 -C 10 alkoxy, C 3 -C 10 cycloalkyl, mercapto, halogen, cyano, carbonyl or amino are mono- or disubstituted.
- R can be C 1 -C 12 alkyl, more preferably C 1 -C 6 alkyl, particularly preferably C 1 -C 4 alkyl, such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, nonyl and its isomers, decyl and its isomers, undecyl and its isomers, dodecyl and its isomers isomer.
- R is C 1 -C 4 alkyl, especially methyl.
- the manufacturing method of polylactic acid according to the present application may directly use lactic acid ester monomers, or may include a step of preparing and obtaining lactic acid ester monomers through an esterification reaction before the polycondensation reaction step.
- the lactic acid ester monomer can be prepared from the esterification reaction of lactic acid and a monohydric alcohol represented by ROH. Specifically, R is as defined above.
- the monohydric alcohol may be selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, cyclohexanemethanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol Alcohol, cetyl alcohol, heptadecanol, stearyl alcohol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, benzyl alcohol, benzene Ethanol, benzyl alcohol, naphthyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propanol, 3-methoxybutanol, vinyl alcohol , 2-aminoethanol, 2-a
- the lactate monomer may be selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, sec-butyl lactate, tert-butyl lactate esters, amyl lactate, isoamyl lactate and esters of lactic acid with C 6 -C 20 monoalcohols.
- lactate monomers are methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, sec-butyl lactate, tert-lactate Butyl ester, amyl lactate, isoamyl lactate.
- this application intends to include all lactic acid esters suitable for polycondensation reactions, it is preferred to use those lactic acid esters that are easy to obtain and preserve for transportation, such as methyl lactate, ethyl lactate, etc., which can significantly reduce the cost of obtaining lactic acid.
- the polycondensation reaction of lactic acid ester can be carried out under the action of a catalyst.
- various catalysts capable of promoting (ie catalyzing) the polycondensation of lactic acid esters can be used.
- the catalyst used in the polycondensation reaction may include a variety of acidic or basic substances.
- the catalyst used in the lactic acid ester polycondensation reaction can be selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, Lewis acid, acid salt, halide, tin salt, stannous salt, zinc salt, titanium salt, antimony salt, One or more of germanium salts, metal oxides, rare earth compounds, phosphotungstic heteropolyacids, inorganic bases, basic salts, sodium alkyl sulfonates, and organic bases.
- preferred catalysts are concentrated sulfuric acid, stannous chloride, and/or stannous octoate.
- the amount of catalyst can be appropriately selected, for example, it can be 0.01 wt% to 50 wt%, based on the amount of lactic acid ester. In some preferred embodiments, the catalyst is used in an amount of 0.5 to 10 wt%, preferably 1 to 5 wt%, based on the amount of lactic acid ester.
- the polycondensation reaction can be carried out at a temperature of 0°C to 350°C, preferably 50°C to 300°C, more preferably 100°C to 250°C, most preferably 100°C to 200°C.
- the polycondensation reaction is carried out at an absolute pressure of 1 Pa to 20 MPa, preferably 10 Pa to 10 MPa, preferably 0.1 kPa to 1 MPa, and more preferably 0.01 MPa to 1 MPa.
- the polycondensation reaction lasts for 0.001 hours to 500 hours, such as 1 hour to 200 hours. Those skilled in the art can adjust the reaction time within an appropriate range as needed.
- the inventors of the present application have found that it is advantageous according to the present application that the polycondensation reaction starting from the lactic acid ester monomer is carried out in steps, for example in two steps, three steps or four steps.
- the polycondensation reaction may be carried out at a first pressure and a first temperature for a first time, and then may be carried out at a second pressure and a second temperature for a second time after changing the degree of vacuum and/or changing the temperature.
- the polycondensation reaction can also be performed at a third pressure and a third temperature for a third time after changing the degree of vacuum and/or changing the temperature.
- the absolute pressure in the first step that is, the first pressure
- the first pressure generally needs to be greater than or equal to atmospheric pressure, for example, it can be from 0.1MPa to 20MPa, for example, from 0.1MPa to 10MPa, or from 0.1MPa to 5MPa.
- the absolute pressure in the second and subsequent steps is generally less than atmospheric pressure, for example from 0.1 kPa to less than 0.1 MPa.
- the temperatures in this step and optional subsequent steps ie the second temperature and if present a third temperature, etc., may be greater than or equal to, preferably greater than, the temperature in the first step, ie the first temperature.
- the polycondensation reaction is carried out in three steps.
- the absolute pressure in the third step that is, the third pressure
- the absolute pressure in the second step that is, the second pressure
- the third temperature can be greater than or equal to, preferably greater than, the second temperature.
- pressure can conveniently promote the discharge of small molecule products of the polycondensation reaction (i.e. monohydric alcohol), thereby further promoting polymerization and thereby increasing the molecular weight of the polymer.
- the discharged small molecule product namely monohydric alcohol
- the discharged monoalcohol can also be recycled to react with lactic acid to produce lactic acid ester, which is obviously very environmentally friendly.
- the product obtained from the reaction can be purified after the polycondensation reaction is completed. Purification can be carried out by methods known in the art.
- the weight average molecular weight of the polylactic acid product thus prepared can be at least greater than 500, generally greater than 1000, preferably greater than 2000 or 2500. In a preferred case, the weight average molecular weight of the polylactic acid product thus prepared can even be greater than 10,000.
- this application also provides a manufacturing method of polylactic acid, including the following steps:
- the polylactic acid prepolymer is subjected to a transesterification reaction with an exchange reagent selected from diols and dicarboxylic acids or their anhydrides, thereby forming an intermediate in which both end groups are hydroxyl or carboxyl groups.
- an exchange reagent selected from diols and dicarboxylic acids or their anhydrides
- step a) the obtained polylactic acid prepolymer can optionally be purified and used in subsequent steps.
- step a) regarding the "polycondensation reaction” and the purification step and what can be used for the condensation The description of the catalyst for the polymerization reaction is the same as above.
- Transesterification is optional. Whether a transesterification step is required depends on the subsequent chain extender used. This transesterification step can be omitted when the chain extender used is, for example, an epoxy resin.
- the manufacturing method of polylactic acid according to the present application may include the following steps:
- the glycol when the transesterification reaction step is adopted, as the transesterification reagent used in the transesterification reaction, the glycol can be selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, and pentanediol. , one or more of hexylene glycol, especially ethylene glycol.
- the dicarboxylic acid or anhydride thereof is selected from the group consisting of terephthalic acid, phthalic acid, One or more of malonic acid, succinic acid, butenedioic acid, glutaric acid, adipic acid, and suberic acid.
- the amount of transesterification agent used is not particularly limited.
- the glycol or dicarboxylic acid may be in a slight excess relative to the end groups of the polylactic acid chain. After the reaction, excess diol or dibasic acid can be distilled off.
- the transesterification reaction may be carried out at a temperature of greater than 0 to 300°C, such as 100°C to 200°C.
- the transesterification reaction can be carried out under an appropriate pressure, such as an absolute pressure of 0.1 kPa to 10 MPa.
- the transesterification reaction time is greater than 0 to 500 hours, for example, 1 to 100 hours.
- Those skilled in the art can select appropriate temperature, pressure and time for transesterification reaction according to actual needs. If necessary, those skilled in the art can choose to use a catalyst well known in the relevant art or not to use a catalyst in the transesterification reaction according to the selected transesterification reagent to promote the reaction.
- a polylactic acid polymer with both terminal groups being hydroxyl or carboxyl groups is obtained, which is also referred to as an intermediate polymer herein.
- polylactic acid in order to further increase the molecular weight of polylactic acid, polylactic acid (herein also referred to as intermediate polymer) can be chain extended.
- the chain extender may be selected from one or more alcohols or amine compounds or epoxy resins with low molecular weight polyfunctional groups containing hydroxyl or amino groups.
- the chain extender may be selected from epoxy resins, diisocyanates and/or dioxazolines.
- Cyanate chain extenders include, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate Isocyanate (IPDI).
- MDI diphenylmethane diisocyanate
- TDI toluene diisocyanate
- HDI hexamethylene diisocyanate
- HMDI dicyclohexyl diisocyanate
- IPDI isophorone diisocyanate
- the chain extension reaction can be carried out at a temperature of greater than 0°C to 300°C, such as 100°C to 200°C.
- the chain extension reaction can be carried out at a pressure of 0.1kPa-10MPa.
- the chain extension reaction is carried out for greater than 0 to 500 hours, such as 1 to 100 hours.
- Those skilled in the art can select appropriate temperature, pressure and time for the chain extension reaction according to actual needs. If necessary, those skilled in the art can choose to use a catalyst well known in the relevant art or not to use a catalyst in the chain extension reaction according to the selected chain extender to promote the reaction.
- the molecular weight of the intermediate polymer can be effectively increased.
- the weight average molecular weight of the polylactic acid thus prepared can be greater than 5,000, even greater than 10,000, preferably greater than 50,000.
- this application also provides polylactic acid prepared according to the above method.
- the raw materials and catalysts used in each embodiment can be obtained from the market or directly obtained according to general synthesis methods.
- the reaction pressure used is approximately atmospheric pressure.
- methyl lactate is used as an example to illustrate the synthesis route of polylactic acid in each embodiment, which can be seen in the following formula:
- MDI was added to the transesterification product obtained in the above step, and chain extension reaction was performed at 160°C for 1 hour to obtain a polylactic acid product with a weight average molecular weight of 7079 and a yield of 72.54%.
- MDI was added to the transesterification product obtained in the above step, and chain extension reaction was performed at 160°C for 1 hour to obtain a polylactic acid product with a weight average molecular weight of 9054 and a yield of 72.27%.
- the polylactic acid product was obtained with a weight average molecular weight of 2052 and a yield of 71.17%.
- the temperature of the first polymer obtained in the above step was raised to 170° C., and the polymer was evacuated at a vacuum degree of 0.05-0.09 MPa for 12 hours to obtain a polymer with a weight average molecular weight of 2357 and a yield of 59.74%.
- the temperature of the first polymer obtained in the above step was raised to 170°C, and vacuum was applied at 0.05-0.09MPa for 24 hours to obtain a polylactic acid polymer with a weight average molecular weight of 2861 and a yield of 56.65%.
- the temperature of the first polymer obtained in the above steps was raised to 170-180°C, and vacuum was evacuated at a vacuum degree of 0.09-0.095 MPa for 48 hours to obtain a polymer with a weight average molecular weight of 5633 and a yield of 59%.
- the temperature of the first polymer obtained in the above steps was raised to 170-185°C, and vacuum was evacuated at a vacuum degree of 0.09-0.096MPa for 96 hours to obtain a polymer with a weight average molecular weight of 10366 and a yield of 59.5%.
- MDI was added in portions to the transesterification product obtained in the above step, and chain extension reaction was carried out at 160°C for 2 hours to obtain a polylactic acid product with a weight average molecular weight of 50224 and a yield of 58.1%.
- MDI was added to the transesterification product obtained in the above step, and chain extension reaction was carried out at 160-170°C for 1 hour to obtain a polylactic acid product with a weight average molecular weight of 15254 and a yield of 55.7%.
- MDI was added to the transesterification product obtained in the above step, and chain extension reaction was carried out at 160-180°C for 2 hours to obtain a polylactic acid product with a weight average molecular weight of 40224 and a yield of 58.1%.
- MDI was added in portions to the transesterification product obtained in the above step, and chain extension reaction was carried out at 140-160°C for 1 hour to obtain a polylactic acid product with a weight average molecular weight of 30,381 and a yield of 56%.
- MDI was added to the transesterification product obtained in the above step, and chain extension reaction was carried out at 160-190°C for 3 hours to obtain a polylactic acid product with a weight average molecular weight of 76562 and a yield of 57.9%.
- Ethylene glycol is added to the first polymer obtained in the above step, and transesterification reaction is carried out at 140 to 170° C. for 8 hours to obtain a transesterification product.
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Abstract
La présente invention concerne un procédé de fabrication d'acide polylactique, ledit procédé comprenant les étapes suivantes : prendre un lactate en tant que matière première monomère, et soumettre celui-ci à une polymérisation par condensation sous l'action d'un catalyseur pour obtenir de l'acide polylactique. Dans le procédé, un lactate est utilisé en tant que matière première, l'efficacité de réaction est supérieure à celle de la polycondensation par déshydratation classique de l'acide lactique, le coût de production est réduit, et le poids moléculaire et les avantages économiques d'un polymère sont augmentés.
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Citations (6)
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US5247059A (en) * | 1992-01-24 | 1993-09-21 | Cargill, Incorporated | Continuous process for the manufacture of a purified lactide from esters of lactic acid |
CA2173616A1 (fr) * | 1993-10-07 | 1995-04-13 | Patrick Richard Gruber | Procede pour la production continue de lactide et de polymeres de lactide |
WO2002060891A1 (fr) * | 2001-01-31 | 2002-08-08 | Toyota Jidosha Kabushiki Kaisha | Procédé de production de lactide et procédé de production d'acide polylactique à partir d'acide lactique fermenté |
JP2002300898A (ja) * | 2001-01-31 | 2002-10-15 | Shimadzu Corp | 発酵乳酸を原料とするラクチドの製造方法及びポリ乳酸の製造方法 |
CN1557853A (zh) * | 2004-02-05 | 2004-12-29 | 哈尔滨工业大学 | 通过熔融/固相缩聚法由乳酸酯直接制备聚乳酸的方法 |
CN110684179A (zh) * | 2019-11-11 | 2020-01-14 | 上海汉禾生物新材料科技有限公司 | 一种高分子量聚乳酸的制备方法 |
-
2022
- 2022-05-18 CN CN202210544466.2A patent/CN117126383A/zh active Pending
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2023
- 2023-05-17 WO PCT/CN2023/094816 patent/WO2023222042A1/fr unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5247059A (en) * | 1992-01-24 | 1993-09-21 | Cargill, Incorporated | Continuous process for the manufacture of a purified lactide from esters of lactic acid |
CA2173616A1 (fr) * | 1993-10-07 | 1995-04-13 | Patrick Richard Gruber | Procede pour la production continue de lactide et de polymeres de lactide |
WO2002060891A1 (fr) * | 2001-01-31 | 2002-08-08 | Toyota Jidosha Kabushiki Kaisha | Procédé de production de lactide et procédé de production d'acide polylactique à partir d'acide lactique fermenté |
CN1369490A (zh) * | 2001-01-31 | 2002-09-18 | 株式会社岛津制作所 | 以发酵乳酸为原料的交酯的制造方法及聚乳酸的制造方法 |
JP2002300898A (ja) * | 2001-01-31 | 2002-10-15 | Shimadzu Corp | 発酵乳酸を原料とするラクチドの製造方法及びポリ乳酸の製造方法 |
CN1557853A (zh) * | 2004-02-05 | 2004-12-29 | 哈尔滨工业大学 | 通过熔融/固相缩聚法由乳酸酯直接制备聚乳酸的方法 |
CN110684179A (zh) * | 2019-11-11 | 2020-01-14 | 上海汉禾生物新材料科技有限公司 | 一种高分子量聚乳酸的制备方法 |
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