CN103467713B - Low-carboxylated biodegradable polyester and production method thereof - Google Patents
Low-carboxylated biodegradable polyester and production method thereof Download PDFInfo
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- CN103467713B CN103467713B CN201310396952.5A CN201310396952A CN103467713B CN 103467713 B CN103467713 B CN 103467713B CN 201310396952 A CN201310396952 A CN 201310396952A CN 103467713 B CN103467713 B CN 103467713B
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 41
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 43
- 230000032050 esterification Effects 0.000 claims abstract description 35
- 238000005886 esterification reaction Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 7
- -1 erythrol ester Chemical class 0.000 claims description 105
- 238000003756 stirring Methods 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 239000002253 acid Substances 0.000 claims description 51
- 239000002994 raw material Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 238000006068 polycondensation reaction Methods 0.000 claims description 28
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tertiry butyl alcohol Natural products CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 4
- XNJDQHLXEBQMDE-UHFFFAOYSA-N 2-(cyclohexyloxymethyl)oxirane Chemical compound C1OC1COC1CCCCC1 XNJDQHLXEBQMDE-UHFFFAOYSA-N 0.000 claims description 4
- RUGWIVARLJMKDM-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)furan Chemical compound C1OC1COCC1=CC=CO1 RUGWIVARLJMKDM-UHFFFAOYSA-N 0.000 claims description 4
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical group OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- XVBXJBGOQQLLAO-UHFFFAOYSA-J [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O Chemical compound [Ti+4].C=C.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O XVBXJBGOQQLLAO-UHFFFAOYSA-J 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 229930003836 cresol Natural products 0.000 claims description 4
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 4
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229940099273 magnesium trisilicate Drugs 0.000 claims description 4
- 229910000386 magnesium trisilicate Inorganic materials 0.000 claims description 4
- 235000019793 magnesium trisilicate Nutrition 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 4
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 claims description 4
- DAKZISABEDGGSV-UHFFFAOYSA-N n-(2-aminoethyl)acetamide Chemical compound CC(=O)NCCN DAKZISABEDGGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229960004249 sodium acetate Drugs 0.000 claims description 4
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229960000314 zinc acetate Drugs 0.000 claims description 4
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims description 3
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 3
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 claims description 3
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 230000007717 exclusion Effects 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- 150000002333 glycines Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229960004502 levodopa Drugs 0.000 claims 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- HISQRFFCSVGSGI-UHFFFAOYSA-N pentadecane-1,2,3-triol Chemical compound CCCCCCCCCCCCC(O)C(O)CO HISQRFFCSVGSGI-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000001361 adipic acid Substances 0.000 abstract description 4
- 239000002516 radical scavenger Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract 2
- 238000006482 condensation reaction Methods 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZHJQNCRLAJBKPV-UHFFFAOYSA-N C(C1CO1)C(C(C(O)CC1CO1)O)O.OCC(C)(CO)C Chemical compound C(C1CO1)C(C(C(O)CC1CO1)O)O.OCC(C)(CO)C ZHJQNCRLAJBKPV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 229920005839 ecoflex® Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of polyester high-molecular materials, and particularly relates to a low-carboxylated biodegradable polyester and a production method thereof. The low-carboxylated biodegradable polyester comprises1,6-adipic acid or/and terephthalic acid and 1,4-butanediol. According to the preparation method of the low-carboxylated biodegradable polyester, the content of carboxyl end groups in the polyester can be furthest reduced by adopting a compound titanium catalyst and a carboxyl scavenger to produce condensation polymerization in the later period of esterification; the catalytic activity of titanium catalyst can be controlled by adding chelate with stabilizing effect, so as to avoid the side degradation reaction caused by the high activity of the catalyst in the later period of condensation reaction and furthest reduce the side reaction in the later period of the condensation reaction, so that the low-carboxylated level of the finished polyester product can be guaranteed, other additives are not additionally needed for modifying the product, the content of carboxyl end groups in the product can be reduced, and the high production cost of the product can be avoided.
Description
Technical field
The present invention relates to polyester-based polymer field of material technology, it is a kind of carboxy lower Biodegradable polyester and its producer
Method.
Background technology
Nowadays, plastics are the class materials forming important complementation with materials such as timber, iron and steel, pottery, cement, have obtained non-
Often it is widely applied, greatly change our life.But, the use of conventional plastic has had resulted in serious " white
Pollution ", this comes from people when focusing on the performance of conventional plastic product, have ignored its environment property received.Conventional plastic is in ring
Decades can be detained in border, even go up a century and be also difficult to thoroughly degrade.Increasingly serious " white ecological pollution " problem has made
Obtain the common recognition that development environment friendly plastic product has become as countries in the world.Under the support of various incentive policies, in the world
Essential high molecular manufacturing enterprise have been developed for multiple degradative plastics products.The trade name of German BASF exploitation
" ecoflex " resin is exactly Typical Representative therein, its entitled " the polybutylene terephthalate (PBT) -co- polyadipate of chemistry
Butanediol ester (pbat) ", is the random copolymer being obtained through high-temperature polycondensation by p-phthalic acid, adipic acid and butanediol, belongs to
In the biodegradable plastic that mechanical property and degradation property are excellent.This resinoid, under certain wet heat condition, can slowly occur
Degraded, first generates the polymer segments that end group is carboxyl and hydroxyl.Afterwards, due to the presence meeting of more end group particularly end carboxyl
Greatly speed up the degradation rate of polyester.Eventually pass through microbial action and become carbon dioxide and water.If in composting conditionses
Under, the degradation rate of this polymer is faster.So, pbat is the friendly macromolecular material that a class environment can receive.But, this
One degradation characteristic also leads to its use under some hygrothermal environments to be extremely limited, such as agricultural mulching.For this reason, being necessary for
Try every possible means to reduce the end group in this kind of naval stores, the particularly content of end carboxyl, to improve this resinoid anti-hydrolytic performance,
Thus delaying degradation rate, to ensure the material mechanical performance under certain use condition and use time.Publication No.
Disclose in 102165012 Chinese patent literature a kind of by styrene, acrylate and/or methacrylate containing epoxy
Base co-polymer and acidic materials scavenger are blended with Biodegradable polyester under certain condition, water-fast to improve Biodegradable polyester
Solution property and the method for melt viscosity.But, the mode one side of this blending increased the cost of product, on the other hand in processing
During easily cause product complexion changed and Partial digestion, additionally, use acid cleaner such as carbodiimide compound in high temperature
Have irritative gass during processing and use to overflow, affect environment.The Chinese patent literature of Publication No. 102131868
In disclose a kind of in the course of the polymerization process solve aliphatic-aromatic copolyester hydrolytic resistance method, specific practice is first to divide
Not Zhun Bei aliphatic and aromatic ester compound, then two kinds of carboxylates are mixed, add phosphorous ground antioxidant and carbonate or
Person's carbonates material purpose hydrophobic to reach final polyester product.Although this method avoids and increases because of blending and modifying
Product cost problem, but, two step esterification process also increase the cost of product, meanwhile, if the degree of polymerization control improper, to
The biodegradability of finished product will produce impact.
Content of the invention
The invention provides a kind of carboxy lower Biodegradable polyester and its production method, overcome above-mentioned prior art no
Foot, its energy existing technology of effectively solving production cost when reducing Biodegradable polyester degradation rate is high and properties of product are unstable
Fixed problem.
One of technical scheme is realized by following measures: a kind of carboxy lower Biodegradable polyester, bag
Include raw materials by weight portion and consist of 40 parts to 100 parts 1,6- adipic acids or/and 1 part to 60 parts p-phthalic acid and 80 parts extremely
100 parts of BDOs, wherein, this carboxy lower Biodegradable polyester obtains as follows: the first step, and needed raw material is placed in
In reactor, and the temperature of material in reactor is raised to 80 DEG C to 100 DEG C, then will add raw material after material mix homogeneously
The metatitanic acid erythrol ester of weight 50ppm to 250ppm, is then 225 DEG C to 230 in pressure for -40kpa extremely -80kpa, temperature
DEG C, stir speed (S.S.) be 50r/min to 100r/min under conditions of carry out esterification, when the esterification water parts by weight collected reach
During to 15 parts to 55 parts, stop esterification；Second step, after esterification terminates, the pressure in reactor is adjusted to normal pressure,
Then add the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm into reactor, after mix homogeneously, add raw material weight
The amount carboxyl remover of 30ppm to the 1000ppm and chelating agen of raw material weight 10ppm to 300ppm, is then 0.5 in pressure
Kpa to 2kpa, temperature are 230 DEG C to 235 DEG C, stir speed (S.S.) is anti-for carrying out precondensation under conditions of 30r/min to 80r/min
Should, when stirring moment of torsion reaches 10n m to 100n m, prepolymerization reaction completes；3rd step, after the completion of prepolymerization reaction,
Pressure is 0pa to 100pa, temperature is 230 DEG C to 235 DEG C, stir speed (S.S.) is contracted under conditions of 30r/min to 80r/min
Poly- reaction, when stirring moment of torsion and reaching 20n m to 80n m, stops polycondensation reaction, after polycondensation reaction terminates, using nitrogen plus
Pressure removes the melt in reactor, obtains carboxy lower Biodegradable polyester with water-bath cooling.
The two of technical scheme are realized by following measures: a kind of life of carboxy lower Biodegradable polyester
Product method, raw materials by weight portion consists of 40 parts to 100 parts 1,6- adipic acids or/and 1 part to 60 parts p-phthalic acid and 80
To 100 parts of BDOs, wherein, the production method of this carboxy lower Biodegradable polyester obtains part in the steps below: the first step,
Needed raw material is placed in reactor, and the temperature of material in reactor is raised to 80 DEG C to 100 DEG C, then material is mixed
Uniformly add the metatitanic acid erythrol ester of raw material weight 50ppm to 250ppm afterwards, be then -40kpa to -80kpa, temperature in pressure
For 225 DEG C to 230 DEG C, stir speed (S.S.) be 50r/min to 100r/min under conditions of carry out esterification, when the esterification collected
When water parts by weight reach 15 parts to 55 parts, stop esterification；Second step, after esterification terminates, by the pressure in reactor
Power is adjusted to normal pressure, then adds the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm into reactor, and mixing is all
Add the carboxyl remover of raw material weight 30ppm to 1000ppm and the chelating agen of raw material weight 10ppm to 300ppm after even, connect
Pressure be 0.5 kpa to 2kpa, temperature be 230 DEG C to 235 DEG C, stir speed (S.S.) be 30r/min to 80r/min condition
Under carry out prepolymerization reaction, when stir moment of torsion reach 10n m to 100n m when, prepolymerization reaction completes；3rd step, precondensation
After the completion of reaction, pressure be 0pa to 100pa, temperature be 230 DEG C to 235 DEG C, stir speed (S.S.) be 30r/min to 80r/min
Under the conditions of carry out polycondensation reaction, when stirring moment of torsion and reaching 20n m to 80n m, stop polycondensation reaction, polycondensation reaction terminates
Afterwards, pressurizeed the melt excluding in reactor using nitrogen, obtains carboxy lower Biodegradable polyester with water-bath cooling.
Further optimization and/or improvements to foregoing invention technical scheme are presented herein below:
Above-mentioned compound Titanium series catalyst count by weight organic titanic compound including 50 parts to 98 parts, 1 part to 50 parts
Organo-silicon compound and 1 part to 10 parts of metal salt compound, wherein, organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid
Tetrem alcohol ester, metatitanic acid four propanol ester, metatitanic acid erythrol ester, tetraisopropyl titanate, metatitanic acid four isobutyl alcohol ester, metatitanic acid four tert-butyl alcohol
Ester, metatitanic acid four isooctanol ester, metatitanic acid four Hexalin ester, metatitanic acid four benzyl alcohol ester, cresol titanium, acetylacetone,2,4-pentanedione oxygen titanium, titanium ethylene glycolate, poly-
One or more of metatitanic acid butyl alcohol ester etc.；Organo-silicon compound be trimethylethoxysilane, dimethyldimethoxysil,ne, two
Methyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyltriethoxy diethyl
TMOS, hexadecyl trimethoxy silane, 3- aminopropyl triethoxysilane, VTES, silicic acid first
One or more of double (trimethylsiloxy group) ethane of ester, silester, silicic acid propyl ester, butyl silicate, 1,2-；Slaine chemical combination
Thing is Quilonorm (SKB), sodium acetate, calcium acetate, cobalt acetate, zinc acetate, manganese acetate, copper acetate, nickel acetate, antimony acetate, acid chloride, second
One or more of sour lanthanum, rubidium acetate, magnesium acetate, magnesium trisilicate, aluminium acetate, aluminium silicate, aluminium acetylacetonate；Or/and, carboxyl disappears
Except agent be (+)-2,3-Epoxy-1-propanol, isopropyl glycidyl ether, n-butyl glycidyl ether, n-octyl glycidyl ether, dodecyl
Glycidyl ether, epoxy soybean oil, cyclohexyl glycidyl ether, benzyl glycidyl ether, furfuryl glycidyl ether, pi-allyl
Glycidyl ether, glycidyl methacrylate, Ethylene glycol diglycidyl ether, 1,4- butanediol diglycidyl ether, new
Neopentyl glycol diglycidyl glycerin ether, 1,2- cylohexanediol diglycidyl ether, 1,4- cylohexanediol diglycidyl ether, isocyanuric acid
One or more of three-glycidyl ester, γ-glycidyl ether oxygen propyl trimethoxy silicane；Or/and, chelate is second two
Alcohol, ethylenediamine, butanediol, 1,4- butanediamine, 2,2- bipyridyl, 2,6- dicarboxyl yl pyridines, dopamine, isopropanolamine, diisopropyl
Hydramine, triisopropanolamine, diethylentriamine, triethylenetetramine, n, n'- double (3- aminopropyl) ethylenediamine, n- (2- ethoxy) second
Diamidogen, n- acetyl ethylenediamine, tetraacetyl ethylene diamine, n, n- dimethyl-ethylenediamine, n, n'- dimethyl-ethylenediamine, tetramethyl second two
Amine, n, n'- diphenyl ethylene diamine, ethylenediaminetetraacetic acid, n- hydroxyethylethylene diamine-n, n', n'- triacetic acid, ethylenediamine tetraacetic methene
One or more of phosphonic acids, polyvinyl alcohol, Polyvinylpyrrolidone.
In the above-mentioned first step, first reactor nitrogen is entered after line replacement, then raw material is placed in reactor；Or/and, the
In one step, after adding metatitanic acid erythrol ester, with nitrogen, the pressure in reactor is adjusted to -40kpa to -80kpa；Or/and, the
In two steps, after esterification terminates, with nitrogen, the pressure in reactor is adjusted to normal pressure；Or/and, in second step, to reaction
After adding compound Titanium series catalyst in kettle, with nitrogen, the pressure in reactor is adjusted to normal pressure extremely -80kpa；Or/and, second
In step, after adding carboxyl remover and chelating agen into reactor, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted
Save 0.5 kpa to 2kpa；Or/and, in the 3rd step, after the completion of prepolymerization reaction, with nitrogen by polycondensation reaction in reactor
Pressure is adjusted to 0pa to 100pa.
In the above-mentioned first step, by 0.1 DEG C/min to 1 DEG C/min programming rate by the temperature of material in reactor be raised to 80 to
100℃；Or/and, in the first step, by 0.1 DEG C/min to 1 DEG C/min programming rate, the temperature of charge in reactor is raised to 225
DEG C carry out esterification to 230 DEG C.
In the above-mentioned first step, under the conditions of stir speed (S.S.) is for 30r/min to 100r/min, stirring 30min will be equal for material mixing
Even；Or/and, stirring after adding the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm in second step into reactor
Speed is for adding carboxyl remover and chelating agen after stirring 15min mix homogeneously under the conditions of 30r/min to 100r/min.
The present invention carries out polycondensation reaction, energy by the phase after esterification using compound Titanium series catalyst and carboxyl scavenger
Enough content of carboxyl end group farthest reducing carboxylate, are simultaneously introduced and have the chelate of Stabilization to control titanium system to be catalyzed
The catalysis activity of agent, it is to avoid the product that the high activity of catalyst caused in polycondensation reaction later stage is degraded side reaction, with maximum limit
Degree ground reduces the side reaction in polycondensation reaction later stage, thus ensureing the carboxy lower level of final polyester product, without additionally adding again
Other additives are modified thus reducing the content of carboxyl end group of product to product, it is to avoid cause production high cost.
Specific embodiment
The present invention is not limited by following embodiments, can technology according to the present invention scheme determine specifically with practical situation
Embodiment.Ppm in the present invention is 1/1000000th.
Embodiment 1, this carboxy lower Biodegradable polyester, consist of 40 parts to 100 part 1,6- including raw materials by weight portion
Adipic acid or/and 1 part to 60 parts p-phthalic acid and 80 parts to 100 parts BDOs, wherein, this carboxy lower biodegradation gathers
Ester is obtained by following production methods: the first step, and needed raw material is placed in reactor, and the temperature liter by material in reactor
To 80 DEG C to 100 DEG C, then will add the metatitanic acid erythrol ester of raw material weight 50ppm to 250ppm after material mix homogeneously, connect
Pressure be -40kpa to -80kpa, temperature be 225 DEG C to 230 DEG C, stir speed (S.S.) be the condition of 50r/min to 100r/min
Under carry out esterification, when the esterification water parts by weight collected reach 15 parts to 55 parts, stop esterification；Second step,
After esterification terminates, the pressure in reactor is adjusted to normal pressure, then into reactor, add raw material weight 50ppm extremely
The compound Titanium series catalyst of 1000ppm, adds the carboxyl remover of raw material weight 30ppm to 1000ppm and former after mix homogeneously
Material weight 10ppm to 300ppm chelating agen, then pressure be 0.5 kpa to 2kpa, temperature be 230 DEG C to 235 DEG C, stir
Mix speed and carry out prepolymerization reaction under conditions of 30r/min to 80r/min, when stirring moment of torsion reaches 10n m to 100n m
When, prepolymerization reaction completes；3rd step, after the completion of prepolymerization reaction, pressure be 0pa to 100pa, temperature be 230 DEG C to 235
DEG C, stir speed (S.S.) be 30r/min to 80r/min under conditions of carry out polycondensation reaction, when stirring moment of torsion reach 20n m to 80n
During m, stop polycondensation reaction, after polycondensation reaction terminates, pressurizeed the melt excluding in reactor using nitrogen, obtains with water-bath cooling
Carboxy lower Biodegradable polyester.
Embodiment 2, this carboxy lower Biodegradable polyester, consist of 40 parts or 100 part 1,6- including raw materials by weight portion
Adipic acid or/and 1 part or 60 parts of p-phthalic acids and 80 parts or 100 parts of BDOs, wherein, this carboxy lower biodegradation gathers
Ester is obtained by following production methods: the first step, and needed raw material is placed in reactor, and the temperature liter by material in reactor
To 80 DEG C or 100 DEG C, then will add the metatitanic acid erythrol ester of raw material weight 50ppm or 250ppm after material mix homogeneously, connect
Pressure be -40kpa or -80kpa, temperature be 225 DEG C or 230 DEG C, stir speed (S.S.) be 50r/min or 100r/min condition
Under carry out esterification, when the esterification water parts by weight collected reach 15 parts or 55 parts, stop esterification；Second step,
After esterification terminates, the pressure in reactor is adjusted to normal pressure, then into reactor add raw material weight 50ppm or
The compound Titanium series catalyst of 1000ppm, adds the carboxyl remover of raw material weight 30ppm or 1000ppm and former after mix homogeneously
Material weight 10ppm or 300ppm chelating agen, then pressure be 0.5 kpa to 2kpa, temperature be 230 DEG C or 235 DEG C, stir
Mix speed and carry out prepolymerization reaction under conditions of 30r/min or 80r/min, when stirring moment of torsion reaches 10n m or 100n m
When, prepolymerization reaction completes；3rd step, after the completion of prepolymerization reaction, pressure be 0pa or 100pa, temperature be 230 DEG C or 235
DEG C, stir speed (S.S.) be 30r/min or 80r/min under conditions of carry out polycondensation reaction, when stirring moment of torsion reach 20n m or 80n
During m, stop polycondensation reaction, after polycondensation reaction terminates, pressurizeed the melt excluding in reactor using nitrogen, obtains with water-bath cooling
Carboxy lower Biodegradable polyester.
Embodiment 3, preferred as above-described embodiment, compound Titanium series catalyst is counted by weight including 50 parts to 98 parts
Organic titanic compound, the metal salt compound of 1 part to 50 parts of organo-silicon compound and 1 part to 10 parts, wherein, organic titanizing
Compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propanol ester, metatitanic acid erythrol ester, tetraisopropyl titanate, metatitanic acid four
Isobutyl alcohol ester, metatitanic acid four tert-butyl alcohol ester, metatitanic acid four isooctanol ester, metatitanic acid four Hexalin ester, metatitanic acid four benzyl alcohol ester, cresol titanium, second
One or more of acyl acetone oxygen titanium, titanium ethylene glycolate, poly- metatitanic acid butyl alcohol ester etc.；Organo-silicon compound are front three base oxethyl silicon
Alkane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy
Base silane, γ-aminopropyltriethoxy diethoxy silane, hexadecyl trimethoxy silane, 3- aminopropyl triethoxysilane, second
Double (trimethylsiloxy group) ethane of thiazolinyl triethoxysilane, methyl silicate, silester, silicic acid propyl ester, butyl silicate, 1,2-
One or more of；Metal salt compound be Quilonorm (SKB), sodium acetate, calcium acetate, cobalt acetate, zinc acetate, manganese acetate, copper acetate,
In nickel acetate, antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, magnesium trisilicate, aluminium acetate, aluminium silicate, aluminium acetylacetonate
More than one；Or/and, carboxyl remover is (+)-2,3-Epoxy-1-propanol, isopropyl glycidyl ether, n-butyl glycidyl ether, just pungent
Base glycidyl ether, dodecyl glycidyl ether, epoxy soybean oil, cyclohexyl glycidyl ether, benzyl glycidyl
Ether, furfuryl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, Ethylene glycol diglycidyl ether, 1,
4- butanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1,2- cylohexanediol diglycidyl ether, 1,4- hexamethylene two
One of alcohol diglycidyl ether, isocyanuric acid three-glycidyl ester, γ-glycidyl ether oxygen propyl trimethoxy silicane with
On；Or/and, chelate is ethylene glycol, ethylenediamine, butanediol, Putriscine, 2,2- bipyridyl, 2,6- dicarboxyl yl pyridines, many
Bar amine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, diethylentriamine, triethylenetetramine, n, double (3- aminopropyl) second of n'-
Diamidogen, n- (2- ethoxy) ethylenediamine, n- acetyl ethylenediamine, tetraacetyl ethylene diamine, n, n- dimethyl-ethylenediamine, n, n'- diformazan
Base ethylenediamine, tetramethylethylenediamine, n, n'- diphenyl ethylene diamine, ethylenediaminetetraacetic acid, n- hydroxyethylethylene diamine-n, n', n'-
One or more of triacetic acid, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, Polyvinylpyrrolidone.
Embodiment 4, preferred as above-described embodiment, in the first step, first reactor nitrogen is entered after line replacement, then will
Raw material is placed in reactor；Or/and, in the first step, after adding metatitanic acid erythrol ester, with nitrogen, the pressure in reactor is adjusted
To -40kpa to -80kpa；Or/and, in second step, after esterification terminates, with nitrogen, the pressure in reactor is adjusted to often
Pressure；Or/and, in second step, after adding compound Titanium series catalyst into reactor, with nitrogen, the pressure in reactor is adjusted to
Normal pressure extremely -80kpa；Or/and, in second step, after adding carboxyl remover and chelating agen into reactor, with nitrogen by reactor
The pressure of interior prepolymerization reaction is adjusted to 0.5 kpa to 2kpa；Or/and, in the 3rd step, after the completion of prepolymerization reaction, use nitrogen
The pressure of polycondensation reaction in reactor is adjusted to 0pa to 100pa by gas.
Embodiment 5, preferred as above-described embodiment, in the first step, will by 0.1 DEG C/min to 1 DEG C/min programming rate
In reactor, the temperature of material is raised to 80 to 100 DEG C；Or/and, in the first step, will by 0.1 DEG C/min to 1 DEG C/min programming rate
Temperature of charge in reactor is raised to 225 DEG C and carries out esterification to 230 DEG C.
Embodiment 6, preferred as above-described embodiment, it is 30r/min to 100r/min bar in stir speed (S.S.) in the first step
Under part, stirring 30min is by material mix homogeneously；Or/and, add raw material weight 50ppm extremely into reactor in second step
Stir 15min mix homogeneously under the conditions of stir speed (S.S.) is for 30r/min to 100r/min after the compound Titanium series catalyst of 1000ppm
Add carboxyl remover and chelating agen afterwards.
The content of carboxyl end group average value ranges of the carboxy lower Biodegradable polyester obtaining according to the above embodiment of the present invention are
10.2 mol/t to 28mol/t, and the content of carboxyl end group average value ranges of the degraded polyester product being obtained according to prior art are
28.5 mol/t to 57.6mol/t；It can thus be seen that the present invention passes through the phase after esterification adopts compound Titanium series catalyst
Carry out polycondensation reaction with carboxyl scavenger, can farthest reduce the content of carboxyl end group of carboxylate, be simultaneously introduced and have surely
Be set for chelate control the catalysis activity of Titanium series catalyst, it is to avoid the high activity of catalyst drew in the polycondensation reaction later stage
The product degraded side reaction rising, to reduce the side reaction in polycondensation reaction later stage to greatest extent, thus ensure final polyester product
Carboxy lower level, without additionally adding other additives that product is modified again thus reducing the content of carboxyl end group of product,
Avoid causing the problem of production high cost.
Claims (18)
1. a kind of carboxy lower Biodegradable polyester it is characterised in that raw materials by weight portion consist of 40 parts to 100 parts 1,6- oneself
Diacid, 1 part to 60 parts p-phthalic acid and 80 parts to 100 parts BDOs, wherein, this carboxy lower Biodegradable polyester is pressed
The method of stating obtains: the first step, and needed raw material is placed in reactor, and the temperature of material in reactor is raised to 80 DEG C extremely
100 DEG C, then will add the metatitanic acid erythrol ester of raw material weight 50ppm to 250ppm after material mix homogeneously, then in pressure
For -40kpa to -80kpa, temperature be 225 DEG C to 230 DEG C, stir speed (S.S.) be 50r/min to 100r/min under conditions of carry out ester
Change reaction, when the esterification water parts by weight collected reach 15 parts to 55 parts, stop esterification；Second step, esterification
After end, the pressure in reactor is adjusted to normal pressure, into reactor, then add raw material weight 50ppm's to 1000ppm
Compound Titanium series catalyst, adds carboxyl remover and the raw material weight of raw material weight 30ppm to 1000ppm after mix homogeneously
The chelating agen of 10ppm to 300ppm, then pressure be 0.5 kpa to 2kpa, temperature be 230 DEG C to 235 DEG C, stir speed (S.S.) be
Carry out prepolymerization reaction under conditions of 30r/min to 80r/min, when stirring moment of torsion reaches 10n m to 100n m, precondensation
Reaction completes；3rd step, after the completion of prepolymerization reaction, pressure be 0pa to 100pa, temperature be 230 DEG C to 235 DEG C, stirring speed
Rate carries out polycondensation reaction under conditions of 30r/min to 80r/min, when stirring moment of torsion reaches 20n m to 80n m, stops
Polycondensation reaction, after polycondensation reaction terminates, pressurizeed the melt excluding in reactor using nitrogen, obtains carboxy lower life with water-bath cooling
Thing degraded polyester；Compound Titanium series catalyst count by weight organic titanic compound including 50 parts to 98 parts, 1 part to 50 parts
The metal salt compound of organo-silicon compound and 1 part to 10 parts, wherein, organic titanic compound is metatitanic acid tetramethyl alcohol ester, metatitanic acid four
Ethanol ester, metatitanic acid four propanol ester, metatitanic acid erythrol ester, tetraisopropyl titanate, metatitanic acid four isobutyl alcohol ester, metatitanic acid four tert-butyl alcohol ester,
Metatitanic acid four isooctanol ester, metatitanic acid four Hexalin ester, metatitanic acid four benzyl alcohol ester, cresol titanium, acetylacetone,2,4-pentanedione oxygen titanium, titanium ethylene glycolate, poly- titanium
One or more of sour butyl alcohol ester；Organo-silicon compound are trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl
Diethoxy silane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane, γ-aminopropyltriethoxy diethoxy
Silane, hexadecyl trimethoxy silane, 3- aminopropyl triethoxysilane, VTES, methyl silicate, silicon
One or more of double (trimethylsiloxy group) ethane of acetoacetic ester, silicic acid propyl ester, butyl silicate, 1,2-；Metal salt compound is
Quilonorm (SKB), sodium acetate, calcium acetate, cobalt acetate, zinc acetate, manganese acetate, copper acetate, nickel acetate, antimony acetate, acid chloride, lanthanum acetate,
One or more of rubidium acetate, magnesium acetate, magnesium trisilicate, aluminium acetate, aluminium silicate, aluminium acetylacetonate；Chelate is ethylene glycol, second
Diamidogen, butanediol, 1,4- butanediamine, 2,2- bipyridyl, 2,6- dicarboxyl yl pyridines, dopamine, isopropanolamine, diisopropanolamine (DIPA),
Triisopropanolamine, diethylentriamine, triethylenetetramine, n, double (3- aminopropyl) ethylenediamine of n'-, n- (2- ethoxy) ethylenediamine,
N- acetyl ethylenediamine, tetraacetyl ethylene diamine, n, n- dimethyl-ethylenediamine, n, n'- dimethyl-ethylenediamine, tetramethylethylenediamine, n,
N'- diphenyl ethylene diamine, ethylenediaminetetraacetic acid, n- hydroxyethylethylene diamine-n, n', n'- triacetic acid, ethylene diamine tetra methylene phosphonic acid,
One or more of polyvinyl alcohol, Polyvinylpyrrolidone.
2. carboxy lower Biodegradable polyester according to claim 1 is it is characterised in that carboxyl remover is (+)-2,3-Epoxy-1-propanol, different
Propyl glycidyl ether, n-butyl glycidyl ether, n-octyl glycidyl ether, dodecyl glycidyl ether, epoxy are big
Oleum Glycines, cyclohexyl glycidyl ether, benzyl glycidyl ether, furfuryl glycidyl ether, allyl glycidyl ether, methyl-prop
Olefin(e) acid ethylene oxidic ester, Ethylene glycol diglycidyl ether, 1,4- butanediol diglycidyl ether, neopentyl glycol 2-glycidyl
Ether, 1,2- cylohexanediol diglycidyl ether, 1,4- cylohexanediol diglycidyl ether, isocyanuric acid three-glycidyl ester, γ-
One or more of glycidyl ether oxygen propyl trimethoxy silicane.
3. carboxy lower Biodegradable polyester according to claim 1 and 2 is it is characterised in that in the first step, first by reactor
Entered after line replacement with nitrogen, then raw material is placed in reactor；Or/and, in the first step, after adding metatitanic acid erythrol ester, use nitrogen
Pressure in reactor is adjusted to -40kpa to -80kpa by gas；Or/and, in second step, after esterification terminates, will with nitrogen
Pressure in reactor is adjusted to normal pressure；Or/and, in second step, after adding compound Titanium series catalyst into reactor, use nitrogen
Pressure in reactor is adjusted to normal pressure extremely -80kpa；Or/and, in second step, add into reactor carboxyl remover and
After chelating agen, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 kpa to 2kpa；Or/and, the 3rd step
In, after the completion of prepolymerization reaction, with nitrogen, the pressure of polycondensation reaction in reactor is adjusted to 0pa to 100pa.
4. carboxy lower Biodegradable polyester according to claim 1 and 2 is it is characterised in that in the first step, by 0.1 DEG C/min
To 1 DEG C/min programming rate, the temperature of material in reactor is raised to 80 to 100 DEG C；Or/and, in the first step, by 0.1 DEG C/min
To 1 DEG C/min programming rate, the temperature of charge in reactor is raised to 225 DEG C and carries out esterification to 230 DEG C.
5. carboxy lower Biodegradable polyester according to claim 3 is it is characterised in that in the first step, by 0.1 DEG C/min to 1
DEG C/temperature of material in reactor is raised to 80 to 100 DEG C by min programming rate；Or/and, in the first step, by 0.1 DEG C/min to 1
DEG C/temperature of charge in reactor is raised to 225 DEG C and carries out esterification to 230 DEG C by min programming rate.
6. carboxy lower Biodegradable polyester according to claim 1 and 2 is it is characterised in that in the first step in stir speed (S.S.) be
Under the conditions of 30r/min to 100r/min, stirring 30min is by material mix homogeneously；Or/and, add former in second step into reactor
Stir under the conditions of stir speed (S.S.) is for 30r/min to 100r/min after the compound Titanium series catalyst of material weight 50ppm to 1000ppm
Carboxyl remover and chelating agen is added after 15min mix homogeneously.
7. carboxy lower Biodegradable polyester according to claim 3 is it is characterised in that in the first step in stir speed (S.S.) be
Under the conditions of 30r/min to 100r/min, stirring 30min is by material mix homogeneously；Or/and, add former in second step into reactor
Stir under the conditions of stir speed (S.S.) is for 30r/min to 100r/min after the compound Titanium series catalyst of material weight 50ppm to 1000ppm
Carboxyl remover and chelating agen is added after 15min mix homogeneously.
8. carboxy lower Biodegradable polyester according to claim 4 is it is characterised in that in the first step in stir speed (S.S.) be
Under the conditions of 30r/min to 100r/min, stirring 30min is by material mix homogeneously；Or/and, add former in second step into reactor
Stir under the conditions of stir speed (S.S.) is for 30r/min to 100r/min after the compound Titanium series catalyst of material weight 50ppm to 1000ppm
Carboxyl remover and chelating agen is added after 15min mix homogeneously.
9. carboxy lower Biodegradable polyester according to claim 5 is it is characterised in that in the first step in stir speed (S.S.) be
Under the conditions of 30r/min to 100r/min, stirring 30min is by material mix homogeneously；Or/and, add former in second step into reactor
Stir under the conditions of stir speed (S.S.) is for 30r/min to 100r/min after the compound Titanium series catalyst of material weight 50ppm to 1000ppm
Carboxyl remover and chelating agen is added after 15min mix homogeneously.
10. a kind of production method of carboxy lower Biodegradable polyester is it is characterised in that raw materials by weight portion consists of 40 parts extremely
100 parts of 1,6- adipic acids, 1 part to 60 parts p-phthalic acid and 80 parts to 100 parts BDOs, wherein, this carboxy lower is biological
The production method of degraded polyester obtains in the steps below: the first step, and needed raw material is placed in reactor, and by reactor
The temperature of material is raised to 80 DEG C to 100 DEG C, then will add the metatitanic acid of raw material weight 50ppm to 250ppm after material mix homogeneously
Erythrol ester, then pressure be -40kpa to -80kpa, temperature be 225 DEG C to 230 DEG C, stir speed (S.S.) be 50r/min extremely
Carry out esterification under conditions of 100r/min, when the esterification water parts by weight collected reach 15 parts to 55 parts, stop ester
Change reaction；Second step, after esterification terminates, the pressure in reactor is adjusted to normal pressure, then adds former into reactor
The compound Titanium series catalyst of material weight 50ppm to 1000ppm, adds the carboxylic of raw material weight 30ppm to 1000ppm after mix homogeneously
Base remover and the chelating agen of raw material weight 10ppm to 300ppm, then pressure be 0.5 kpa to 2kpa, temperature be 230
DEG C to 235 DEG C, stir speed (S.S.) be 30r/min to 80r/min under conditions of carry out prepolymerization reaction, when stirring moment of torsion reach
During 10n m to 100n m, prepolymerization reaction completes；3rd step, after the completion of prepolymerization reaction, pressure be 0pa to 100pa,
Temperature is 230 DEG C to 235 DEG C, stir speed (S.S.) carries out polycondensation reaction under conditions of 30r/min to 80r/min, when stirring moment of torsion
When reaching 20n m to 80n m, stop polycondensation reaction, after polycondensation reaction terminates, pressurizeed using nitrogen molten in exclusion reactor
Body, obtains carboxy lower Biodegradable polyester with water-bath cooling；Compound Titanium series catalyst is counted by weight including 50 parts to 98 parts
Organic titanic compound, the metal salt compound of 1 part to 50 parts of organo-silicon compound and 1 part to 10 parts；Organic titanic compound
For metatitanic acid tetramethyl alcohol ester, metatitanic acid tetrem alcohol ester, metatitanic acid four propanol ester, metatitanic acid erythrol ester, tetraisopropyl titanate, metatitanic acid four isobutyl
Alcohol ester, metatitanic acid four tert-butyl alcohol ester, metatitanic acid four isooctanol ester, metatitanic acid four Hexalin ester, metatitanic acid four benzyl alcohol ester, cresol titanium, levulinic
One or more of ketone oxygen titanium, titanium ethylene glycolate, poly- metatitanic acid butyl alcohol ester；Organo-silicon compound are trimethylethoxysilane, diformazan
Base dimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, Cyclohexyl Methyl Dimethoxysilane,
γ-aminopropyltriethoxy diethoxy silane, hexadecyl trimethoxy silane, 3- aminopropyl triethoxysilane, vinyl three
In double (trimethylsiloxy group) ethane of Ethoxysilane, methyl silicate, silester, silicic acid propyl ester, butyl silicate, 1,2- one
More than kind；Metal salt compound be Quilonorm (SKB), sodium acetate, calcium acetate, cobalt acetate, zinc acetate, manganese acetate, copper acetate, nickel acetate,
One of antimony acetate, acid chloride, lanthanum acetate, rubidium acetate, magnesium acetate, magnesium trisilicate, aluminium acetate, aluminium silicate, aluminium acetylacetonate
More than；Chelate is ethylene glycol, ethylenediamine, butanediol, 1,4- butanediamine, 2,2- bipyridyl, 2,6- dicarboxyl yl pyridines, DOPA
Amine, isopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, diethylentriamine, triethylenetetramine, n, double (3- aminopropyl) second two of n'-
Amine, n- (2- ethoxy) ethylenediamine, n- acetyl ethylenediamine, tetraacetyl ethylene diamine, n, n- dimethyl-ethylenediamine, n, n'- dimethyl
Ethylenediamine, tetramethylethylenediamine, n, n'- diphenyl ethylene diamine, ethylenediaminetetraacetic acid, n- hydroxyethylethylene diamine-n, n', n'- tri-
One or more of acetic acid, ethylene diamine tetra methylene phosphonic acid, polyvinyl alcohol, Polyvinylpyrrolidone.
The production method of 11. carboxy lower Biodegradable polyesters according to claim 10 is it is characterised in that carboxyl remover
Shrink for (+)-2,3-Epoxy-1-propanol, isopropyl glycidyl ether, n-butyl glycidyl ether, n-octyl glycidyl ether, dodecyl
Glycerin ether, epoxy soybean oil, cyclohexyl glycidyl ether, benzyl glycidyl ether, furfuryl glycidyl ether, allyl glycidyl
Glycerin ether, glycidyl methacrylate, Ethylene glycol diglycidyl ether, 1,4- butanediol diglycidyl ether, new penta 2
Alcohol diglycidyl ether, 1,2- cylohexanediol diglycidyl ether, 1,4- cylohexanediol diglycidyl ether, isocyanuric acid three contract
One or more of water glyceride, γ-glycidyl ether oxygen propyl trimethoxy silicane.
The production method of the 12. carboxy lower Biodegradable polyesters according to claim 10 or 11 is it is characterised in that the first step
In, first reactor nitrogen is entered after line replacement, then raw material is placed in reactor；Or/and, in the first step, add metatitanic acid four
After butyl alcohol ester, with nitrogen, the pressure in reactor is adjusted to -40kpa to -80kpa；Or/and, in second step, esterification is tied
Pressure in reactor is adjusted to normal pressure with nitrogen by Shu Hou；Or/and, in second step, add composite titanium system into reactor and urge
After agent, with nitrogen, the pressure in reactor is adjusted to normal pressure extremely -80kpa；Or/and, in second step, add into reactor
After carboxyl remover and chelating agen, with nitrogen, the pressure of the prepolymerization reaction in reactor is adjusted to 0.5 kpa to 2kpa；
Or/and, in the 3rd step, after the completion of prepolymerization reaction, with nitrogen, the pressure of polycondensation reaction in reactor is adjusted to 0pa extremely
100pa.
13. according to claim 10 11 or described carboxy lower Biodegradable polyester production method it is characterised in that first
In step, by 0.1 DEG C/min to 1 DEG C/min programming rate, the temperature of material in reactor is raised to 80 to 100 DEG C；Or/and, first
In step, by 0.1 DEG C/min to 1 DEG C/min programming rate, the temperature of charge in reactor is raised to 225 DEG C and is esterified to 230 DEG C
Reaction.
14. according to the production method of claim 12 or described carboxy lower Biodegradable polyester it is characterised in that in the first step,
By 0.1 DEG C/min to 1 DEG C/min programming rate, the temperature of material in reactor is raised to 80 to 100 DEG C；Or/and, in the first step,
By 0.1 DEG C/min to 1 DEG C/min programming rate, the temperature of charge in reactor is raised to 225 DEG C and carries out esterification to 230 DEG C.
The production method of the 15. carboxy lower Biodegradable polyesters according to claim 10 or 11 is it is characterised in that the first step
In under the conditions of stir speed (S.S.) is for 30r/min to 100r/min stirring 30min by material mix homogeneously；Or/and, in second step to
After the compound Titanium series catalyst of addition raw material weight 50ppm to 1000ppm in reactor in stir speed (S.S.) for 30r/min extremely
Carboxyl remover and chelating agen is added after stirring 15min mix homogeneously under the conditions of 100r/min.
The production method of 16. carboxy lower Biodegradable polyesters according to claim 12 it is characterised in that in the first step
Stir speed (S.S.) be under the conditions of 30r/min to 100r/min stirring 30min by material mix homogeneously；Or/and, to reaction in second step
Adding in kettle after the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm in stir speed (S.S.) is 30r/min to 100r/min
Under the conditions of add carboxyl remover and chelating agen after stirring 15min mix homogeneously.
The production method of 17. carboxy lower Biodegradable polyesters according to claim 13 it is characterised in that in the first step
Stir speed (S.S.) be under the conditions of 30r/min to 100r/min stirring 30min by material mix homogeneously；Or/and, to reaction in second step
Adding in kettle after the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm in stir speed (S.S.) is 30r/min to 100r/min
Under the conditions of add carboxyl remover and chelating agen after stirring 15min mix homogeneously.
The production method of 18. carboxy lower Biodegradable polyesters according to claim 14 it is characterised in that in the first step
Stir speed (S.S.) be under the conditions of 30r/min to 100r/min stirring 30min by material mix homogeneously；Or/and, to reaction in second step
Adding in kettle after the compound Titanium series catalyst of raw material weight 50ppm to 1000ppm in stir speed (S.S.) is 30r/min to 100r/min
Under the conditions of add carboxyl remover and chelating agen after stirring 15min mix homogeneously.
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| CN110922511A (en) * | 2018-09-20 | 2020-03-27 | 陈建添 | Method for esterifying a copolymer |
| CN112876659A (en) * | 2021-01-18 | 2021-06-01 | 山东瑞丰高分子材料股份有限公司 | Preparation method of boiling-resistant PBAT composite material |
| CN114853999B (en) * | 2022-04-08 | 2023-12-19 | 万华化学集团股份有限公司 | PBAT resin and preparation method thereof |
| CN114656688B (en) * | 2022-04-11 | 2023-08-25 | 山东瑞丰高分子材料股份有限公司 | Multifunctional auxiliary agent for synthesizing degradable polyester, and preparation method and application thereof |
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