WO2023222042A1 - 一种高分子量聚乳酸的制造方法 - Google Patents
一种高分子量聚乳酸的制造方法 Download PDFInfo
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- 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
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- 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
本文提供了一种聚乳酸的制造方法，该方法以乳酸酯为单体原料，在催化剂作用下缩聚反应成聚乳酸。由于该方法以乳酸酯为原料，反应效率高于常规的乳酸脱水缩聚的反应效率，降低了生产成本，增加了聚合物分子量和经济效益。
Description
相关申请的交叉引用
本申请要求于2022年5月18日向中国国家知识产权局提交的第202210544466.2号专利申请的权益和优先权，在此将它们的全部内容通过引用整体并入本文中。
本申请涉及可降解材料合成技术领域。具体而言，本申请涉及一种新的制造聚乳酸的方法，特别是从乳酸酯单体的缩聚反应制备得到聚乳酸的方法。此外，本申请还涉及通过该方法制造得到的聚乳酸、特别是高分子量的聚乳酸。
聚乳酸(PLA)是一种具有优秀的生物可降解性和相容性的高分子聚合物。现在工业上合成聚乳酸主要的原料是乳酸，而乳酸又可以从大自然中直接获得(如粮食发酵)，聚乳酸的降解产物为无污染的二氧化碳和水，能够通过植物光合作用在自然界中实现绿色循环。聚乳酸作为一种完全绿色可降解的材料，对环境几乎没有污染，主要用作医疗药品、环保材料、塑料日用品、纺织服装面料、农用地膜以及装饰品和健身器材等。在环保、绿色、和谐、可持续发展是当今经济社会发展的方向的大环境下，这种无毒、无害、无刺激性的高分子材料应运而生。
当前聚乳酸的主要两类合成方法为直接聚合法和丙交酯开环聚合法。这两种方法均有其各自的优势和不足。直接聚合法主要是乳酸脱水聚合得到聚乳酸，但是深度脱水很难进行。一般采用高沸点溶剂(如二甲醚、甲苯、二甲苯等)与水共沸，从而将水排出反应体系，该溶剂能够溶解聚合物但不参与反应。副产物丙交酯通过溶剂回流带回反应体系避免了PLA分解现象，获得含水量低、相对分子量较高PLA，因此该方法也被称为共沸精馏法。因为高聚物难溶的特性，溶液聚合法需要消耗大量的溶
剂，容易对环境造成污染。同时高沸点有机溶剂的使用会使工艺流程变得复杂，提高设备的成本。而且提纯聚合物相对困难，得到的产品通常会含有残留的有机溶剂难以去除。而这种直接聚合法制得的聚乳酸分子量往往偏低。
另一种乳酸直接聚合还有熔融缩聚法，是指熔融缩聚形成的低聚物经过造粒和结晶干燥后，再将该低聚物处于合适的温度条件下进行进一步的聚合，从而将小的聚乳酸链连接起来。虽然熔融－固相缩聚法能够提升PLA的结晶度和相对分子质量，但是该方法、对设备的要求较高，一般都是在很高的真空度下进行反应才能得到高分子量的PLA，在工业上普及还有非常大的难度。
丙交酯开环聚合发是研究者们研究最多的一种方法，开环聚合法的一般步骤为：以乳酸为原料合成丙交酯，再在不同条件下将丙交酯开环聚合成聚乳酸，具体工艺流程一共有三个步骤，其分别为：丙交酯的制备，纯化及开环。以丙交酯为原料的间接聚合法虽然可以制得高分子量的聚乳酸产品，但步骤相对繁琐，成本过高。
因此，仍然需要开发一种成本低廉、工艺相对简单的提供聚乳酸、特别是高分子量聚乳酸的方法。
发明内容
针对现有技术的不足，本申请提供了一种成本低、工艺简单、能够得到高分子量聚乳酸的制造方法。
为实现以上目的，本申请首先在一个方面中提供了一种新的聚乳酸的制造方法，在该方法中，使乳酸酯单体发生缩聚反应，从而得到聚乳酸。
在另一方面中还提供了一种聚乳酸的制造方法，所述方法包括：
a)使乳酸酯单体发生缩聚反应，从而得到聚乳酸预聚物，以及任选地，对所述聚乳酸预聚物进行提纯处理；
b)任选地，使所述聚乳酸预聚物与选自二元醇和二元羧酸或其酸酐中一种的交换试剂发生酯交换反应，从而形成两端基均为羟基或羧基的中间体聚合物；
c)使所述中间体聚合物与扩链剂发生扩链反应，从而得到高分子量的聚乳酸。
在所述缩聚反应中的乳酸酯单体具有如下的结构式：
其中R表示取代或未经取代的C1-C20烃基或取代或未经取代的C1-C20杂烃基。乳酸酯的缩聚反应可以在催化剂的作用下进行。在缩聚反应中使用的所述催化剂为适合的酸性或碱性物质，用量为基于乳酸酯的用量的0.01wt％-50wt％。缩聚反应可以在0℃至350℃、优选50℃至300℃、再优选100℃至250℃、最优选100℃至200℃的温度下和/或在1Pa至20MPa、优选10Pa至10MPa、再优选0.1kPa至1MPa的绝对压力下进行0.001小时至500小时、例如1小时至200小时。
优选地，缩聚反应可以分步进行，例如分两步、分三步或分四步进行，其中第一步中的绝对压力大于等于大气压，例如从0.1MPa至20MPa，在第二步和任选的后续步骤中的绝对压力小于大气压，例如从0.1kPa至小于0.1MPa，和/或在第二步和任选的后续步骤中的温度大于等于第一步中的温度。
优选地，所述缩聚反应分三步进行，其中第三步的绝对压力小于等于、优选小于第二步的绝对压力和/或第三步中的温度大于等于、优选大于第二步中的温度。
酯交换反应在大于0至300℃，例如100℃至200℃的温度下进行0.01小时至500小时，例如1小时至100小时。
扩链反应在大于0至300℃，例如100℃至200℃的温度下进行大于0.01小时至500小时，例如1至100小时。扩链剂为选自含羟基或氨基的低分子量多官能团的醇类或胺类化合物中的一种或多种，例如，选自二异氰酸酯、二噁唑啉和环氧树脂，例如二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、环氧树脂，优选二苯基甲烷二异氰酸酯。
在又一方面中，本申请还提供了通过上述方法制造得到的聚乳酸。
所述聚乳酸具有的重均分子量大于500；或重均分子量大于或1000；或重均分子量大于2000；或重均分子量大于5000；或重均分子量大于10000。在适当的情况下，聚乳酸的重均分子量可以大于50000，甚至大于100000。
根据本申请的聚乳酸的制造方法具有如下的有益效果：
该方法以乳酸酯为单体原料，在催化剂作用下直接缩聚就可以合成高分子量的聚乳酸产品，而且反应效率远远高于常规的乳酸脱水制备工艺的反应效率，大大提高反应的聚合进行程度，增加分子量和产率，从而提升最后聚乳酸产品的品质和整体的生产效率。本申请在降低成本的同时有效提高聚乳酸合成分子量。
特别地，由乳酸酯制备PLA，聚合效率高于传统乳酸脱水聚合的效率。这样不仅可以提高反应效率还可以大幅降低聚乳酸的生产成本，是一条新的工业生产工艺路线，具有非常重要的意义和广阔的发展前景。
为了能够详细地理解本申请的技术特征和内容，下面将更详细地描述本申请的优选实施方式。虽然实施例中描述了本申请的优选实施方式，然而应该理解，可以以各种形式实现本申请而不应被这里阐述的实施方式所限制。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
定义
在本文中使用的“烃基”是指仅由氢和碳构成的一价基团。烃基包括脂肪族烃基和芳香族烃基，例如烷基、烯基、炔基、环烷基、环烯基、芳基(例如苯基或苄基)等。在本文中，Cx表示所修饰基团中具有X个碳原子。
“杂烃基”是指其中至少一个碳、但不是所有的碳被杂原子替换的烃基。
在本文中，杂原子可以选自卤素原子(氟、氯、溴、碘)、磷、氮、硫、氧等。
在本文中使用的“大气压”，即指1个标准大气压，约为0.1MPa。
在本文中，“聚乳酸”是指具有如下所示结构的重复单元为主链的聚酯类聚合物。在本文中，聚乳酸的(重均)分子量至少为500(g/mol)，一般可达1000以上，即，重复单元数n可以为至少7，一般为15以上。可以理解的是，在聚乳酸中会因为所应用的具体工艺而存在极少量的其他端基或者链接基团，但是并不影响聚乳酸主链结构的表示。
本申请的发明人意在提供一种新的改善的聚乳酸制备方法。在现有技术中，聚乳酸一般可以通过乳酸的直接缩聚和丙交酯开环的缩聚方法制备获得。然而，通过乳酸的直接(脱水)缩聚法获得的聚乳酸通常有分子量低和进一步脱水非常困难的缺点。
而乳酸酯(例如乳酸甲酯)是传统工业发酵获得乳酸过程中的重要中间体。乳酸酯在化工和医药领域中作为重要的溶剂和中间体原料，也有广泛的应用，例如应用于医药、树脂涂料、胶粘剂、清洗剂、干洗液，印刷油墨等领域。
本申请的发明人则首次意外地发现，当使用乳酸酯作为单体发生缩聚反应脱醇缩合时可以方便地获得高分子量和产量高的聚乳酸。
因此，根据本申请，提供了一种聚乳酸的制造方法，包括使乳酸酯单体发生缩聚反应，从而得到聚乳酸。
在该缩聚反应中，原则上可以使用各种合适的乳酸酯。但是为了方便缩聚反应的进行，乳酸酯具有如下结构式：
其中R表示取代或未经取代的C1-C20烃基或取代或未经取代的C1-C20杂烃基。
在一些实施方案中，R为选自直链或支链C1-C20烷基、直链或支链C2-C20烯基、直链或支链C2-C20炔基、C3-C20环烷基、C3-C20环烯基、C6-C20芳基、C3-C20杂芳基、C3-C20杂环烷基、C3-C20杂环烯基、C4-C20杂芳烷基中的一种的基团，其中所述基团为未经取代的或者被选自C1-C10
烷基、C1-C10烷氧基、C3-C10环烷基、巯基、卤素、氰基、羰基或氨基中的取代基单取代或双取代。
在一些优选的实施方案中，R可以为C1-C12烷基，再优选C1-C6烷基，特别优选为C1-C4烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基及其同分异构体、己基及其同分异构体、庚基及其同分异构体、辛基及其同分异构体、壬基及其同分异构体、癸基及其同分异构体、十一烷基及其同分异构体、十二烷基及其及其同分异构体。在一个特别优选的实施方案中，R为C1-C4烷基，特别是甲基。
根据本申请的聚乳酸的制造方法可以直接使用乳酸酯单体，也可以在缩聚反应步骤之前包括通过酯化反应制备获得乳酸酯单体的步骤。在一些实施方案中，乳酸酯单体可以由乳酸与由ROH表示的一元醇的酯化反应制备得到。具体而言，R如上文所定义。或者，一元醇可以选自甲醇、乙醇、丙醇、丁醇、戊醇、己醇、庚醇、环己烷甲醇、辛醇、壬醇、癸醇、十一醇、十二醇、十四醇、十六醇、十七醇、十八醇、环戊醇、环己醇、2-甲基环己醇、3-甲基环己醇、4-甲基环己醇、苯甲醇、苯乙醇、二苯甲醇、萘甲醇、糠醇、四氢糠醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、丙醇、3-甲氧基丁醇、乙烯醇、2-氨基乙醇、2-(乙氨基)乙醇、2-(二甲氨基)乙醇、异丙醇、异丁醇、仲丁醇、叔丁醇、2-甲基-1-丁醇、异戊醇、仲戊醇、3-戊醇、叔戊醇、仲异戊醇、4-甲基-2-戊醇、2-己醇、2-乙基丁醇、2-甲基戊醇、2-甲基-2-戊醇、2-甲基-3-戊醇、3-乙基-3-戊醇、2-庚醇、3-庚醇、2-辛醇、2-乙基己醇、3,5,5-三甲基己醇、2,6-二甲基-4-庚醇，等。
在一些优选的实施方案中，乳酸酯单体可以选自乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸仲丁酯、乳酸叔丁酯、乳酸戊酯、乳酸异戊酯以及乳酸与C6-C20一元醇形成的酯。在根据本申请的方法中，特别优选的乳酸酯单体是乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸仲丁酯、乳酸叔丁酯、乳酸戊酯、乳酸异戊酯。尽管本申请意图包括所有适合缩聚反应的乳酸酯，但是优选地使用那些容易获得并保存运输的乳酸酯，例如乳酸甲酯、乳酸乙酯等，这样可以显著降低获得乳酸的成本。
可以理解的是，乳酸酯的缩聚反应可以在催化剂的作用下进行的。
原则上可以使用能够促进(即催化)乳酸酯进行缩聚的各种催化剂。具体而言，在缩聚反应中使用的催化剂可以包括多种酸性或碱性物质。例如，乳酸酯缩聚反应中使用的催化剂可以为选自硫酸、盐酸、磷酸、羧酸、Lewis酸、酸式盐、卤化物、锡盐、亚锡盐、锌盐、钛盐、锑盐、锗盐、金属氧化物、稀土化合物、磷钨杂多酸、无机碱、碱式盐、烷基磺酸钠、有机碱中的一种或多种。在一些实施方案中，优选的催化剂是浓硫酸、氯化亚锡和/或辛酸亚锡。
在乳酸酯的缩聚反应中，可以适当选择催化剂的用量，例如可以为0.01wt％至50wt％，基于乳酸酯的用量计。在一些优选的实施方案中，催化剂的用量为0.5wt％至10wt％，优选1wt％至5wt％，基于乳酸酯的用量计。
在一些实施方案中，该缩聚反应可以在0℃至350℃、优选50℃至300℃、再优选100℃至250℃、最优选100℃至200℃的温度下进行。
在一些优选的实施方案中，该缩聚反应在1Pa至20MPa、优选10Pa至10MPa、优选0.1kPa至1MPa、再优选0.01MPa至1MPa的绝对压力下进行。
在一些优选的实施方案中，该缩聚反应持续进行0.001小时至500小时，例如1小时至200小时。本领域技术人员可以根据需要对反应时长在适当范围内进行调节。
本申请的发明人发现，根据本申请有利的是，从乳酸酯单体开始的缩聚反应分步进行，例如分两步、三步或四步进行。
例如，缩聚反应可以在第一压力第一温度下持续进行第一时间，然后可以在改变真空度和/或改变温度后在第二压力第二温度下进行第二时间。优选地，缩聚反应还可以在改变真空度和/或改变温度后在第三压力第三温度下进行第三时间。这里，第一步中的绝对压力，即第一压力，一般需要大于等于大气压，例如可以从0.1MPa至20MPa，例如从0.1MPa至10MPa或者从0.1MPa至5MPa。在优选的实施方案中，在第二步和后续步骤中的绝对压力，即第二压力和如果存在的第三压力等，一般小于大气压，例如从0.1kPa至小于0.1MPa。在优选的实施方案中，在第二
步和任选的后续步骤中的温度，即第二温度和如果存在的第三温度等，可以大于等于、优选大于第一步中的温度，即第一温度。
在进一步优选的实施方案中，缩聚反应分三步进行。此时，有利的是，第三步中的绝对压力，即第三压力可以小于等于、优选小于第二步中的绝对压力，即第二压力。同样有利的是，第三温度可以大于等于、优选大于第二温度。
无意于受理论所束缚，发明人认为，在第一步中的适当高压有利于减少单体的挥发损失，促进聚合反应的启动并初步生成聚合物，通过在随后升高反应温度和/或降低压力(抽真空)可以方便地促进缩聚反应的小分子产物(即一元醇)的排出，由此进一步促进了聚合，由此增加了聚合物的分子量。另外，排出的小分子产物即一元醇甚至还可以回收重复利用。例如，排出的一元醇还可以循环利用去和乳酸反应制备乳酸酯，这显然是非常环保的。
作为备选的优化步骤，可以在缩聚反应全部完成后，对反应所得到的产物进行提纯处理。可以采用本领域中公知的方式进行提纯。
由此制备得到的聚乳酸产品的重均分子量最少也可以大于500，一般大于1000，优选大于2000或2500。在优选的情况中，由此制备得到的聚乳酸产品的重均分子量甚至可以大于10000。
为了进一步增加最终聚乳酸的分子量，可以在缩聚反应后对所得产物进行扩链。因此，本申请还提供了一种聚乳酸的制造方法，包括以下步骤：
a)使乳酸酯单体发生缩聚反应，从而得到聚乳酸预聚物；
b)任选地，使所述聚乳酸预聚物与选自二元醇和二元羧酸或其酸酐中一种的交换试剂发生酯交换反应，从而形成两端基均为羟基或羧基的中间体聚合物；和
c)使所述中间体聚合物与扩链剂发生扩链反应，从而得到高分子量的聚乳酸。
在步骤a)中，还可以任选地对所得到的聚乳酸预聚物进行提纯处理，用于后续步骤。
在该方法中，步骤a)中关于“缩聚反应”和提纯步骤以及可用于缩
聚反应的催化剂的描述与上文相同。
酯交换反应是任选的。是否需要酯交换反应步骤取决于后续采用的扩链剂。当所使用的扩链剂为例如环氧树脂时，可以省略该酯交换步骤。
此时，根据本申请的聚乳酸的制造方法可以包括以下步骤：
a’)使乳酸酯单体发生缩聚反应，从而得到聚乳酸预聚物；和
c’)使所述聚乳酸预聚物与选自环氧树脂的扩链剂发生扩链反应，从而得到高分子量的聚乳酸。
在根据本申请方法的一些实施方案中，在采用酯交换反应步骤时，作为在酯交换反应中使用的酯交换试剂，二元醇可以选自乙二醇、丙二醇、丁二醇、戊二醇、己二醇中的一种或多种，特别优选乙二醇。
在根据本申请方法的一些实施方案中，在采用酯交换反应步骤时，作为在酯交换反应中使用的酯交换试剂，二元羧酸或其酸酐选自对苯二甲酸、邻苯二甲酸、丙二酸、丁二酸、丁烯二酸、戊二酸、己二酸、辛二酸中的一种或多种。
在酯交换反应的步骤中，对酯交换剂的用量没有特别的限制。一般情况下，所述二元醇或二元羧酸相对于与聚乳酸链端基可以略微过量。反应后可以蒸馏除去多余的二元醇或二元酸。
酯交换反应可以在大于0至300℃，例如100℃至200℃的温度下进行。酯交换反应可以在适当的压力例如0.1kPa-10MPa的绝对压力下进行。酯交换反应时间进行大于0至500小时，例如1至100个小时。本领域技术人员可以根据实际需要选择合适的温度、压力和时间用于酯交换反应。如有需要，本领域技术人员可以根据所选用的酯交换试剂在酯交换反应中选择使用相关领域熟知的催化剂或者不使用催化剂，以促进反应的发生。
在酯交换反应完成之后，即在步骤b)完成之后，得到了两头端基均为羟基或羧基的聚乳酸的聚合物，在本文中也称为中间体聚合物。
在优选的实施方案中，为了进一步增加聚乳酸的分子量，可以对聚乳酸(这里也称为中间体聚合物)进行扩链。扩链剂可以选自含羟基或氨基的低分子质量多官能团的醇类或胺类化合物或环氧树脂中的一种或多种。例如，扩链剂可以选自环氧树脂、二异氰酸酯和/或二噁唑啉。二异
氰酸酯类扩链剂包括例如二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)。对于酯交换后两端基为羧基的聚乳酸一般选用噁唑啉类扩链剂，而对于酯交换后两端基为羟基的聚乳酸一般选用二异氰酸酯类扩链剂。对于环氧树脂扩链剂，则可以省略酯交换反应步骤。
本领域技术人员可以根据需要选择扩链剂的用量。一般而言，扩链剂的用量相对于聚合物的端基不可过量，可以适当减少用量。扩链反应可以在大于0至300℃，例如100℃至200℃的温度下进行。扩链反应可以在0.1kPa-10MPa的压力下进行。扩链反应进行大于0至500小时，例如1至100小时。本领域技术人员可以根据实际需要选择合适的温度、压力和时间用于扩链反应。如有需要，本领域技术人员可以根据所选用的扩链剂在扩链反应中选择使用相关领域熟知的催化剂或者不使用催化剂，以促进反应的发生。
在扩链反应完成之后，即在步骤c)之后，可以有效地提高中间体聚合物的分子量。由此制备得到的聚乳酸的重均分子量可以大于5000，甚至大于10000，优选大于50000。
因此，本申请还提供了根据上述方法制备得到的聚乳酸。
根据本申请的制备方法制备聚乳酸的优点将在下面参考具体实施例得到进一步证实。
实施例
在各实施例中使用的原料物质和催化剂均可以从市场获得或者根据一般的合成方法直接获得。另外，在各实施例中未明确指明时，所使用的反应压力约为大气压。
为了方便说明，以乳酸甲酯为例示意各实施例中聚乳酸的合成路线可参见下式：
步骤a)
步骤b)：酯交换反应：
步骤c)：扩链反应：
实施例1
将150g乳酸乙酯和3wt％的浓硫酸(98％)放入搅拌反应釜中，在0.5MPa压力下和170℃下反应25小时，得到聚乳酸，重均分子量为1539，收率为92％。
实施例2
将150g乳酸丁酯和5wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和160～180℃下反应18小时，得到聚乳酸，重均分子量为1735，收率为86％。
实施例3
将50g乳酸甲酯和2.5wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应16小时，得到聚乳酸，重均分子量为563，收率为79.86％。
实施例4
将150g乳酸异戊酯和1wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和160～175℃下反应32小时，得到聚乳酸，重均分子量为723，收率为94.5％。
实施例5
将50g乳酸甲酯和2.5wt％的浓硫酸(98％)放入带有回流的搅拌
反应釜中，在0.2MPa压力和140℃下反应16小时，得到聚乳酸预聚物。
然后改变压力，在温度为140℃，抽真空4小时，0.05-0.09MPa真空度，得到聚乳酸，重均分子量为1750，收率为69.6％。
实施例6
将50g乳酸甲酯和2.5wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后改变压力，在温度为140℃，抽真空4小时，0.05-0.09MPa真空度，得到聚乳酸，重均分子量为2350，收率为73.23％。
实施例7
将50g乳酸甲酯和2.5wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应16小时，得到聚乳酸预聚物。
然后改变压力，在温度为140℃，抽真空4小时，0.05-0.09MPa真空度，得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中加入MDI，在160℃下进行扩链反应1小时，得到聚乳酸产物，重均分子量为7079，收率为72.54％。
实施例8
将50g乳酸甲酯和2.5wt％的浓硫酸(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，温度为140℃，抽真空4小时，0.05-0.09MPa真空度，得到第一聚合物。
然后加入乙二醇，在140℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中加入MDI，在160℃下进行扩链反应1小时，得到聚乳酸产物，重均分子量为9054，收率为72.27％。
实施例9
将100g乳酸乙酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和150℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，温度为140℃，抽真空24小时，得到聚合物。得到聚乳酸产物，重均分子量为2052，收率为71.17％。
实施例10
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，温度为140℃，抽真空12小时，得到聚合物，重均分子量为1326，收率为58.26％。
实施例11
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，温度为140℃，抽真空12小时，得到第一聚合物。
向上述步骤所得第一聚合物中升高温度至170℃，0.05-0.09MPa真空度下抽真空12小时，得到聚合物，重均分子量为2357，收率为59.74％。
实施例12
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
向上述步骤所得第一聚合物中升高温度至170℃，0.05-0.09MPa下抽真空24小时，得到聚乳酸聚合物，重均分子量为2861，收率为56.65％。
实施例13
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应
釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140～155℃，抽真空36小时，得到第一聚合物。
向上述步骤所得第一聚合物中升高温度至170～180℃，0.09-0.095MPa真空度下抽真空48小时，得到聚合物，重均分子量为5633，收率为59％。
实施例14
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140-160℃，抽真空48小时，得到第一聚合物。
向上述步骤所得第一聚合物中升高温度至170～185℃，0.09-0.096MPa真空度下抽真空96小时，得到聚合物，重均分子量为10366，收率为59.5％。
实施例15
将100g乳酸甲酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空4小时，得到聚合物，重均分子量为863，收率为65.56％。
实施例16
将100g乳酸甲酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到聚合物，重均分子量为1033，收率为62.1％。
实施例17
将50g乳酸乙酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜
中，在大气压和140℃下反应32小时，得到预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
然后升高温度至170℃，0.05-0.09MPa真空度下抽真空12小时，得到聚合物，重均分子量为1689，收率为63％。
实施例18
将50g乳酸甲酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
然后升高温度至170℃，0.05-0.09MPa真空度下抽真空24小时，得到聚合物，重均分子量为2045，收率为62％。
实施例19
将50g乳酸甲酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
然后升高温度至170℃，0.05-0.09MPa真空度下抽真空36小时，得到聚合物，重均分子量为2257，收率为61％。
实施例20
将50g乳酸甲酯和2.5wt％的辛酸亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
然后在0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
然后升高温度至170℃，0.05-0.09MPa真空度下抽真空48小时，得到聚合物，重均分子量为3251，收率为60％。
实施例21
将100g乳酸甲酯，1wt％的辛酸亚锡和3.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
在0.05-0.09MPa真空度，温度为140-150℃，抽真空22小时。然后升高温度至170-185℃，0.09-0.096MPa真空度下抽真空80小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中分加入MDI，在160℃下进行扩链反应2小时，得到聚乳酸产品，重均分子量为50224，收率58.1％。
实施例22
将100g乳酸甲酯和2wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，温度为140℃，抽真空20小时，升高温度至170～180℃，0.09-0.095MPa真空度下抽真空48小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140-170℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中加入MDI，在160-170℃下进行扩链反应1小时，得到聚乳酸产品，重均分子量为15254，收率为55.7％。
实施例23
将100g乳酸甲酯和3wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到聚乳酸预聚物。
向预聚步骤所得预聚物中增加0.05-0.09MPa真空度，在温度为140～160℃，抽真空20小时，升高温度至170～185℃，0.09～0.095MPa真空度下抽真空72小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140～170℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中加入MDI，在160～180℃下进行扩链反应2小时，得到聚乳酸产品，重均分子量为40224，收率为58.1％。
实施例24
将100g乳酸甲酯，2wt％的氧化锌(98％)和2％对甲基苯磺酸放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
向预聚步骤所得预聚物中增加0.05-0.09MPa真空度，在温度为140～150℃，抽真空24小时，升高温度至170～180℃，0.09-0.096MPa真空度下抽真空72小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140～150℃下进行酯交换反应4小时，得到酯交换产物。
向上述步骤所得酯交换产物中分加入MDI，在140～160℃下进行扩链反应1小时，得到聚乳酸产品，重均分子量为30381，收率为56％。
实施例25
将100g乳酸甲酯和4wt％的氯化亚锡(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应48小时，得到聚乳酸预聚物。
然后在0.05-0.09MPa真空度，在温度为140～160℃，抽真空56小时，升高温度至170～190℃，0.09～0.098MPa真空度下抽真空96小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140-170℃下进行酯交换反应6小时，得到酯交换产物。
向上述步骤所得酯交换产物中加入MDI，在160～190℃下进行扩链反应3小时，得到聚乳酸产品，重均分子量为76562，收率为57.9％。
实施例26
将100g乳酸甲酯和5wt％的氯化亚锡(98％)放入带有回流的搅拌反应釜中，在大气压和140℃下反应48小时，得到聚乳酸预聚物。
然后在0.095MPa真空度，在温度为140～165℃，抽真空72小时，
升高温度至170～195℃，0.09～0.099MPa真空度下抽真空120小时得到第一聚合物。
向上述步骤所得第一聚合物中加入乙二醇，在140～170℃下进行酯交换反应8小时，得到酯交换产物。
向上述步骤所得酯交换产物加入MDI，在160～190℃下进行扩链反应5小时，得到聚乳酸产品，重均分子量为106852，收率为59％。
实施例27
将100g乳酸甲酯和3.5wt％的氯化亚锡放入带有回流搅拌的反应器中，在大气压和140℃下反应32小时，得到预聚物。
向上述步骤所得预聚物中增加0.05-0.09MPa真空度，在温度为140-150℃，抽真空40小时，得到第一聚合物。
然后升高温度至160-180℃，0.09-0.096MPa真空度下抽真空92小时，得到聚合物，重均分子量为13272，收率为58％。
实施例28
将100g乳酸甲酯，3.5wt％的氯化亚锡和1.5％对甲基苯磺酸放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
向上述步骤所得预聚物中增加0.05-0.09MPa真空度，在温度为140-160℃℃，抽真空50小时，得到第一聚合物。
然后升高温度至160-180℃，0.09-0.098MPa真空度下抽真空96小时，得到聚合物，重均分子量为20596，收率为57％。
实施例29
将100g乳酸甲酯和2.5wt％的氯化亚锡放入带有回流的搅拌反应釜中，在大气压和140℃下反应32小时，得到预聚物。
向上述步骤所得预聚物中增加0.05-0.09MPa真空度，在温度为140℃，抽真空12小时，得到第一聚合物。
然后升高温度至165-175℃，0.05-0.09MPa真空度下抽真空72小
时，得到聚合物，重均分子量为3809，收率为57.9％。
以上已经描述了本申请的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离本申请主旨的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
Claims (10)
- 聚乳酸的制造方法，包括使乳酸酯单体发生缩聚反应，从而得到聚乳酸。
- 聚乳酸的制造方法，包括：a)使乳酸酯单体发生缩聚反应，从而得到聚乳酸预聚物，以及任选地，对所述聚乳酸预聚物进行提纯处理；b)任选地，使所述聚乳酸预聚物与选自二元醇和二元羧酸或其酸酐中任一种的交换试剂发生酯交换反应，从而形成两端基均为羟基或羧基的中间体聚合物；以及c)使所述中间体聚合物与扩链剂发生扩链反应，从而得到高分子量的聚乳酸。
- 根据权利要求1或2所述的方法，其中，所述乳酸酯单体具有如下的结构式：
其中R表示取代或未经取代的C1-C20烃基或取代或未经取代的C1-C20杂烃基；优选地，R为选自直链或支链C1-C20烷基、直链或支链C2-C20烯基、直链或支链C2-C20炔基、C3-C20环烷基、C3-C20环烯基、C6-C20芳基、C3-C20杂芳基、C3-C20杂环烷基、C3-C20杂环烯基、C4-C20杂芳烷基中的一种的基团，其中所述基团为未经取代的或者被选自C1-C10烷基、C1-C10烷氧基、C3-C10环烷基、巯基、卤素、氰基、羰基或氨基中的取代基单取代或双取代；再优选地，R为C1-C20烷基，更优选C1-C12烷基，再优选C1-C6烷基，特别优选为C1-C4烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基及其同分异构体、己基及其同分异构体、庚基及其同分异构体、辛基及其同分异构体、壬基及其同分异构 体、癸基及其同分异构体、十一烷基及其同分异构体、十二烷基及其及其同分异构体。 - 根据权利要求3所述的方法，其中，所述乳酸酯单体是由乳酸与由ROH表示的一元醇形成的，其中R如权利要求3中所定义；或者所述乳酸酯单体选自乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸异丙酯、乳酸丁酯、乳酸异丁酯、乳酸仲丁酯、乳酸叔丁酯、乳酸戊酯、乳酸异戊酯以及乳酸与C6-C20一元醇形成的酯中的一种或多种。
- 根据权利要求1或2所述的方法，其中，所述缩聚反应在催化剂的作用下进行，其中所述催化剂为酸性或碱性物质，优选选自硫酸、盐酸、磷酸、羧酸、Lewis酸、酸式盐、卤化物、锡盐、亚锡盐、锌盐、钛盐、锑盐、锗盐、金属氧化物、稀土化合物、磷钨杂多酸、无机碱、碱式盐、烷基磺酸钠、有机碱中的一种或多种，优选脂肪酸亚锡和氯化亚锡；任选地，所述催化剂用量为基于乳酸酯的用量的0.01wt％至50wt％，优选0.5wt％至10wt％，更优选1wt％至5wt％。
- 根据权利要求1或2所述的方法，其中，所述缩聚反应在0℃至350℃、优选50℃至300℃、再优选100℃至250℃、最优选100℃至200℃的温度下和/或在1Pa至20MPa、优选10Pa至10MPa、再优选0.1kPa至1MPa的绝对压力下进行0.001小时至500小时、例如1小时至200小时。
- 根据权利要求1或2所述的方法，其中，所述缩聚反应分步进行，例如分两步、三步或四步进行，其中第一步中的绝对压力大于等于大气压，例如从0.1MPa至20MPa，在第二步和任选的后续步骤中的绝对压力小于大气压，例如从0.1kPa至小于0.1MPa，和/或在第二步和任选的后续步骤中的温度大于等于第一步中的温度；优选地，所述缩聚反应分三步进行，其中第三步的绝对压力小于等于、优选小于第二步的绝对压力和/或第三步中的温度大于等于、优选大于第二步中的温度。
- 如权利要求2所述的方法，其中，所述酯交换反应在大于0至300℃，例如100℃至200℃的温度下进行0.01小时至500小时，例如1小时至100小时；和/或所述二元醇为选自乙二醇、丙二醇、丁二醇、戊二醇和己二醇中的一种或多种；和/或所述二元羧酸为选自对苯二甲酸、邻苯二甲酸、丙二酸、丁二酸、丁烯二酸、戊二酸、己二酸和辛二酸中的一种或多种。
- 如权利要求2所述的方法，其中，所述扩链剂为选自含羟基或氨基的低分子量多官能团的醇类或胺类化合物和环氧树脂中的一种或多种，优选选自二异氰酸酯、二噁唑啉、环氧树脂，其中二异氰酸酯类扩链剂例如有二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、二环己基二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)；和/或所述扩链反应在大于0至300℃，例如100℃至200℃的温度下进行0.01至500小时，例如1至100小时。
- 通过权利要求1至9任一项的方法制造得到的聚乳酸，优选所述聚乳酸具有的重均分子量大于500；或重均分子量大于或1000；或重均分子量大于2000；或重均分子量大于5000；或重均分子量大于10000，或重均分子量大于50000。
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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 (en) * | 1993-10-07 | 1995-04-13 | Patrick Richard Gruber | Continuous process for the manufacture of lactide and lactide polymers |
| 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 |
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- 2022-05-18 CN CN202210544466.2A patent/CN117126383A/zh active Pending
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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 (en) * | 1993-10-07 | 1995-04-13 | Patrick Richard Gruber | Continuous process for the manufacture of lactide and lactide polymers |
| 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 |
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| 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 |
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| 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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