CN114195998A - Process for preparing high-strength polyglycolic acid by continuous polycondensation - Google Patents
Process for preparing high-strength polyglycolic acid by continuous polycondensation Download PDFInfo
- Publication number
- CN114195998A CN114195998A CN202111615435.3A CN202111615435A CN114195998A CN 114195998 A CN114195998 A CN 114195998A CN 202111615435 A CN202111615435 A CN 202111615435A CN 114195998 A CN114195998 A CN 114195998A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- polycondensation
- polycondensation reaction
- polyglycolic acid
- strength
- 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
Links
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 220
- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 55
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 110
- 238000005086 pumping Methods 0.000 claims description 47
- 230000003068 static effect Effects 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 4
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 claims description 4
- WCCCBUXURHZPQL-GHMZBOCLSA-N (4s)-4-tert-butyl-2-[[(4s)-4-tert-butyl-4,5-dihydro-1,3-oxazol-2-yl]methyl]-4,5-dihydro-1,3-oxazole Chemical compound CC(C)(C)[C@H]1COC(CC=2OC[C@@H](N=2)C(C)(C)C)=N1 WCCCBUXURHZPQL-GHMZBOCLSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- UGDSCHVVUPHIFM-UHFFFAOYSA-N 1,1,1-tris(aminomethyl)ethane Chemical compound NCC(C)(CN)CN UGDSCHVVUPHIFM-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- DVPBWLLOGOINDW-UHFFFAOYSA-N 2-(5-bromo-1h-indol-3-yl)acetamide Chemical compound C1=C(Br)C=C2C(CC(=O)N)=CNC2=C1 DVPBWLLOGOINDW-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 229940063673 spermidine Drugs 0.000 claims description 2
- 229940063675 spermine Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- -1 acetate compound Chemical class 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 90
- 230000018044 dehydration Effects 0.000 description 23
- 238000006297 dehydration reaction Methods 0.000 description 23
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 16
- 239000000155 melt Substances 0.000 description 15
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- 241000555745 Sciuridae Species 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 229920005692 JONCRYL® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 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 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000928259 Homo sapiens NADPH:adrenodoxin oxidoreductase, mitochondrial Proteins 0.000 description 1
- 102100036777 NADPH:adrenodoxin oxidoreductase, mitochondrial Human genes 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OVSARSKQWCLSJT-UHFFFAOYSA-N n,n-di(propan-2-yl)aniline Chemical compound CC(C)N(C(C)C)C1=CC=CC=C1 OVSARSKQWCLSJT-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/785—Preparation processes characterised by the apparatus used
Abstract
The invention discloses a process for preparing high-strength polyglycolic acid by continuous polycondensation, which takes glycolic acid, methyl glycolate or ethyl glycolate as a polymerization monomer, carries out polycondensation reaction step by adjusting the reaction temperature, the reaction pressure and a stirring device of a first polycondensation reaction kettle, a second polycondensation reaction kettle, a third polycondensation reaction kettle and a fourth polycondensation reaction kettle, and arranges a mixer between the third polycondensation reaction kettle and the fourth polycondensation reaction kettle to realize the full mixing of the product of the third polycondensation reaction kettle and a chain extender. The raw materials and the chain extender adopted by the process are easy to obtain, the process route is simple, and continuous production can be realized. Meanwhile, polyglycolic acid is in a liquid state in the reaction process and can be fully mixed with the chain extender for reaction. The polyglycolic acid prepared by the method has the weight average molecular weight of more than 10 ten thousand, the tensile strength of more than 120MPa, and the performance of the polyglycolic acid is equivalent to that of polyglycolic acid obtained by ring-opening polymerization of glycolide.
Description
The technical field is as follows:
the invention relates to the field of polymer preparation, in particular to a process for preparing high-strength polyglycolic acid through continuous polycondensation.
Background art:
polyglycolic acid (PGA), also known as polyglycolic acid, has a wide range of applications in various fields due to its good mechanical properties, biodegradability and biocompatibility, and is an important member in the field of biodegradable materials. In the field of daily life, PGA can be used for manufacturing disposable degradable articles for daily use, such as toothbrush handles, combs, disposable lunch boxes, wrappages and the like. In the biomedical application field, PGA is mainly used as degradable medical suture, drug controlled release carrier, fracture fixation material, tissue engineering scaffold, suture reinforcement material and the like. In the field of oil and gas development, PGA can be used for bridge plugs, fracturing balls, temporary plugging agents and the like.
At present, the preparation process of polyglycolic acid mainly comprises two processes: the method has simple process route, wide monomer raw material source and easy operation, can only obtain polyglycolic acid with lower polymerization degree, has lower mechanical property, and can meet the use requirement by further treatment. For example, patent CN106432696A discloses a method for preparing stretch-proof polyglycolic acid, which comprises the steps of using glycolic acid as a raw material, dehydrating the glycolic acid in a vacuum condition, mixing the obtained glycolic acid oligomer with a catalyst to react to obtain a polyglycolic acid intermediate product, adding a chain extender TDI, and heating to react to increase the molecular weight of the polyglycolic acid. However, the reaction temperature of the above invention is below the melting point of polyglycolic acid, polyglycolic acid is solid and cannot react with the chain extender sufficiently, the improvement of product performance is limited, and continuous production cannot be achieved. Meanwhile, the used chain extender TDI mainly reacts with hydroxyl in oligoglycolic acid, so that the prepared polymer has a large terminal carboxyl value, is degraded too fast and has low practicability. Patent CN112831031A discloses a method for preparing polyglycolic acid, which uses two poly-glycolic acids with different molecular weights as raw materials to carry out reaction. The higher molecular weight polyglycolic acid starting material has a molecular weight 20 to 100 times that of the lower one. The molecular weights of the two materials are greatly different, and the reaction system has the problem of non-homogeneous phase, so that the reaction efficiency is influenced. From the results of the experiments, the difference between the molecular weight of the polyglycolic acid starting material having a relatively high molecular weight to that of the final product was not so large (only about 3 times), and the increase in the molecular weight of the polymer was limited. The glycolide is prepared by ring-opening polymerization of glycolide, and a monomer glycolide is prepared by the processes of polycondensation, cracking, purification and the like of glycolic acid or glycolates, and has complex preparation process and harsh glycolide storage conditions; for example, patent CN101616907A discloses a method for preparing glycolide for polymerization, which comprises dissolving glycolic acid oligomer in a depolymerization solvent with high boiling point, distilling off glycolide produced by the cracking and the depolymerization solvent at high temperature and low pressure, and further purifying. Patent CN10461969A provides a method for purifying glycolide by gas-liquid countercurrent extraction of crude glycolide obtained by cracking glycolic acid oligomer, thereby obtaining glycolide suitable for polymerization.
The invention content is as follows:
the invention provides a process for preparing high-strength polyglycolic acid by continuous polycondensation, aiming at solving the problems that the conventional glycolic acid direct dehydration polycondensation can only obtain polyglycolic acid with lower polymerization degree, the improvement of solid phase chain extension performance is limited, the process flow for preparing high-molecular polyglycolic acid by ring-opening polymerization of glycolide is long, the equipment is complex, glycolide monomers are difficult to prepare and store and the like.
The invention is implemented by the following technical scheme: a process for preparing high-strength polyglycolic acid by continuous polycondensation is characterized by comprising the following steps:
(1) continuously injecting a polymerized monomer or a polymerized monomer aqueous solution and a polycondensation catalyst into a first polycondensation reaction kettle at a certain speed (the speed is determined according to actual working conditions), and slowly pumping water or a volatile polycondensation product out of a system at 90-120 ℃ and under the pressure of 50-300kPa, so that the number-average polymerization degree (the polymerization degree of a polymer is represented by the number of structural units) of the polymer product in the first polycondensation reaction kettle reaches 1-5;
(2) continuously injecting the polymer product obtained in the step (1) into a second polycondensation reaction kettle, and further pumping water or volatile polycondensation product out of the system at the temperature of 110-;
(3) continuously injecting the polymer product obtained in the step (2) into a third polycondensation reaction kettle, and further pumping water or the volatile polycondensation product out of the system at the temperature of 150-;
(4) continuously injecting the polymer product obtained in the step (3) into a mixer, and simultaneously continuously injecting a chain extender into the mixer, so that the polymer product obtained in the step (3) and the chain extender are fully mixed;
(5) injecting the mixture obtained in the step (4) into a fourth polycondensation reaction kettle, and further pumping water or the volatile polycondensation product out of the system under the conditions of 200-270 ℃ and 0.01-5kPa to ensure that the weight average molecular weight of the obtained polymer product reaches more than 10 ten thousand.
Preferably, the polymerizable monomer is any one of glycolic acid, methyl glycolate or ethyl glycolate.
Preferably, the mass of the added polycondensation catalyst is 0.1-10% of the mass of the added polymerization monomer.
Preferably, the aqueous monomer solution is an aqueous glycolic acid solution, and the concentration of the aqueous glycolic acid solution at 20 ℃ is between 30% and 70% by mass (mass concentration ═ solute mass/solution mass) × 100%).
Preferably, the mass of the polycondensation catalyst added is 0.1 to 10% of the mass of glycolic acid in the aqueous glycolic acid solution.
Preferably, the polycondensation catalyst is any one or a combination of more than one of metal oxide, metal chloride hydrate or organic metal compound.
Preferably, the metal oxide is an oxide of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; the metal chloride is a chloride of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; the metal chloride hydrate is a chloride hydrate of tin, antimony, aluminum, zirconium, iron, zinc or bismuth.
Preferably, the organometallic compound is an acetate-based compound of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; or a tin, antimony, aluminum, zirconium, iron, zinc or bismuth octoate-based compound; or an acetylacetonate group of tin, antimony, aluminum, zirconium, iron, zinc or bismuth.
Preferably, the first polycondensation reaction kettle, the second polycondensation reaction kettle and the third polycondensation reaction kettle are vertical reaction kettles, and the fourth polycondensation reaction kettle is a horizontal reaction kettle.
Preferably, stirrers are arranged in the first polycondensation reaction kettle, the second polycondensation reaction kettle and the third polycondensation reaction kettle; and a stirring device is arranged in the fourth polycondensation reaction kettle, and the stirring device is any one of a squirrel-cage stirrer, a horizontal disc stirrer or a double-screw extruder.
Preferably, the mixer is a mechanically stirred mixer or a static mixer.
Preferably, the chain extender is any one or a combination of one or more of alcohols having 2 or more hydroxyl groups in the molecular structure, phenols having 2 or more hydroxyl groups, amines having 2 or more amino groups, bisoxazoline compounds, compounds having 1 or more epoxy groups, or compounds having 1 or more carbodiimide groups. Chain extenders are used to link two or more short polymer chains to increase the molecular weight of the polymer. Meanwhile, the chain extender can react with carboxyl in the polyglycolic acid to reduce the terminal carboxyl value of the obtained polymer and improve the service property of the polymer.
Preferably, the alcohol containing 2 or more hydroxyl groups is ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, pentaerythritol or diethylene glycol;
the phenols containing 2 or more than 2 hydroxyl groups are bisphenol A, resorcinol or hydroquinone;
the amine containing 2 or more amino groups is ethylenediamine, hexamethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, N-dihydroxy (diisopropyl) aniline, methylcyclohexanediamine, 4 '-methylenebis (2, 6-diethylaniline), 4' -methylene-bis (3-chloro-2, 6-diethylaniline), 4 '-bis-sec-butylaminodiphenylmethane, 3-chloro-3' -ethyl-4, 4 '-diaminodiphenylmethane, 4' -methylenebis (2-ethyl) aniline, 4 '-methylenebis (2-ethyl-6-methylaniline), 4' -methylenebis (cyclohexylamine), tris (2-aminoethyl) amine, or a salt thereof, 2- (aminomethyl) -2-methyl-1, 3-propanediamine, spermidine, spermine, or triethylenetetramine;
the bisoxazoline compound is 2,2 ' -methylenebis [ (4, S) -4-phenyl-2-oxazoline ], 2 ' -isopropylidenebis [ (4R) -4-benzyl-2-oxazoline ] or 2,2 ' -methylenebis [ (4S) -4-tert-butyl-2-oxazoline ];
the compound containing 1 or more than 1 epoxy group is bisphenol A diglycidyl ether, resorcinol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, glycerol triglycidyl ether or oligomer with a side group containing an epoxy group;
the compound containing 1 or more carbodiimide groups is dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, polymeric carbodiimide or BioAdimide 100.
Preferably, when the compound containing 1 or more carbodiimide groups is used as a chain extender, an auxiliary catalyst which is favorable for improving the reaction rate is added at the same time, and the auxiliary catalyst is 4-dimethylaminopyridine; the mass ratio of the addition amount of the auxiliary catalyst to the addition amount of the compound containing 1 or more carbodiimide groups is (1: 30) - (1): 1.
preferably, the chain extender is diluted with an organic solvent, preferably an organic solvent capable of forming an azeotropic system with water, such as toluene, xylene, tetrahydrofuran, anisole, for convenient transportation and metering.
Preferably, the mass fraction of the chain extender in the organic solvent is 1-50%.
Preferably, in the step (4), the ratio of the injection rate of the chain extender to the injection rate of the polymerization monomer or the aqueous solution of the polymerization monomer and the polycondensation catalyst in the step (1) is 1:30 to 1: 150.
The invention has the advantages that: the raw materials and the chain extender adopted by the process are easy to obtain, the process route is simple, and continuous production can be realized. Meanwhile, polyglycolic acid is in a liquid state in the reaction process and can be fully mixed with the chain extender for reaction. The polyglycolic acid prepared by the method has the weight average molecular weight of more than 10 ten thousand, the tensile strength of more than 120MPa, and the performance of the polyglycolic acid is equivalent to that of polyglycolic acid obtained by ring-opening polymerization of glycolide.
The specific implementation mode is as follows:
the principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
continuously injecting 70 mass percent glycolic acid aqueous solution and stannous oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous oxide is 1 percent of the mass of the glycolic acid in the glycolic acid aqueous solution, the temperature of the first polycondensation reaction kettle is set to be 110 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; pumping the polymer product generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 150 ℃, and the pressure of the second polycondensation reaction kettle is 50kPa, so as to obtain the polymer product with the number average polymerization degree of 18; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 200 ℃, and the pressure is 5kPa, so that the polymer product with the number average polymerization degree of 82 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting bisphenol A diglycidyl ether into the static mixer at the speed of 5kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 240 ℃ and the pressure was set at 0.5kPa to obtain a polymer having a number average degree of polymerization of 950 and a weight average molecular weight of 14.2 ten thousand.
Example 2:
continuously injecting 70 mass percent aqueous glycolic acid solution and zinc oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added zinc oxide is 1% of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to be 120 ℃, and the pressure is 70kPa, so as to obtain a polymer product with the number average polymerization degree of 4; pumping the polymer product generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 160 ℃, and the pressure is 30kPa, so as to obtain the polymer product with the number average polymerization degree of 20; and further pumping the polymer product into a third polycondensation reaction kettle for continuous dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 200 ℃, and the pressure is 3kPa, so that the polymer product with the number-average polymerization degree of 91 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting trimethylolpropane into the static mixer at the speed of 3kg/hr, fully mixing by the static mixer, pumping into a fourth polycondensation reaction kettle, wherein the fourth polycondensation reaction kettle adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer so as to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 250 ℃ and the pressure was set at 0.5kPa to obtain a polymer having a number average degree of polymerization of 990 and a weight average molecular weight of 15.1 ten thousand.
Example 3:
continuously injecting 70 mass percent aqueous glycolic acid solution and stannous chloride into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous chloride is 0.5 percent of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to be 100 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number average polymerization degree of 5; pumping the polymer product generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 150 ℃, and the pressure of the second polycondensation reaction kettle is 50kPa, so as to obtain the polymer product with the number average polymerization degree of 18; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 190 ℃, and the pressure is 2kPa, so that the polymer product with the number average polymerization degree of 89 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting glycerol triglycidyl ether into the static mixer at the speed of 6kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 240 ℃ and the pressure was 0.1kPa, whereby a polymer having a number-average degree of polymerization of 1200 and a weight-average molecular weight of 17.2 ten thousand was obtained.
Example 4:
continuously injecting 70 mass percent aqueous glycolic acid solution and antimony oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added antimony oxide is 1% of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to 95 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to 145 ℃, and the pressure of the second polycondensation reaction kettle is 40kPa, so as to obtain a polymer product with the number average polymerization degree of 16; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 180 ℃, and the pressure is 2kPa, so that the polymer product with the number average polymerization degree of 65 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting hexamethylene diamine into the static mixer at the speed of 5kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 230 ℃ and the pressure was set at 0.3kPa, whereby a polymer having a number average degree of polymerization of 960 and a weight average molecular weight of 15.2 ten thousand was obtained.
Example 5:
continuously injecting 70 mass percent aqueous glycolic acid solution and antimony oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added antimony oxide is 1% of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to 95 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to 145 ℃, and the pressure of the second polycondensation reaction kettle is 40kPa, so as to obtain a polymer product with the number average polymerization degree of 16; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 180 ℃, and the pressure is 2kPa, so that the polymer product with the number average polymerization degree of 65 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously injecting 2, 2' -methylene bis [ (4S) -4-tert-butyl-2-oxazoline ] into the static mixer at the speed of 5kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 230 ℃ and the pressure was set at 0.5kPa, whereby a polymer having a number average degree of polymerization of 920 and a weight average molecular weight of 14.1 ten thousand was obtained.
Example 6:
continuously injecting 70 mass percent aqueous glycolic acid solution and stannous octoate into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous octoate is 0.6 percent of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to be 100 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number-average polymerization degree of 4; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 160 ℃, and the pressure is 30kPa, so as to obtain a polymer product with the number average polymerization degree of 18; and further pumping the polymer product into a third polycondensation reaction kettle for continuous dehydration, wherein the temperature of the third polycondensation reaction kettle is set to 190 ℃, and the pressure is 3kPa, so that the polymer product with the number-average polymerization degree of 86 is obtained. Continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, and simultaneously continuously injecting a toluene solution dissolved with BioAdimide 100 and 4-dimethylaminopyridine into the static mixer at the speed of 25kg/hr, wherein the mass fraction of the BioAdimide 100 in the solution is 20%, and the mass fraction of the 4-dimethylaminopyridine in the solution is 2%; and after fully mixed by the static mixer, pumping the mixture into a fourth polycondensation reaction kettle, wherein the fourth polycondensation reaction kettle adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer so as to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 235 ℃ and the pressure was 0.2kPa, whereby 1630 as a number average degree of polymerization and 25.6 ten thousand as a weight average molecular weight were obtained.
Example 7:
continuously injecting 70 mass percent glycolic acid aqueous solution and stannous chloride into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous chloride is 1.3 percent of the mass of glycolic acid in the glycolic acid aqueous solution, the temperature of the first polycondensation reaction kettle is set to be 120 ℃, and the pressure is 80kPa, so as to obtain a polymer product with the number-average polymerization degree of 4; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 170 ℃, and the pressure is 60kPa, so as to obtain a polymer product with the number-average polymerization degree of 19; and further pumping the polymer product into a third polycondensation reaction kettle for continuous dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 200 ℃, and the pressure is 5kPa, so that the polymer product with the number average polymerization degree of 79 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting 20 mass percent of Joncryl ADR-4368 dimethylbenzene solution into the static mixer at the speed of 20kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set to 250 ℃ and the pressure was set to 0.7kPa, whereby a polymer having a number average degree of polymerization of 1870 and a weight average molecular weight of 29.4 ten thousand was obtained.
Example 8:
continuously injecting 70 mass percent glycolic acid aqueous solution and stannous chloride into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous chloride is 0.7 percent of the mass of glycolic acid in the glycolic acid aqueous solution, the temperature of the first polycondensation reaction kettle is set to be 110 ℃, and the pressure is 80kPa, so as to obtain a polymer product with the number-average polymerization degree of 4; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 160 ℃, and the pressure of the second polycondensation reaction kettle is 50kPa, so as to obtain a polymer product with the number average polymerization degree of 15; and further pumping the polymer product into a third polycondensation reaction kettle for continuous dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 190 ℃, and the pressure is 4kPa, so that the polymer product with the number-average polymerization degree of 84 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting a 10 mass percent toluene solution of bisphenol A into the static mixer at the speed of 30kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 240 ℃ and the pressure was set at 0.2kPa to obtain a polymer having a number average degree of polymerization of 830 and a weight average molecular weight of 12.7 ten thousand.
Example 9:
continuously injecting 70 mass percent aqueous glycolic acid solution and zirconia into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added zirconia is 1% of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set at 110 ℃, and the pressure is 80kPa, so as to obtain a polymer product with the number average polymerization degree of 4; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 150 ℃, and the pressure is 40kPa, so as to obtain a polymer product with the number average polymerization degree of 17; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 190 ℃, and the pressure is 2kPa, so that the polymer product with the number average polymerization degree of 78 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting 20 mass percent of Joncryl ADR-4368 dimethylbenzene solution into the static mixer at the speed of 20kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 250 ℃ and the pressure was 0.2kPa, whereby a polymer having a number average polymerization degree of 1940 and a weight average molecular weight of 31.9 ten thousand was obtained.
Example 10:
continuously injecting 70 mass percent aqueous glycolic acid solution and zinc acetate dihydrate into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added zinc acetate dihydrate is 1.5 percent of the mass of the glycolic acid in the aqueous glycolic acid solution, the temperature of the first polycondensation reaction kettle is set to be 100 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number average polymerization degree of 5; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 160 ℃, and the pressure is 60kPa, so as to obtain a polymer product with the number average polymerization degree of 16; and further pumping the polymer product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to 210 ℃, and the pressure is 1kPa, so that the polymer product with the number average polymerization degree of 93 is obtained. And continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, simultaneously continuously injecting diethyl toluenediamine into the static mixer at the speed of 3kg/hr, fully mixing by the static mixer, and pumping into a fourth polycondensation reaction kettle which adopts a horizontal reaction kettle and is internally provided with a squirrel cage type stirrer to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set at 235 ℃ and the pressure was set at 0.1kPa, whereby a polymer having a number average degree of polymerization of 890 and a weight average molecular weight of 13.4 ten thousand was obtained.
Example 11:
continuously injecting 99% of methyl glycolate and stannous oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the adding mass of the stannous oxide is 1% of the adding mass of the 99% of the methyl glycolate, the temperature of the first polycondensation reaction kettle is set to be 120 ℃, and the pressure is 190kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; pumping the polymer product generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 170 ℃, and the pressure of the second polycondensation reaction kettle is 50kPa, so as to obtain the polymer product with the number average polymerization degree of 15; and further pumping the polymer product into a third polycondensation reaction kettle for continuous reaction, wherein the temperature of the third polycondensation reaction kettle is set to 210 ℃, and the pressure is 1kPa, so that the polymer product with the number-average polymerization degree of 88 is obtained. Continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, and simultaneously continuously injecting a toluene solution dissolved with dicyclohexylcarbodiimide and 4-dimethylaminopyridine into the static mixer at the speed of 15kg/hr, wherein the mass fraction of the dicyclohexylcarbodiimide in the solution is 20%, and the mass fraction of the 4-dimethylaminopyridine is 1%; and after fully mixed by the static mixer, pumping the mixture into a fourth polycondensation reaction kettle, wherein the fourth polycondensation reaction kettle adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer so as to improve the reaction efficiency. The temperature of the fourth polycondensation reaction vessel was set at 240 ℃ and the pressure was set at 0.3kPa to obtain a polymer having a number average degree of polymerization of 780 and a weight average molecular weight of 11.7 ten thousand.
Example 12:
continuously injecting 99% of ethyl glycolate and stannous oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the adding mass of the stannous oxide is 1% of the adding mass of the 99% of the ethyl glycolate, the temperature of the first polycondensation reaction kettle is set to be 120 ℃, and the pressure is 170kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; pumping the polymer product melt generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 170 ℃, and the pressure is 10kPa, so as to obtain a polymer product with the number average polymerization degree of 13; and further pumping the polymer product into a third polycondensation reaction kettle for dealcoholization, wherein the temperature of the third polycondensation reaction kettle is set to be 210 ℃, and the pressure is 1kPa, so that the polymer product with the number average polymerization degree of 63 is obtained. Continuously injecting the polymer product produced in the third polycondensation reaction kettle into a static mixer, and simultaneously injecting a toluene solution dissolved with dicyclohexylcarbodiimide and 4-dimethylaminopyridine into the static mixer at the speed of 15kg/hr, wherein the mass fraction of the dicyclohexylcarbodiimide in the solution is 20%, and the mass fraction of the 4-dimethylaminopyridine is 1%; and after fully mixed by the static mixer, pumping the mixture into a fourth polycondensation reaction kettle, wherein the fourth polycondensation reaction kettle adopts a horizontal reaction kettle and is internally provided with a squirrel-cage stirrer so as to improve the reaction efficiency. The temperature of the fourth polycondensation reaction vessel was set to 250 ℃ and the pressure was set to 0.05kPa, whereby a polymer having a number average degree of polymerization of 790 and a weight average molecular weight of 12.3 ten thousand was obtained.
Comparative example:
comparative example: continuously injecting 70 mass percent glycolic acid aqueous solution and stannous oxide into a first polycondensation reaction kettle at the rate of 300kg/hr, wherein the mass of the added stannous oxide is 1 percent of the mass of the glycolic acid in the glycolic acid aqueous solution, the temperature of the first polycondensation reaction kettle is set to be 110 ℃, and the pressure is 90kPa, so as to obtain a polymer product with the number-average polymerization degree of 3; and pumping the polymer product generated in the first polycondensation reaction kettle into a second polycondensation reaction kettle by a melt pump, wherein the temperature of the second polycondensation reaction kettle is set to be 150 ℃, and the pressure of the second polycondensation reaction kettle is 50kPa, so that the polymer product with the number average polymerization degree of 18 is obtained. And further pumping the product into a third polycondensation reaction kettle for dehydration, wherein the temperature of the third polycondensation reaction kettle is set to be 200 ℃, and the pressure is 5kPa, so that a polymer product with the number average polymerization degree of 82 is obtained. And pumping the polymer product produced in the third polycondensation reaction kettle into a fourth polycondensation reaction kettle, wherein the fourth polycondensation reaction kettle adopts a horizontal reaction kettle, and a squirrel-cage stirrer is arranged in the fourth polycondensation reaction kettle to improve the dehydration efficiency. The temperature of the fourth polycondensation reaction vessel was set to 240 ℃ and the pressure was 0.5kPa, whereby a product having a number average degree of polymerization of 190 and a weight average molecular weight of 2.1 ten thousand was obtained.
The polymers 1 to 12 obtained in examples 1 to 12 and the comparative polymer obtained in comparative example were each subjected to the measurement of molecular weight, melt index and tensile strength by the following methods:
(1) and (3) determination of melt index: drying a polyglycolic acid sample to be measured until the water content is lower than 200ppm, and adding about 10g of the sample into a melt index instrument for measurement; the parameters measured by the melt index meter are as follows: the temperature was 250 ℃ and the load was 2.16 kg.
(2) And (3) measuring the molecular weight: drying a polyglycolic acid sample to be detected until the water content is lower than 200 ppm; placing about 1g of sample in a square die, heating in a hot press at 260 ℃ for 3 minutes, keeping the pressure at 5.0MPa for 1 minute, and transferring to a cooling water-cooling tablet press at 4 ℃ for cooling to prepare amorphous polyglycolic acid; dissolving the amorphous polyglycolic acid in hexafluoroisopropanol with 5mM sodium trifluoroacetate to prepare a solution having a concentration of about 1%; the solution was filtered through a 0.45um PTFE filter and subjected to Gel Permeation Chromatography (GPC) for molecular weight measurement; taking polymethyl methacrylate as a standard sample to carry out molecular weight calibration; the GPC test conditions were as follows:
a chromatographic column: Shodex-806M;
column temperature: 40 ℃;
eluent: 5mM sodium trifluoroacetate in hexafluoroisopropanol;
flow rate: 1mL/min
A detector: an RI detector;
a chromatographic device: shimadzu LC-20 ADXR.
(3) And (3) testing tensile strength: drying the polyglycolic acid resin to be detected until the water content is lower than 200 ppm; preparing standard sample strips by an injection molding machine (GB/T1040.2-2006 plastic tensile property measurement); the specification of the tensile sample strip is a 1A dumbbell type sample strip; the test method is tested according to GB/T1040.1-2018, and the stretching speed is 1 mm/min.
The test data are shown in the following table:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit of the present invention are intended to be included within the scope of the present invention.
Claims (17)
1. A process for preparing high-strength polyglycolic acid by continuous polycondensation is characterized by comprising the following steps:
(1) continuously injecting a polymerized monomer or a polymerized monomer water solution and a polycondensation catalyst into the first polycondensation reaction kettle at a certain speed, and slowly pumping water or a volatile polycondensation product out of the system at 90-120 ℃ and under the pressure of 50-300kPa, so that the number average polymerization degree of the polymer product in the first polycondensation reaction kettle reaches 1-5;
(2) continuously injecting the polymer product obtained in the step (1) into a second polycondensation reaction kettle, and further pumping water or volatile polycondensation product out of the system at the temperature of 110-;
(3) continuously injecting the polymer product obtained in the step (2) into a third polycondensation reaction kettle, and further pumping water or the volatile polycondensation product out of the system at the temperature of 150-;
(4) continuously injecting the polymer product obtained in the step (3) into a mixer, and simultaneously continuously injecting a chain extender into the mixer, so that the polymer product obtained in the step (3) and the chain extender are fully mixed;
(5) injecting the mixture obtained in the step (4) into a fourth polycondensation reaction kettle, and further pumping water or the volatile polycondensation product out of the system under the conditions of 200-270 ℃ and 0.01-5kPa to ensure that the weight average molecular weight of the obtained polymer product reaches more than 10 ten thousand.
2. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 1, wherein the polymeric monomer is any one of glycolic acid, methyl glycolate or ethyl glycolate.
3. The process for preparing the high-strength polyglycolic acid through the continuous polycondensation as claimed in claim 2, wherein the mass of the added polycondensation catalyst is 0.1-10% of the mass of the added polymeric monomer.
4. The process for preparing high-strength polyglycolic acid through continuous polycondensation according to claim 1, wherein the aqueous solution of the polymeric monomers is an aqueous glycolic acid solution, and the concentration of the aqueous glycolic acid solution at 20 ℃ is between 30 and 70 percent by mass.
5. The process for preparing high-strength polyglycolic acid through continuous polycondensation according to claim 4, wherein the mass of the polycondensation catalyst added is 0.1 to 10% of the mass of glycolic acid in the aqueous glycolic acid solution.
6. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 1, wherein the polycondensation catalyst is any one or more of metal oxide, metal chloride hydrate or organometallic compound.
7. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 6, wherein the metal oxide is an oxide of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; the metal chloride is a chloride of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; the metal chloride hydrate is a chloride hydrate of tin, antimony, aluminum, zirconium, iron, zinc or bismuth.
8. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 6, wherein the organometallic compound is an acetate compound of tin, antimony, aluminum, zirconium, iron, zinc or bismuth; or a tin, antimony, aluminum, zirconium, iron, zinc or bismuth octoate-based compound; or an acetylacetonate group of tin, antimony, aluminum, zirconium, iron, zinc or bismuth.
9. The process for preparing high-strength polyglycolic acid through continuous polycondensation according to claim 1, wherein the first polycondensation reaction kettle, the second polycondensation reaction kettle and the third polycondensation reaction kettle are vertical reaction kettles, and the fourth polycondensation reaction kettle is a horizontal reaction kettle.
10. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 9, wherein a stirrer is disposed in each of the first polycondensation reaction vessel, the second polycondensation reaction vessel and the third polycondensation reaction vessel; and a stirring device is arranged in the fourth polycondensation reaction kettle, and the stirring device is any one of a squirrel-cage stirrer, a horizontal disc stirrer or a double-screw extruder.
11. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 1, wherein the mixer is a mechanical mixer or a static mixer.
12. The process for preparing high-strength polyglycolic acid by continuous polycondensation according to claim 1, wherein the chain extender is one or a combination of one or more of alcohols having 2 or more hydroxyl groups in the molecular structure, phenols having 2 or more hydroxyl groups, amines having 2 or more amino groups, bisoxazoline compounds, compounds having 1 or more epoxy groups or 1 or more carbodiimide groups.
13. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 12, where the alcohols containing 2 or more hydroxyl groups are ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, pentaerythritol or diethylene glycol;
the phenols containing 2 or more than 2 hydroxyl groups are bisphenol A, resorcinol or hydroquinone;
the amine containing 2 or more amino groups is ethylenediamine, hexamethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, methylcyclohexanediamine, 4 '-methylenebis (2, 6-diethylaniline), 4' -methylene-bis (3-chloro-2, 6-diethylaniline), 4 '-bis-sec-butylaminodiphenylmethane, 3-chloro-3' -ethyl-4, 4 '-diaminodiphenylmethane, 4' -methylenebis (2-ethyl) aniline, 4 '-methylenebis (2-ethyl-6-methylaniline), 4' -methylenebis (cyclohexylamine), tris (2-aminoethyl) amine, 2- (aminomethyl) -2-methyl-1, 3-propanediamine, spermidine, spermine or triethylenetetramine;
the bisoxazoline compound is 2,2 ' -methylenebis [ (4, S) -4-phenyl-2-oxazoline ], 2 ' -isopropylidenebis [ (4R) -4-benzyl-2-oxazoline ] or 2,2 ' -methylenebis [ (4S) -4-tert-butyl-2-oxazoline ];
the compound containing 1 or more than 1 epoxy group is bisphenol A diglycidyl ether, resorcinol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, glycerol triglycidyl ether or oligomer with a side group containing an epoxy group.
The compound containing 1 or more carbodiimide groups is dicyclohexylcarbodiimide, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride or polymeric carbodiimide.
14. The continuous polycondensation process for preparing high-strength polyglycolic acid according to claim 13, wherein an auxiliary catalyst is added simultaneously when the compound containing 1 or more carbodiimide groups is used as a chain extender, wherein the auxiliary catalyst is 4-dimethylaminopyridine; the mass ratio of the addition amount of the auxiliary catalyst to the addition amount of the compound containing 1 or more carbodiimide groups is (1: 30) - (1): 1.
15. the continuous polycondensation process for preparing high-strength polyglycolic acid according to any one of claims 12 to 14, wherein the chain extender is diluted with an organic solvent, and the organic solvent is any one of toluene, xylene, tetrahydrofuran or anisole.
16. The process for preparing high-strength polyglycolic acid through continuous polycondensation according to claim 15, wherein the mass fraction of the chain extender in the organic solvent is 1% to 50%.
17. The process for preparing high-strength polyglycolic acid through continuous polycondensation according to claim 1, wherein in the step (4), the ratio of the injection rate of the chain extender to the injection rate of the polymerization monomer or the aqueous solution of the polymerization monomer and the polycondensation catalyst in the step (1) is 1:30 to 1: 150.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111615435.3A CN114195998A (en) | 2021-12-27 | 2021-12-27 | Process for preparing high-strength polyglycolic acid by continuous polycondensation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111615435.3A CN114195998A (en) | 2021-12-27 | 2021-12-27 | Process for preparing high-strength polyglycolic acid by continuous polycondensation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114195998A true CN114195998A (en) | 2022-03-18 |
Family
ID=80656785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111615435.3A Pending CN114195998A (en) | 2021-12-27 | 2021-12-27 | Process for preparing high-strength polyglycolic acid by continuous polycondensation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114195998A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116284698A (en) * | 2023-02-21 | 2023-06-23 | 内蒙古久泰新材料科技股份有限公司 | Production process for simultaneously preparing various molecular weight gradient degradable materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051729A (en) * | 2002-07-18 | 2004-02-19 | Asahi Kasei Chemicals Corp | Process for producing shaped product of glycolic acid copolymer |
| CN111087580A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing polyglycolic acid |
| US20210395444A1 (en) * | 2018-10-29 | 2021-12-23 | Pujing Chemical Industry Co., Ltd. | Controlled Production of Polyglycolic Acid and Glycolide |
-
2021
- 2021-12-27 CN CN202111615435.3A patent/CN114195998A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004051729A (en) * | 2002-07-18 | 2004-02-19 | Asahi Kasei Chemicals Corp | Process for producing shaped product of glycolic acid copolymer |
| CN111087580A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing polyglycolic acid |
| US20210395444A1 (en) * | 2018-10-29 | 2021-12-23 | Pujing Chemical Industry Co., Ltd. | Controlled Production of Polyglycolic Acid and Glycolide |
Non-Patent Citations (1)
| Title |
|---|
| 张巧玲等, 国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116284698A (en) * | 2023-02-21 | 2023-06-23 | 内蒙古久泰新材料科技股份有限公司 | Production process for simultaneously preparing various molecular weight gradient degradable materials |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111019126B (en) | Polyester amide and preparation method thereof | |
| US20130267675A1 (en) | Process for producing polylactic acid and reactors for use in said process | |
| CN106957415A (en) | It is a kind of for composite catalyst of carbon dioxide, expoxy propane and lactide ternary polymerization and preparation method thereof | |
| AU2006307959A1 (en) | Polyamides formed from meta-xylylenediamine and adipic acid and having an amino end group content of less than 15 mmol/kg | |
| CN103804663A (en) | Aliphatic series-polylactic acid segmented copolymer and preparation method thereof | |
| CN101525411B (en) | Method for producing poly-lactic acid products | |
| CN105585695B (en) | Method for preparing poly-caprolactone-lactide in supercritical carbon dioxide in random copolymerization mode | |
| CN114195998A (en) | Process for preparing high-strength polyglycolic acid by continuous polycondensation | |
| CN113292719A (en) | Polyamide resin containing imide structure and preparation method thereof | |
| CN105732569B (en) | Purification method of crude lactide and preparation method of high molecular weight polylactic acid | |
| JP5416829B2 (en) | Method for producing heat-resistant polyamide | |
| CN1583819A (en) | Synthesis of polylactate in supercrilical fluid of CO2 | |
| CN117004007B (en) | Crystalline aliphatic polycarbonate with high molecular weight and high mechanical property and preparation method thereof | |
| CN1260267C (en) | Process for producing high branched poly ester with unsaturated end group | |
| CN112469761A (en) | Controlled production of polyglycolic acid and glycolide | |
| CN103910878B (en) | A kind of lysine synthesis semi-aromatic nylon and preparation method thereof | |
| CN109320699B (en) | Thermoplastic aliphatic-aromatic copolyester elastomer and preparation method thereof | |
| CN110467726B (en) | High-melting-point bio-based polyesteramide and preparation method thereof | |
| CN104955886B (en) | Porous material, its production method and its continuous producing apparatus | |
| CN108191815B (en) | Method for producing L-lactide by using L-lactic acid | |
| CN112028868A (en) | Preparation method of glycolide | |
| CN114213634B (en) | Continuous preparation process of alkyd oligomer | |
| CN104710614A (en) | Preparation method of branched nylon resin | |
| CN112759760B (en) | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof | |
| KR101813397B1 (en) | Method for preparing polyamide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220318 |