CN117126383A - Method for preparing high molecular weight polylactic acid - Google Patents
Method for preparing high molecular weight polylactic acid Download PDFInfo
- Publication number
- CN117126383A CN117126383A CN202210544466.2A CN202210544466A CN117126383A CN 117126383 A CN117126383 A CN 117126383A CN 202210544466 A CN202210544466 A CN 202210544466A CN 117126383 A CN117126383 A CN 117126383A
- Authority
- CN
- China
- Prior art keywords
- acid
- lactate
- polylactic acid
- hours
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 108
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 49
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000004310 lactic acid Substances 0.000 claims abstract description 17
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000005809 transesterification reaction Methods 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 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 17
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 17
- 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
- 150000003903 lactic acid esters Chemical class 0.000 claims description 15
- 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 14
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 14
- -1 lactate ester Chemical class 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 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
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229940116333 ethyl lactate Drugs 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000000746 purification Methods 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
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920000647 polyepoxide Polymers 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
- 150000001298 alcohols Chemical class 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
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-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
- 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
- 239000003795 chemical substances by application Substances 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
- 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
- 125000000304 alkynyl 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
- 125000000392 cycloalkenyl group Chemical group 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- IXXMVXXFAJGOQO-UHFFFAOYSA-N tert-butyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC(C)(C)C IXXMVXXFAJGOQO-UHFFFAOYSA-N 0.000 claims description 3
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl 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
- 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
- 239000002253 acid Chemical class 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 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
- 125000004366 heterocycloalkenyl 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
- 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
- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- 239000011964 heteropoly acid Substances 0.000 claims 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- 150000002918 oxazolines Chemical class 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 36
- 238000010992 reflux Methods 0.000 description 29
- 238000005086 pumping Methods 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 16
- 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
- 239000002904 solvent Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000463 material Substances 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
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-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
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 2
- 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
- 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-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
- 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
- 239000004593 Epoxy Substances 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
- 230000015572 biosynthetic process 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
- 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
- 230000004151 fermentation Effects 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 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
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- 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
- 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
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 229920003180 amino resin Polymers 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
- 230000009286 beneficial effect Effects 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
- 229910052799 carbon Inorganic materials 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
- 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
- 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
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 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
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 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
- 239000000976 ink Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 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
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 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
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 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
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The method takes lactate as a monomer raw material, and performs polycondensation reaction under the action of a catalyst to obtain the polylactic acid. The method uses the lactate as the raw material, the reaction efficiency is higher than that of the conventional lactic acid dehydration polycondensation, the production cost is reduced, and the molecular weight and the economic benefit of the polymer are increased.
Description
Technical Field
The application relates to the technical field of synthesis of degradable materials. In particular, the present application relates to a novel method for producing polylactic acid, and in particular, to a method for producing polylactic acid from polycondensation reaction of lactate monomers. The present application also relates to polylactic acid, especially high molecular weight polylactic acid, produced by the method.
Background
Polylactic acid (PLA) is a high molecular polymer having excellent biodegradability and compatibility. At present, the main raw material for industrially synthesizing polylactic acid is lactic acid, the lactic acid can be directly obtained from the nature (such as grain fermentation), degradation products of the polylactic acid are pollution-free carbon dioxide and water, and green circulation can be realized in the nature through plant photosynthesis. Polylactic acid is used as a completely green degradable material, has little pollution to the environment, and is mainly used as medical drugs, environment-friendly materials, plastic daily necessities, textile clothing fabrics, agricultural mulching films, ornaments, fitness equipment and the like. In the large environment with environmental protection, green, harmony and sustainable development being the current economic and social development direction, the nontoxic, harmless and nonirritating polymer material is generated.
The main two types of synthesis methods of polylactic acid at present are a direct polymerization method and a lactide ring-opening polymerization method. Both of these methods have their respective advantages and disadvantages. The direct polymerization method mainly comprises the step of dehydrating and polymerizing lactic acid to obtain polylactic acid, but deep dehydration is difficult to carry out. High boiling point solvents (e.g., dimethyl ether, toluene, xylene, etc.) are typically employed to azeotrope with water to drive the water out of the reaction system, which solvents are capable of dissolving the polymer but do not participate in the reaction. The byproduct lactide is brought back to the reaction system through solvent reflux, so that the PLA decomposition phenomenon is avoided, and the PLA with low water content and relatively high molecular weight is obtained, so that the method is also called an azeotropic distillation method. Because of the poorly soluble nature of the polymer, the solution polymerization process requires a large amount of solvent and is prone to environmental pollution. Meanwhile, the use of high-boiling organic solvents complicates the process flow and increases the cost of equipment. Moreover, purification of the polymer is relatively difficult, and the resulting product will often contain residual organic solvents that are difficult to remove. The molecular weight of the polylactic acid prepared by the direct polymerization method is often lower.
Another direct polymerization of lactic acid is also known as melt polycondensation, which means that the oligomer formed by melt polycondensation is granulated, crystallized and dried, and then the oligomer is further polymerized under a proper temperature condition, so that small polylactic acid chains are connected. Although melt-solid phase polycondensation can improve the crystallinity and relative molecular mass of PLA, the method has high requirements on equipment, and generally, PLA with high molecular weight can be obtained by performing the reaction under a high vacuum degree, which is also very difficult to popularize in industry.
Lactide ring-opening polymerization is one of the most studied methods by researchers, and the general steps of the ring-opening polymerization method are as follows: the method comprises the steps of synthesizing lactide by taking lactic acid as a raw material, and then ring-opening polymerizing the lactide into polylactic acid under different conditions, wherein the specific process flow comprises three steps: and (3) preparing, purifying and ring-opening lactide. Although the indirect polymerization method using lactide as raw material can prepare polylactic acid products with high molecular weight, the steps are relatively complicated and the cost is too high.
Thus, there remains a need to develop a method of providing polylactic acid, particularly high molecular weight polylactic acid, which is inexpensive and relatively simple in process.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a manufacturing method which has low cost and simple process and can obtain high molecular weight polylactic acid.
In order to achieve the above object, the present application provides, in one aspect, a novel method for producing polylactic acid, in which a lactic acid ester monomer is subjected to polycondensation reaction to obtain polylactic acid.
In another aspect, there is also provided a method for producing polylactic acid, the method comprising:
a) Subjecting lactate ester monomers to polycondensation reaction to obtain polylactic acid prepolymer, and optionally, subjecting the polylactic acid prepolymer to purification treatment;
b) Optionally, a step of transesterifying the polylactic acid prepolymer with an exchange agent selected from a diol and a dicarboxylic acid or an anhydride thereof, thereby forming an intermediate polymer having hydroxyl or carboxyl groups at both end groups;
c) And (3) carrying out chain extension reaction on the intermediate polymer and a chain extender, thereby obtaining the polylactic acid with high molecular weight.
The lactate ester in the polycondensation reaction has the following structural formula:
wherein R represents a substituted or unsubstituted C 1 -C 20 Hydrocarbyl or substituted or unsubstituted C 1 -C 20 Heterohydrocarbyl groups. The polycondensation reaction of the lactic acid ester may be performed under the action of a catalyst. The catalyst used in the polycondensation reaction is suitably an acidic or basic substance in an amount of 0.01% to 50% by weight based on the amount of lactate. The polycondensation reaction may be carried out at a temperature of from 0 ℃ to 350 ℃, preferably from 50 ℃ to 300 ℃, more preferably from 100 ℃ to 250 ℃, most preferably from 100 ℃ to 200 ℃ and/or at an absolute pressure of from 1Pa to 20MPa, preferably from 10Pa to 10MPa, more preferably from 0.1kPa to 1MPa, for from 0.001 hours to 500 hours, for example from 1 hour to 200 hours.
Preferably, the polycondensation reaction may be carried out stepwise, for example in two steps, in three steps or in four steps, wherein the absolute pressure in the first step is equal to or higher than the atmospheric pressure, for example from 0.1MPa to 20MPa, the absolute pressure in the second step and optionally in the subsequent step is lower than the atmospheric pressure, for example from 0.1kPa to less than 0.1MPa, and/or the temperature in the second step and optionally in the subsequent step is equal to or higher than the temperature in the first step.
Preferably, the polycondensation reaction is carried out in three steps, wherein the absolute pressure of the third step is equal to or less than, preferably less than, the absolute pressure of the second step and/or the temperature in the third step is equal to or greater than, preferably greater than, the temperature in the second step.
The transesterification reaction is carried out at a temperature of greater than 0 to 300 ℃, for example 100 to 200 ℃, for 0.01 to 500 hours, for example 1 to 100 hours.
The chain extension reaction is carried out at a temperature of greater than 0 to 300 ℃, for example 100 to 200 ℃, for greater than 0.01 to 500 hours, for example 1 to 100 hours. The chain extender is one or more selected from low molecular weight polyfunctional alcohols or amines containing hydroxyl or amino groups, for example, selected from diisocyanates, bisoxazolines and epoxy resins, such as diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate (IPDI), epoxy resins, preferably diphenylmethane diisocyanate.
In still another aspect, 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 1000; or a weight average molecular weight greater than 2000; or a weight average molecular weight greater than 5000; or a weight average molecular weight greater than 10000. Where appropriate, the weight average molecular weight of the polylactic acid may be greater than 50000, even greater than 100000.
The method for manufacturing polylactic acid has the following beneficial effects:
the method takes the lactate as a monomer raw material, and can synthesize the polylactic acid product with high molecular weight through direct polycondensation under the action of the catalyst, and the reaction efficiency is far higher than that of the conventional lactic acid dehydration preparation process, so that the polymerization progress of the reaction is greatly improved, the molecular weight and the yield are increased, and the quality of the final polylactic acid product and the overall production efficiency are improved. The application can effectively improve the synthetic molecular weight of polylactic acid while reducing the cost.
In particular, PLA is produced from lactate esters with a polymerization efficiency that is higher than that of conventional lactic acid dehydrate polymerizations. Therefore, the method not only can improve the reaction efficiency, but also can greatly reduce the production cost of the polylactic acid, is a new industrial production process route, and has very important significance and wide development prospect.
Detailed Description
So that the technical features and content of the present application can be understood in detail, preferred embodiments of the present application will be described in more detail below. While the preferred embodiments of the present application have been described in the examples, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Definition of the definition
"hydrocarbyl" as used herein refers to a monovalent group consisting of only hydrogen and carbon. Hydrocarbyl groups include aliphatic and aromatic hydrocarbon groups such as alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl (e.g., phenyl or benzyl), and the like. Herein, C x Representing the modified group having X carbon atoms.
"heterohydrocarbyl" refers to a hydrocarbon group in which at least one, but not all, of the carbons are replaced by heteroatoms.
Herein, the heteroatom may be selected from halogen atoms (fluorine, chlorine, bromine, iodine), phosphorus, nitrogen, sulfur, oxygen, and the like.
As used herein, "atmospheric pressure" refers to 1 standard atmospheric pressure, about 0.1MPa.
Herein, "polylactic acid" refers to a polyester-based polymer having a repeating unit having the structure shown below as a main chain. In this context, polylactic acid has a (weight average) molecular weight of at least 500 (g/mol), typically up to 1000 or more, i.e. the number n of repeating units may be at least 7, typically 15 or more. It is understood that there may be very little other end groups or linking groups in the polylactic acid due to the specific process applied, but this does not affect the representation of the polylactic acid backbone structure.
The inventors of the present application have intended to provide a new and improved process for producing polylactic acid. In the prior art, polylactic acid can be generally prepared by a direct polycondensation method of lactic acid and a polycondensation method of lactide ring opening. However, polylactic acid obtained by the direct (dehydrated) polycondensation method of lactic acid generally has disadvantages of low molecular weight and further dehydration is very difficult.
And lactate (e.g., methyl lactate) is an important intermediate in the traditional industrial fermentation process for obtaining lactic acid. Lactic acid esters are also widely used as important solvents and intermediate materials in the chemical and pharmaceutical fields, for example in the fields of medicine, resin coatings, adhesives, cleaning agents, dry cleaning solutions, printing inks, etc.
The inventors of the present application have unexpectedly found for the first time that polylactic acid having a high molecular weight and a high yield can be conveniently obtained when polycondensation reaction dealcoholization polycondensation is performed using a lactic acid ester as a monomer.
Thus, according to the present application, there is provided a method for producing polylactic acid, comprising subjecting a lactate monomer to a polycondensation reaction to obtain polylactic acid.
In this polycondensation reaction, various suitable lactic acid esters can in principle be used. However, to facilitate the polycondensation reaction, the lactate has the following structural formula:
wherein R represents a substituted or unsubstituted C 1 -C 20 Hydrocarbyl or substituted or unsubstituted C 1 -C 20 Heterohydrocarbyl groups.
In some embodiments, R is selected from the group consisting of straight or branched C 1 -C 20 Alkyl, straight or branched C 2 -C 20 Alkenyl, straight-chain 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 Heterocycloalkenyl, C 4 -C 20 A group of one of the heteroaralkyl groups, wherein the group is unsubstituted or selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, C 3 -C 10 A substituent in cycloalkyl, mercapto, halogen, cyano, carbonyl or amino is mono-or di-substituted.
In some preferred embodiments, R may beC 1 -C 12 Alkyl, more preferably C 1 -C 6 Alkyl, particularly preferably C 1 -C 4 Alkyl groups 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. In a particularly preferred embodiment, R is C 1 -C 4 Alkyl, especially methyl.
The method for producing polylactic acid according to the present application may use the lactic acid ester monomer directly or may include a step of producing the lactic acid ester monomer by an esterification reaction before the polycondensation reaction step. In some embodiments, the lactate ester may be prepared from the esterification of lactic acid with a monohydric alcohol represented by ROH. Specifically, R is as defined above. Alternatively, the monohydric alcohol may be selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, cyclohexane methanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, heptadecanol, octadecanol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, benzyl alcohol, phenethyl alcohol, benzhydrol, naphthalene methanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxybutanol, vinyl alcohol, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (dimethylamino) ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-1-butanol, isopentanol, sec-pentanol, 3-pentanol, tert-amyl alcohol, sec-isopentanol, 4-methyl-2-pentanol, 2-hexanol, 2-ethylbutanol, 2-methylpentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-ethyl-3-pentanol, 2-heptanol, 3-heptanol, 2-ethyl-2, 6, 5-hexanol, and the like.
In some preferred embodiments, the lactate 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, and lactic acidAmyl ester, isoamyl lactate, lactic acid and C 6 -C 20 Esters of monohydric alcohols. In the process according to the application, particularly preferred lactic acid esters are methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, sec-butyl lactate, tert-butyl lactate, pentyl lactate, isopentyl lactate. Although the present application is intended to include all lactic acid esters suitable for polycondensation, preferably those readily available and storable for transportation, such as methyl lactate, ethyl lactate, etc., are used, which can significantly reduce the cost of obtaining lactic acid.
It will be appreciated that the polycondensation of the lactate ester may be carried out in the presence of a catalyst. In principle, various catalysts which are capable of promoting (i.e. catalyzing) the polycondensation of lactic acid esters can be used. Specifically, the catalyst used in the polycondensation reaction may include various acidic or basic substances. For example, the catalyst used in the lactate polycondensation reaction may be one or more selected from sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, lewis acid, acid salts, halides, tin salts, stannous salts, zinc salts, titanium salts, antimony salts, germanium salts, metal oxides, rare earth compounds, phosphotungstic heteropolyacids, inorganic bases, basic salts, sodium alkyl sulfonates, organic bases. In some embodiments, the preferred catalyst is concentrated sulfuric acid, stannous chloride, and/or stannous octoate.
In the polycondensation reaction of the lactic acid ester, the amount of the catalyst may be appropriately selected, and for example, may be 0.01 to 50% by weight based on the amount of the lactic acid ester used. In some preferred embodiments, the catalyst is used in an amount of 0.5wt% to 10wt%, preferably 1wt% to 5wt%, based on the amount of lactate used.
In some embodiments, the polycondensation reaction may be carried out at a temperature of from 0 ℃ to 350 ℃, preferably from 50 ℃ to 300 ℃, more preferably from 100 ℃ to 250 ℃, most preferably from 100 ℃ to 200 ℃.
In some preferred embodiments, the polycondensation reaction is carried out at an absolute pressure of from 1Pa to 20MPa, preferably from 10Pa to 10MPa, preferably from 0.1kPa to 1MPa, and more preferably from 0.01MPa to 1MPa.
In some preferred embodiments, the polycondensation reaction is continued for 0.001 hours to 500 hours, for example 1 hour to 200 hours. The reaction time can be adjusted within an appropriate range as required by those skilled in the art.
The inventors of the present application found that it is advantageous according to the present application to carry out the polycondensation reaction starting from the lactate monomer in steps, for example in two, three or four steps.
For example, the polycondensation reaction may be run at a first pressure and a first temperature for a first time, and then may be run at a second pressure and a second temperature after changing the vacuum and/or changing the temperature. Preferably, the polycondensation reaction may also be carried out at a third pressure and a third temperature for a third time after the vacuum level and/or the temperature are changed. Here, the absolute pressure in the first step, i.e., the first pressure, is generally required to be equal to or greater than the atmospheric pressure, and may be, for example, from 0.1MPa to 20MPa, for example, from 0.1MPa to 10MPa or from 0.1MPa to 5MPa. In a preferred embodiment, the absolute pressure in the second and subsequent steps, i.e. the second pressure and if present the third pressure, etc., is typically less than atmospheric pressure, e.g. from 0.1kPa to less than 0.1MPa. In a preferred embodiment, the temperature in the second and optionally subsequent steps, i.e. the second temperature and if present the third temperature etc. may be equal to or higher, preferably higher than the temperature in the first step.
In a further preferred embodiment, the polycondensation reaction is carried out in three steps. In this case, the absolute pressure in the third step, i.e. the third pressure, may advantageously be equal to or higher, preferably higher than the absolute pressure in the third step, i.e. the third pressure. It is also advantageous that the third temperature may be equal to or higher than, preferably the second temperature.
Without being bound by theory, the inventors believe that a suitably high pressure in the first step is advantageous in reducing the volatilization loss of the monomer, promoting the start-up of the polymerization reaction and preliminary formation of the polymer, and that the evacuation of the small molecule product (i.e. monohydric alcohol) of the polycondensation reaction can be conveniently promoted by subsequently increasing the reaction temperature and/or reducing the pressure (vacuum-pumping), thereby further promoting the polymerization and thus increasing the molecular weight of the polymer. In addition, the discharged small molecular products, namely monohydric alcohols, can be recycled. For example, the discharged monohydric alcohol can also be recycled for reaction with lactic acid to produce lactate, which is obviously very environmentally friendly.
As an alternative optimization step, the product obtained by the reaction may be subjected to purification treatment after the polycondensation reaction is completed. Purification can be performed in a manner well known in the art.
The polylactic acid products thus prepared may also have a minimum weight average molecular weight of more than 500, typically more than 1000, preferably more than 2000 or 2500. In a preferred case, the weight average molecular weight of the polylactic acid product thus prepared may even be more than 10000.
In order to further increase the molecular weight of the final polylactic acid, the resulting product may be chain-extended after the polycondensation reaction. Therefore, the application also provides a method for manufacturing polylactic acid, which comprises the following steps:
a) Subjecting lactate ester monomers to polycondensation reaction to obtain polylactic acid prepolymer, and optionally, subjecting the polylactic acid prepolymer to purification treatment;
b) Optionally, a step of transesterifying the polylactic acid prepolymer with an exchange agent selected from a diol and a dicarboxylic acid or an anhydride thereof, thereby forming an intermediate polymer having hydroxyl or carboxyl groups at both end groups; and
c) And (3) carrying out chain extension reaction on the intermediate polymer and a chain extender, thereby obtaining the polylactic acid with high molecular weight.
In this process, the description in step a) regarding the "polycondensation reaction" and the purification step and the catalysts that can be used for the polycondensation reaction is the same as above.
Transesterification is optional. Whether a transesterification step is required depends on the chain extender to be used later. When the chain extender used is, for example, an epoxy resin, this transesterification step may be omitted.
In some embodiments of the process according to the application, when a transesterification step is employed, as transesterification reagent used in the transesterification reaction, the glycol may be selected from one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, with ethylene glycol being particularly preferred.
In some embodiments of the process according to the application, when a transesterification step is employed, the dicarboxylic acid or anhydride thereof is selected from one or more of terephthalic acid, phthalic acid, malonic acid, succinic acid, butenedioic acid, glutaric acid, adipic acid, suberic acid as the transesterification reagent used in the transesterification reaction.
In the step of the transesterification reaction, the amount of the transesterification agent is not particularly limited. In general, the diol or dicarboxylic acid may be present in a slight excess relative to the terminal groups of the polylactic acid chain. Excess glycol or diacid can be distilled off after the reaction.
The transesterification reaction may be carried out at a temperature of greater than 0 to 300 ℃, for example 100 to 200 ℃. The transesterification reaction may be carried out at a suitable pressure, for example, an absolute pressure of 0.1kPa to 10 MPa. The transesterification reaction time is carried out for more than 0 to 500 hours, for example 1 to 100 hours. The person skilled in the art can choose the appropriate temperature, pressure and time for the transesterification reaction according to the actual needs. If desired, one skilled in the art may choose to use or not use catalysts well known in the relevant art in the transesterification reaction depending on the transesterification reagent selected to facilitate the reaction.
After the transesterification reaction is completed, i.e. after step b) is completed, a polymer of polylactic acid is obtained having hydroxyl or carboxyl groups at both end groups, also referred to herein as intermediate polymer.
In a preferred embodiment, the polylactic acid (also referred to herein as an intermediate polymer) may be chain extended in order to further increase the molecular weight of the polylactic acid. The chain extender can be selected from one or more of low molecular weight multifunctional alcohol or amine compounds containing hydroxyl or amino or epoxy resin. For example, the chain extender may be selected from epoxy, diisocyanate and/or bisoxazoline. Diisocyanate-based chain extenders include, for example, diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate (IPDI). The polylactic acid with carboxyl groups at the two end groups after transesterification generally adopts oxazoline chain extenders, and the polylactic acid with shrinkage groups at the two end groups after transesterification generally adopts diisocyanate chain extenders. For epoxy chain extenders, the transesterification step may be omitted.
The amount of chain extender used can be selected by one skilled in the art as desired. In general, the amount of chain extender used is not excessively large relative to the terminal groups of the polymer, and may be suitably reduced. The chain extension reaction may be carried out at a temperature of greater than 0 to 300 ℃, for example 100 to 200 ℃. The chain extension reaction may be carried out at a pressure of 0.1kPa to 10 MPa. The chain extension reaction is carried out for more than 0 to 500 hours, for example 1 to 100 hours. Those skilled in the art can select appropriate temperatures, pressures and times for the chain extension reaction according to actual needs. If desired, one skilled in the art may choose to use or not use catalysts well known in the relevant art in the chain extension reaction depending on the chain extender selected to promote the reaction.
After the chain extension reaction is completed, i.e. after step c), the molecular weight of the intermediate polymer can be effectively increased. The polylactic acid thus prepared may have a weight average molecular weight of more than 5000, even more than 10000, preferably more than 50000.
Therefore, the application also provides the polylactic acid prepared by the method.
The advantages of preparing polylactic acid according to the preparation method of the present application will be further confirmed with reference to specific examples below.
Examples
The starting materials and catalysts used in the examples were either commercially available or obtained directly according to the general synthetic methods. In addition, the reaction pressure used was about atmospheric pressure when not explicitly indicated in the examples.
For convenience of explanation, the synthetic route of polylactic acid in each example is illustrated by methyl lactate as follows:
step a)
Step b): transesterification:
step c): chain extension reaction:
example 1
150g of ethyl lactate and 3wt% of concentrated sulfuric acid (98%) were placed in a stirred tank reactor and reacted at 170℃under a pressure of 0.5MPa for 25 hours to give polylactic acid having a weight average molecular weight of 1539 and a yield of 92%.
Example 2
150g of butyl lactate and 5wt% of concentrated sulfuric acid (98%) are placed into a stirring reaction kettle with reflux and reacted for 18 hours at 160-180 ℃ under atmospheric pressure to obtain polylactic acid with the molecular weight of 1735 and the yield of 86%.
Example 3
50g of methyl lactate and 2.5wt% of concentrated sulfuric acid (98%) were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 16 hours to give polylactic acid having a molecular weight of 563 and a yield of 79.86%.
Example 4
150g of isoamyl lactate and 1wt% of concentrated sulfuric acid (98%) are placed in a stirred reaction kettle with reflux and reacted at 160-175 ℃ for 32 hours under atmospheric pressure to obtain polylactic acid with a molecular weight of 723 and a yield of 94.5%.
Example 5
50g of methyl lactate and 2.5wt% of concentrated sulfuric acid (98%) were placed in a stirred tank reactor with reflux and reacted at a pressure of 0.2MPa and a temperature of 140℃for 16 hours to obtain a polylactic acid prepolymer.
Then changing the pressure, vacuumizing for 4 hours at the temperature of 140 ℃, and obtaining the polylactic acid with the molecular weight of 1750 and the yield of 69.6 percent at the vacuum degree of 0.05-0.09 MPa.
Example 6
50g of methyl lactate and 2.5wt% of concentrated sulfuric acid (98%) were placed in a stirred reaction vessel with reflux, and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then changing the pressure, vacuumizing for 4 hours at the temperature of 140 ℃ and the vacuum degree of 0.05-0.09MPa to obtain the polylactic acid with the molecular weight of 2350 and the yield of 73.23 percent.
Example 7
50g of methyl lactate and 2.5wt% of concentrated sulfuric acid (98%) were placed in a stirred reaction vessel with reflux, and reacted at 140℃under atmospheric pressure for 16 hours to obtain a polylactic acid prepolymer.
Then changing the pressure, vacuumizing for 4 hours at the temperature of 140 ℃ and the vacuum degree of 0.05-0.09MPa to obtain the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification at 140 ℃ for 4 hours to obtain a transesterification product.
MDI is added into the transesterification product obtained in the above step, and chain extension reaction is carried out for 1 hour at 160 ℃ to obtain polylactic acid product with molecular weight of 7079 and yield of 72.54%.
Example 8
50g of methyl lactate and 2.5wt% of concentrated sulfuric acid (98%) were placed in a stirred reaction vessel with reflux, and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 4 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa and the vacuum degree of 0.05-0.09MPa, thus obtaining the first polymer.
Then adding glycol, and carrying out transesterification reaction for 4 hours at 140 ℃ to obtain a transesterification product.
MDI is added into the transesterification product obtained in the above step, and chain extension reaction is carried out for 1 hour at 160 ℃ to obtain polylactic acid product with molecular weight of 9054 and yield of 72.27%.
Example 9
100g of ethyl lactate and 2.5wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at atmospheric pressure and 150℃for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 24 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, so as to obtain the polymer. The polylactic acid product is obtained, the molecular weight is 2052, and the yield is 71.17%.
Example 10
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, so as to obtain the polymer with the molecular weight of 1326 and the yield of 58.26 percent.
Example 11
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
And (3) raising the temperature to 170 ℃ in the first polymer obtained in the step, and vacuumizing for 12 hours at the vacuum degree of 0.05-0.09MPa to obtain the polymer with the molecular weight of 2357 and the yield of 59.74%.
Example 12
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
And (3) raising the temperature to 170 ℃ in the first polymer obtained in the step, and vacuumizing for 24 hours under the pressure of 0.05-0.09MPa to obtain the polylactic acid polymer with the weight average molecular weight of 2861 and the yield of 56.65%.
Example 13
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 36 hours at the temperature of 140-155 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
And (3) raising the temperature to 170-180 ℃ in the first polymer obtained in the step, and vacuumizing for 48 hours at the vacuum degree of 0.09-0.095MPa to obtain the polymer with the molecular weight of 5633 and the yield of 59%.
Example 14
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 48 hours at the temperature of 140-160 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
And (3) raising the temperature to 170-185 ℃ in the first polymer obtained in the step, and vacuumizing for 96 hours at the vacuum degree of 0.09-0.096MPa to obtain the polymer with the molecular weight of 10366 and the yield of 59.5%.
Example 15
Prepolymerization: 100g of methyl lactate and 2.5wt% of stannous octoate were placed in a stirred tank reactor with reflux, and at atmospheric pressure and 140℃for 32 hours, to obtain a polylactic acid prepolymer.
Polymerization: then vacuum pumping is carried out for 4 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, so as to obtain the polymer with the molecular weight of 863 and the yield of 65.56 percent.
Example 16
Prepolymerization: 100g of methyl lactate and 2.5wt% of stannous octoate were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a polylactic acid prepolymer.
Polymerization: then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, so that the polymer is obtained, the molecular weight is 1033, and the yield is 62.1%.
Example 17
Prepolymerization: 50g of ethyl lactate and 2.5wt% of stannous octoate were placed in a stirred tank reactor with reflux and reacted at atmospheric pressure and 140℃for 32 hours to obtain a prepolymer.
Polymerization: then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
Then the temperature is increased to 170 ℃, and vacuum is pumped for 12 hours under the vacuum degree of 0.05-0.09MPa, thus obtaining the polymer with the molecular weight of 1689 and the yield of 63 percent.
Example 18
Prepolymerization: 50g of methyl lactate and 2.5% by weight of stannous octoate were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
Polymerization: then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
Then raising the temperature to 170 ℃, and vacuumizing for 24 hours at the vacuum degree of 0.05-0.09MPa to obtain the polymer with the molecular weight of 2045 and the yield of 62 percent.
Example 19
Prepolymerization: 50g of methyl lactate and 2.5% by weight of stannous octoate were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
Polymerization: then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
Then raising the temperature to 170 ℃, and vacuumizing for 36 hours at the vacuum degree of 0.05-0.09MPa to obtain the polymer with the molecular weight of 2257 and the yield of 61%.
Example 20
Prepolymerization: 50g of methyl lactate and 2.5% by weight of stannous octoate were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
Polymerization: then vacuum pumping is carried out for 12 hours at the temperature of 140 ℃ under the vacuum degree of 0.05-0.09MPa, and the first polymer is obtained.
Then the temperature is increased to 170 ℃, and the vacuum is pumped for 48 hours under the vacuum degree of 0.05-0.09MPa, thus obtaining the polymer with the molecular weight of 3251 and the yield of 60 percent.
Example 21
100g of methyl lactate, 1% by weight of stannous octoate and 3.5% by weight of stannous chloride were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
Vacuum-pumping at 140-150deg.C under 0.05-0.09MPa for 22 hr. Then raising the temperature to 170-185 ℃ and vacuumizing for 80 hours under the vacuum degree of 0.09-0.096MPa to obtain the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification at 140 ℃ for 4 hours to obtain a transesterification product.
MDI is added to the ester exchange product obtained in the above steps, chain extension reaction is carried out for 2 hours at 160 ℃ to obtain polylactic acid product with molecular weight of 50224 and yield of 58.1%.
Example 22
100g of methyl lactate and 2wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at atmospheric pressure and 140℃for 32 hours to obtain a polylactic acid prepolymer.
Then vacuum-pumping for 48 hours under the vacuum degree of 0.09-0.095MPa and the temperature of 140 ℃ for 20 hours, raising the temperature to 170-180 ℃ and vacuum-pumping for 48 hours under the vacuum degree of 0.09-0.09 MPa to obtain the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification at 140-170 ℃ for 4 hours to obtain a transesterification product.
MDI is added into the transesterification product obtained in the above step, chain extension reaction is carried out for 1 hour at 160-170 ℃ to obtain polylactic acid product with molecular weight of 15254 and yield of 55.7%.
Example 23
100g of methyl lactate and 3wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at atmospheric pressure and 140℃for 32 hours to obtain a polylactic acid prepolymer.
And (3) adding vacuum degree of 0.05-0.09MPa into the prepolymer obtained in the prepolymerization step, vacuumizing for 20 hours at the temperature of 140-160 ℃, raising the temperature to 170-185 ℃ and vacuumizing for 72 hours at the vacuum degree of 0.09-0.095MPa to obtain the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification at 140-170 ℃ for 4 hours to obtain a transesterification product.
MDI is added into the transesterification product obtained in the above steps, chain extension reaction is carried out for 2 hours at 160-180 ℃ to obtain polylactic acid product with molecular weight of 40224 and yield of 58.1%.
Example 24
100g of methyl lactate, 2% by weight of zinc oxide (98%) and 2% of p-toluenesulfonic acid were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
Adding 0.05-0.09MPa vacuum degree into the prepolymer obtained in the prepolymerization step, vacuumizing for 24 hours at the temperature of 140-150 ℃, raising the temperature to 170-180 ℃ and vacuumizing for 72 hours at the vacuum degree of 0.09-0.096MPa to obtain a first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification at 140-150 ℃ for 4 hours to obtain a transesterification product.
MDI is added to the ester exchange product obtained in the above steps, chain extension reaction is carried out for 1 hour at 140-160 ℃ to obtain polylactic acid product with molecular weight of 30381 and yield of 56%.
Example 25
100g of methyl lactate and 4wt% of stannous chloride (98%) were placed in a stirred reaction vessel with reflux and reacted at 140℃under atmospheric pressure for 48 hours to obtain a polylactic acid prepolymer.
Then vacuum-pumping for 56 hours at 140-160 ℃ under the vacuum degree of 0.05-0.09MPa, raising the temperature to 170-190 ℃ and vacuum-pumping for 96 hours under the vacuum degree of 0.09-0.098MPa to obtain the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification reaction at 140-170 ℃ for 6 hours to obtain a transesterification product.
MDI is added into the transesterification product obtained in the above steps, chain extension reaction is carried out for 3 hours at 160-190 ℃ to obtain polylactic acid product with molecular weight of 76562 and yield of 57.9%.
Example 26
100g of methyl lactate and 5wt% of stannous chloride (98%) were placed in a stirred reaction vessel with reflux and reacted at 140℃under atmospheric pressure for 48 hours to obtain a polylactic acid prepolymer.
Then vacuum pumping is carried out for 72 hours at the temperature of 140-165 ℃ under the vacuum degree of 0.095MPa, the temperature is increased to 170-195 ℃ and vacuum pumping is carried out for 120 hours under the vacuum degree of 0.09-0.099 MPa, thus obtaining the first polymer.
And adding ethylene glycol into the first polymer obtained in the step, and carrying out transesterification reaction for 8 hours at 140-170 ℃ to obtain a transesterification product.
Adding MDI into the ester exchange product obtained in the above steps, and carrying out chain extension reaction for 5 hours at 160-190 ℃ to obtain the polylactic acid product with the molecular weight of 106852 and the yield of 59%.
Example 27
100g of methyl lactate and 3.5wt% of stannous chloride were placed in a reactor with reflux stirring and reacted at atmospheric pressure and 140℃for 32 hours to obtain a prepolymer.
And (3) adding vacuum degree of 0.05-0.09MPa into the prepolymer obtained in the step, and vacuumizing for 40 hours at the temperature of 140-150 ℃ to obtain a first polymer.
Then raising the temperature to 160-180 ℃, vacuumizing for 92 hours under the vacuum degree of 0.09-0.096MPa, and obtaining the polymer with the molecular weight of 13272 and the yield of 58%.
Example 28
100g of methyl lactate, 3.5% by weight of stannous chloride and 1.5% of p-toluenesulfonic acid were placed in a stirred tank reactor with reflux and reacted at 140℃under atmospheric pressure for 32 hours to obtain a prepolymer.
And (3) adding vacuum degree of 0.05-0.09MPa into the prepolymer obtained in the step, and vacuumizing for 50 hours at the temperature of 140-160 ℃ to obtain a first polymer.
Then the temperature is increased to 160-180 ℃, and vacuum is pumped for 96 hours under the vacuum degree of 0.09-0.098MPa, thus obtaining the polymer with molecular weight of 20596 and yield of 57 percent.
Example 29
100g of methyl lactate and 2.5wt% of stannous chloride were placed in a stirred reaction vessel with reflux and reacted at atmospheric pressure and 140℃for 32 hours to obtain a prepolymer.
And (3) adding vacuum degree of 0.05-0.09MPa into the prepolymer obtained in the step, and vacuumizing for 12 hours at the temperature of 140 ℃ to obtain a first polymer.
Then the temperature is increased to 165-175 ℃, and the vacuum is pumped for 72 hours under the vacuum degree of 0.05-0.09MPa, thus obtaining the polymer with the molecular weight of 3809 and the yield of 57.9 percent.
The foregoing description of embodiments of the application has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit of the application.
Claims (10)
1. A method for producing polylactic acid, which comprises subjecting a lactic acid ester monomer to polycondensation reaction to obtain polylactic acid.
2. A method for producing polylactic acid, comprising:
a) Subjecting lactate ester monomers to polycondensation reaction to obtain polylactic acid prepolymer, and optionally, subjecting the polylactic acid prepolymer to purification treatment;
b) Optionally, a step of transesterifying the polylactic acid prepolymer with an exchanging agent selected from any one of a diol and a dicarboxylic acid or an anhydride thereof, thereby forming an intermediate polymer having hydroxyl groups or carboxyl groups at both end groups; and
c) And (3) carrying out chain extension reaction on the intermediate polymer and a chain extender, thereby obtaining the polylactic acid with high molecular weight.
3. The method of claim 1 or 2, wherein the lactate has the following structural formula:
wherein R represents a substituted or unsubstituted C 1 -C 20 Hydrocarbyl radicals or radicalsSubstituted or unsubstituted C 1 -C 20 Heterohydrocarbyl groups;
preferably, R is selected from linear or branched C 1 -C 20 Alkyl, straight or branched C 2 -C 20 Alkenyl, straight-chain 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 Heterocycloalkenyl, C 4 -C 20 A group of one of the heteroaralkyl groups, wherein the group is unsubstituted or selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, C 3 -C 10 A substituent in cycloalkyl, mercapto, halogen, cyano, carbonyl or amino is mono-or di-substituted;
still more preferably, R is C 1 -C 20 Alkyl, more preferably C 1 -C 12 Alkyl, more preferably C 1 -C 6 Alkyl, particularly preferably C 1 -C 4 Alkyl groups 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.
4. A process according to claim 3, wherein the lactate is formed from lactic acid and a monohydric alcohol represented by ROH, wherein R is as defined in claim 3; or alternatively
The lactic acid ester is selected from methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, sec-butyl lactate, tert-butyl lactate, amyl lactate, isoamyl lactate, and lactic acid and C 6 -C 20 One or more of the esters of monohydric alcohols.
5. The method according to claim 1 or 2, wherein,
the polycondensation reaction is carried out under the action of a catalyst, wherein the catalyst is an acidic or basic substance, preferably one or more selected from sulfuric acid, hydrochloric acid, phosphoric acid, carboxylic acid, lewis acid, acid salt, halide, tin salt, stannous salt, zinc salt, titanium salt, antimony salt, germanium salt, metal oxide, rare earth compound, phosphotungstic heteropolyacid, inorganic base, basic salt, sodium alkyl sulfonate and organic base, preferably stannous fatty acid and stannous chloride;
optionally, the catalyst is used in an amount of 0.01 to 50wt%, preferably 0.5 to 10wt%, more preferably 1 to 5wt%, based on the amount of lactate.
6. The process according to claim 1 or 2, characterized in that the polycondensation reaction is carried out at a temperature of 0 ℃ to 350 ℃, preferably 50 ℃ to 300 ℃, still preferably 100 ℃ to 250 ℃, most preferably 100 ℃ to 200 ℃ and/or at an absolute pressure of 1Pa to 20MPa, preferably 10Pa to 10MPa, still preferably 0.1kPa to 1MPa for 0.001 to 500 hours, such as 1 hour to 200 hours.
7. The process according to claim 1 or 2, wherein the polycondensation reaction is carried out stepwise, e.g. in two, three or four steps, wherein the absolute pressure in the first step is greater than or equal to atmospheric pressure, e.g. from 0.1MPa to 20MPa, the absolute pressure in the second and optional subsequent steps is less than atmospheric pressure, e.g. from 0.1kPa to less than 0.1MPa, and/or the temperature in the second and optional subsequent steps is greater than or equal to the temperature in the first step;
preferably, the polycondensation reaction is carried out in three steps, wherein the absolute pressure of the third step is equal to or less than, preferably less than, the absolute pressure of the second step and/or the temperature in the third step is equal to or greater than, preferably greater than, the temperature in the second step.
8. The method of claim 2, wherein the transesterification reaction is carried out at a temperature of greater than 0 to 300 ℃, such as 100 to 200 ℃ for 0.01 to 500 hours, such as 1 to 100 hours; and/or
The dihydric alcohol is one or more selected from ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol; and/or
The dicarboxylic acid is one or more selected from terephthalic acid, phthalic acid, malonic acid, succinic acid, butenedioic acid, glutaric acid, adipic acid and suberic acid.
9. The method according to claim 2, wherein the chain extender is one or more selected from the group consisting of low molecular weight polyfunctional alcohols or amines containing hydroxyl or amino groups and epoxy resins, preferably selected from the group consisting of diisocyanates, oxazolines, epoxy resins, wherein the diisocyanate-based chain extender is exemplified by diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexyl diisocyanate (HMDI), isophorone diisocyanate (IPDI); and/or
The chain extension reaction is carried out at a temperature of greater than 0 to 300 ℃, for example 100 to 200 ℃ for 0.01 to 500 hours, for example 1 to 100 hours.
10. Polylactic acid produced by the method of any one of claims 1 to 9, preferably having a weight average molecular weight of greater than 500; or a weight average molecular weight greater than or 1000; or a weight average molecular weight greater than 2000; or a weight average molecular weight greater than 5000; or a weight average molecular weight greater than 10000, or a weight average molecular weight greater than 50000.
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|---|---|---|---|
| CN202210544466.2A CN117126383A (en) | 2022-05-18 | 2022-05-18 | Method for preparing high molecular weight polylactic acid |
| PCT/CN2023/094816 WO2023222042A1 (en) | 2022-05-18 | 2023-05-17 | Manufacturing method for high-molecular-weight polylactic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210544466.2A CN117126383A (en) | 2022-05-18 | 2022-05-18 | Method for preparing high molecular weight polylactic acid |
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| CN202210544466.2A Pending CN117126383A (en) | 2022-05-18 | 2022-05-18 | Method for preparing high molecular weight polylactic acid |
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| WO (1) | WO2023222042A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6326458B1 (en) * | 1992-01-24 | 2001-12-04 | Cargill, Inc. | Continuous process for the manufacture of lactide and lactide polymers |
| US5247059A (en) * | 1992-01-24 | 1993-09-21 | Cargill, Incorporated | Continuous process for the manufacture of a purified lactide from esters of lactic acid |
| JP4048764B2 (en) * | 2001-01-31 | 2008-02-20 | トヨタ自動車株式会社 | Method for producing lactide using fermented lactic acid as raw material and method for producing polylactic acid |
| EP1357119B1 (en) * | 2001-01-31 | 2011-05-11 | Toyota Jidosha Kabushiki Kaisha | Process for producing lactide and process for producing polylactic acid starting with fermented lactic acid |
| CN1247653C (en) * | 2004-02-05 | 2006-03-29 | 哈尔滨工业大学 | Process for direct preparation of poly-lactic acid from lactic acid by melt/solid phase polycondensation |
| CN110684179B (en) * | 2019-11-11 | 2021-10-26 | 上海汉禾生物新材料科技有限公司 | Preparation method of high-molecular-weight polylactic acid |
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