CN109666132A - A kind of linear randomly biodegradable copolymer ester and preparation method - Google Patents
A kind of linear randomly biodegradable copolymer ester and preparation method Download PDFInfo
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- CN109666132A CN109666132A CN201710964774.XA CN201710964774A CN109666132A CN 109666132 A CN109666132 A CN 109666132A CN 201710964774 A CN201710964774 A CN 201710964774A CN 109666132 A CN109666132 A CN 109666132A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 35
- 150000002148 esters Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 59
- 229920001634 Copolyester Polymers 0.000 claims abstract description 22
- -1 aliphatic ester Chemical class 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 7
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 35
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- 125000001118 alkylidene group Chemical group 0.000 claims description 21
- 230000032050 esterification Effects 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052725 zinc Chemical group 0.000 claims description 4
- 239000011701 zinc Chemical group 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- RWXOJQGSZWUIEJ-UHFFFAOYSA-K lanthanum(3+);octadecanoate Chemical compound [La+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RWXOJQGSZWUIEJ-UHFFFAOYSA-K 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920000229 biodegradable polyester Polymers 0.000 description 6
- 239000004622 biodegradable polyester Substances 0.000 description 6
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 2
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 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 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FUOAPOGJEXMTHV-UHFFFAOYSA-N C(C)(C)O[La] Chemical compound C(C)(C)O[La] FUOAPOGJEXMTHV-UHFFFAOYSA-N 0.000 description 1
- KLPPPZWWHMSHBQ-UHFFFAOYSA-N C(C)(C)O[Nd] Chemical compound C(C)(C)O[Nd] KLPPPZWWHMSHBQ-UHFFFAOYSA-N 0.000 description 1
- UGTDZBCNPGQORY-UHFFFAOYSA-N C(C)(C)O[Sc] Chemical compound C(C)(C)O[Sc] UGTDZBCNPGQORY-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- BDPKIAVSVWWQBT-UHFFFAOYSA-M O[Sn]C1=CC=CC=C1 Chemical compound O[Sn]C1=CC=CC=C1 BDPKIAVSVWWQBT-UHFFFAOYSA-M 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- JLGJJUHHVPEZII-UHFFFAOYSA-N acetic acid;tris(2-methylpropyl)tin Chemical compound CC(O)=O.CC(C)C[Sn](CC(C)C)CC(C)C JLGJJUHHVPEZII-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- UDTKQJPDQDGBEG-UHFFFAOYSA-N aminomethyl(phenyl)tin Chemical compound NC[Sn]C1=CC=CC=C1 UDTKQJPDQDGBEG-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VDEKURXOWJYWCG-UHFFFAOYSA-N dodecyltin Chemical compound CCCCCCCCCCCC[Sn] VDEKURXOWJYWCG-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- PJNIZDVDNWEBNQ-UHFFFAOYSA-N neodymium;octadecanoic acid Chemical compound [Nd].CCCCCCCCCCCCCCCCCC(O)=O PJNIZDVDNWEBNQ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to polymeric material fields, disclose a kind of linear randomly biodegradable copolymer ester and preparation method.The copolyesters has aliphatic ester structural unit and aromatic ester structural unit, the melt index that the copolyesters uses ISO 1133-2005 method to measure under 150 DEG C, 2.16kg load is 3.5-5.2g/10min, and the melt index for using ISO 1133-2005 method to measure under 190 DEG C, 2.16kg load is 10-20g/10min.Copolyesters of the present invention has lower melt index, and molecular weight with higher, tensile mechanical properties are preferable.
Description
Technical field
The present invention relates to polymeric material fields, more particularly to a kind of linear random biodegradable copolymer ester and system
Preparation Method.
Background technique
Be now widely used for industry and daily life in thermoplastic aromatic polyester have excellent heat stability can and
Mechanical property, it is easy to process, it is cheap.For example, polyethylene terephthalate (PET) and polybutylene terephthalate
Ester (PBT), is widely used in the manufacture of fiber, film and container.However, these aromatic polyesters are difficult to after use is discarded
Degradation, microorganism is also not observed so far has any apparent directly degradation to aromatic polyester such as PET, PBT.In order to combine
The excellent performance of aromatic polyester, since the 1980s, those skilled in the art are dedicated to synthctic fat-aromatic copolyester
The research of ester, i.e., introduce aromatic segments in aliphatic polyester, both ensure that the copolyesters has the Optimality of aromatic polyester
Can, in turn ensure the biodegradable of the copolyesters.For example, by aliphatic dibasic acid or derivatives thereof, aliphatic dihydroxy alcohol,
Aromatic acid or derivatives thereof can prepare biodegradable aliphatic-aromatic copolyester.The copolyesters is with moral
The production of BASF AG, stateTo represent, raw material 1,6- adipic acid (AA), 1,4-butanediol (BDO), to benzene two
Formic acid dimethyl ester (DMT), production technology are as follows: esterification occurs for AA and BDO, and ester exchange reaction occurs for DMT and BDO, then
Esterification products and transesterification product is set to carry out copolycondensation together.
Chinese patent application CN1807485A is disclosed by aromatic acid or carboxylate, aliphatic dihydroxy alcohol, fat
The system of race's binary acid or derivatives thereof prepares linear random fat/aromatic copolyesters, joined rare earth catalyst in preparation process
System, fat/aromatic copolyesters molecular weight with higher of preparation.However, with the development of processed and applied, this linear nothing
Rule fat/aromatic copolyesters also expose some performance deficiencies, for example melt index is higher, are difficult to meet the need of processing aspect
It asks, therefore under the premise of not changing product structure, the biodegradable copolymer ester for preparing low melt index becomes to have very much must
It wants.
Summary of the invention
The purpose of the invention is to overcome the melt index of the Biodegradable Copolyester of existing method preparation is higher to lack
It falls into, a kind of linear randomly biodegradable copolymer ester and preparation method is provided.
To achieve the goals above, one aspect of the present invention provides a kind of linear random biodegradable copolymer ester, this is total
Polyester has aromatic ester structural unit shown in aliphatic ester structural unit shown in formula (1) and formula (2),
Wherein, R1' and R3' identical or different, and it is each independently selected from alkylidene；R2' selected from by alkylidene and cycloalkylidene
The group of composition；R4' it is arlydene；The copolyesters is measured under 150 DEG C, 2.16kg load using ISO 1133-2005 method
Melt index be 3.5-5.2g/10min, using the molten of ISO 1133-2005 method measurement under 190 DEG C, 2.16kg load
Melting index is 10-20g/10min.
The present invention also provides a kind of preparation methods of linear random biodegradable copolymer ester, this method comprises:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates, starts to vacuumize, and precondensation is first carried out under the first low vacuum, then under the first high vacuum
Polycondensation reaction is carried out, polymer P 1 is made, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum
Power；
(2) component b and component c are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction；
Wherein, the component a is at least one of aromatic acid and the acid anhydrides of aromatic acid；The component
B is aliphatic dihydroxy alcohol；The component c is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and alicyclic ring
At least one of the acid anhydrides of race's binary acid；
First catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)nAt least one of compound or
Their mixture, wherein M is titanium, antimony or zinc, and n is the valence state of M, R1For C1-C10Alkyl, R2For C1-C30Alkyl；
Second catalyst is at least one organo-tin compound；
The third catalyst is that at least one chemical formula is RE (R3)3Compound, wherein RE is thulium,
R3For selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4At least one of COO- group, R4For C1-C30Alkyl.
The present invention also provides the linear random biodegradable copolymer esters prepared by the above method.
The linear random biodegradable copolymer ester prepared according to the method described in the present invention has lower melt index,
Physical and mechanical property is excellent, can satisfy the demand of processing aspect.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Linear random biodegradable copolymer ester of the present invention have aliphatic ester structural unit shown in formula (1) and
Aromatic ester structural unit shown in formula (2).
In formula (1) and (2), R1' and R3' identical or different, and it is each independently selected from alkylidene, such as can be C2-
The alkylidene of C10.The alkylidene of the C2-C10 can be straight-chain alkyl-sub or the alkylidene with branch.Under preferable case,
R1' and R3' it is each independently selected from the alkylidene of C2-C8, the more preferably alkylidene of C2-C6.
In formula (1) and (2), R2' selected from the group being made of alkylidene and cycloalkylidene, such as can be the Asia of C1-C12
The cycloalkylidene of alkyl or C3-C12.The alkylidene of the C1-C12 can be straight-chain alkyl-sub or the alkylidene with branch.
Under preferable case, R2' the alkylidene for being C1-C8, the more preferably alkylidene of C2-C6.
In formula (1) and (2), R4' it is arlydene, the preferably arlydene of C6-C12.The arlydene can for
The group of at least one phenyl ring, naphthalene nucleus and anthracene nucleus.Under preferable case, R4' it is following arlydene:
Wherein, R5、R6、R7、R8、R9And R10It is each independently hydrogen, C1-C4Alkyl, F, Cl ,-NO2,-CN or-OR11,
Wherein, R11For C1-C4Alkyl.
In the present invention, the linear random biodegradable copolymer ester uses ISO under 150 DEG C, 2.16kg load
The melt index of 1133-2005 method measurement is 3.5-5.2g/10min, specifically, such as can be 3.5g/10min, 3.8g/
10min、4g/10min、4.1g/10min、4.2g/10min、4.3g/10min、4.4g/10min、4.5g/10min、4.6g/
10min, 4.7g/10min, 4.8g/10min, 4.9g/10min, 5.0g/10min, 5.1g/10min, 5.2g/10min and this
The arbitrary value in range that any two in a little point values are constituted.
In the present invention, the linear random biodegradable copolymer ester uses ISO under 190 DEG C, 2.16kg load
The melt index of 1133-2005 method measurement is 10-20g/10min, specifically, such as can be 10g/10min, 11g/
10min、12g/10min、13g/10min、14g/10min、14.5g/10min、15g/10min、15.5g/10min、16g/
10min、16.5g/10min、17g/10min、17.5g/10min、18g/10min、18.5g/10min、19g/10min、
The arbitrary value in range that any two in 19.5g/10min, 20g/10min and these point values are constituted.
In the present invention, the number-average molecular weight of the linear random biodegradable copolymer ester can be 50,000-6.5 ten thousand, excellent
It is selected as 5.2 ten thousand -6.4 ten thousand.In the present invention, the number-average molecular weight of polymer is measured according to gel permeation chromatography (GPC) method.
In the present invention, the weight average molecular weight of the linear random biodegradable copolymer ester can be 100,000-13 ten thousand, excellent
It is selected as 10.5 ten thousand -12.5 ten thousand.In the present invention, the weight average molecular weight of polymer is measured according to gel permeation chromatography (GPC) method.
In the present invention, the elongation at break of the linear random biodegradable copolymer ester can be 500-2200%,
Preferably 700-2000%.In the present invention, the elongation at break of copolyesters is measured according to the method for ASTM D638-03.
In the present invention, the fracture tensile strength of the linear random biodegradable copolymer ester can be 8.0-35MPa,
Preferably 10-32MPa.In the present invention, the fracture tensile strength of copolyesters is measured according to the method for ASTM D638-03.
In the present invention, the glass transition temperature of the linear random biodegradable copolymer ester can be for -32 DEG C extremely
30℃.In the present invention, the glass transition temperature of copolyesters is measured according to differential scanning calorimeter (DSC) measuring method.
It is of the present invention that linearly randomly the preparation method of biodegradable copolymer ester includes:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates, starts to vacuumize, and precondensation is first carried out under the first low vacuum, then under the first high vacuum
Polycondensation reaction is carried out, polymer P 1 is made, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum
Power；
(2) component b and component c are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction, until esterification terminates；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction.
In method of the present invention, the component c is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, alicyclic ring
At least one of race's binary acid and the acid anhydrides of cycloaliphatic diacid.The chemical general formula of the aliphatic dibasic acid can be
HOOC-R13- COOH, wherein R13It can be the alkylidene of C1-C12, and the alkylidene of the C1-C12 can be straight chained alkyl
Or the alkylidene with branch.Under preferable case, R13It is C3-C10 for the alkylidene of C1-C8 namely the aliphatic dibasic acid
Aliphatic dibasic acid, the more preferably aliphatic dibasic acid of C3-C7.The cycloaliphatic diacid can be for at least one
The binary acid of cycloaliphatic ring.Under preferable case, the cycloaliphatic diacid is the cycloaliphatic diacid of C5-C10.
In method of the present invention, the component b is aliphatic dihydroxy alcohol, the preferably binary aliphatic of C2-C6
Alcohol.The chemical general formula of the aliphatic dihydroxy alcohol can be HO-R12- OH, wherein R12It can be C2-10Alkylidene, and R12It can
Think straight chained alkyl or the alkyl with branch.Under preferable case, the component b be selected from ethylene glycol, propylene glycol, butanediol,
At least one of pentanediol, hexylene glycol, heptandiol and ethohexadiol.
In method of the present invention, the component a is in the acid anhydrides of aromatic acid and aromatic acid
It is at least one.The chemical general formula of the aromatic acid can be HOOC-Ar-COOH, wherein Ar can be for at least one
The group of a phenyl ring, naphthalene nucleus and anthracene nucleus, under preferable case, Ar is following aryl:
Wherein, R5、R6、R7、R8、R9And R10It is each independently hydrogen, C1-C4Alkyl, F, Cl ,-NO2,-CN or-OR11,
Wherein, R11For C1-C4Alkyl.
A preferred embodiment of the invention, the component c are selected from C3-C10Aliphatic dibasic acid, C3-C10
Aliphatic dibasic acid acid anhydrides, C5-C10Cycloaliphatic diacid and C5-C10Cycloaliphatic diacid acid anhydrides at least one
Kind；The component b is 1,4- butanediol；The component a is terephthalic acid (TPA) and/or terephthalic anhydride.According to the preferred reality
Linear random biodegradable copolymer ester molecular weight with higher and good tensile mechanical properties prepared by the mode of applying.
In method of the present invention, first catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)n
At least one of compound or their mixture, wherein M be titanium, antimony or zinc, n be M valence state, R1For C1-C10Alkane
Base, R2For C1-C30Alkyl.In order to make the Biodegradable polyester finally prepared that there is the molecular weight that further increases and smaller
Molecular weight distribution index, while improving the tensile mechanical properties of Biodegradable polyester finally prepared, first catalysis
Agent is preferably selected from the oxide and titanyl compound of alkoxytitanium, antimony acetate, zinc acetate, the oxide of zinc, antimony at least
It is a kind of.In further preferred situation, first catalyst is selected from butyl titanate (Ti (OC4H9)4), titanium isopropoxide, two
At least one of titanium oxide, antimony oxide, antimony acetate and zinc acetate.
In method of the present invention, second catalyst is at least one organo-tin compound.It is final in order to make
The Biodegradable polyester of preparation has the molecular weight and lesser molecular weight distribution index further increased, while improving final
The tensile mechanical properties of the Biodegradable polyester of preparation, second catalyst are preferably selected from Dibutyltin oxide, oxidation
Aminomethyl phenyl tin, tetraethyl tin, oxidation Hexaethyl tin, oxidation six cyclohexyl, two tin, oxidation two (dodecyl) tin, triethyl group hydroxyl
Ji Xi, fentin hydroxide, acetic acid triisobutyl tin, dibutyltin diacetate, tin dilaurate stannous phenide, monobutyl tri-chlorination
In tin, tributyltin chloride, dibutyltin sulfide, butylhydroxy tin oxide, methane stannonic acid, ethyl stannonic acid and butyl stannonic acid extremely
Few one kind.In further preferred situation, second catalyst is selected from Dibutyltin oxide, tetraethyl tin, triphenyl hydroxyl
Tin, dibutyltin diacetate, tin dilaurate stannous phenide, monobutyl-tin-trichloride, tributyltin chloride, dibutyltin sulfide,
At least two mixture in butylhydroxy tin oxide, methane stannonic acid, ethyl stannonic acid and butyl stannonic acid.In this case,
The content of each component of the third catalyst can be 10-90 moles of %, preferably 30-70 moles of %.
In method of the present invention, the third catalyst is that at least one chemical formula is RE (R3)3Compound,
Wherein, RE is thulium, R3For selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4In COO- group extremely
Few one kind, R4For C1-C30Alkyl.In order to make the Biodegradable polyester finally prepared have the molecular weight that further increases and
Lesser molecular weight distribution index, while improving the tensile mechanical properties of Biodegradable polyester finally prepared, described the
It is RE (R in chemical formula in three catalyst3)3Compound in, RE is preferably lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium or scandium；Institute
Stating halogen is chlorine or bromine, and the alkoxy is C3-C6Alkoxy, the aryloxy group be include at least one phenyl ring and/or naphthalene nucleus
Aryloxy group, R4For C1-C20Alkyl.In further preferred situation, RE is selected from lanthanum, cerium, praseodymium, neodymium or scandium, and the halogen is
Chlorine or bromine, the alkyl in the alkoxy are isopropyl, normal-butyl or isopentyl, and the aryl in the aryloxy group is 2,6-, bis- uncle
Butyl -4- aminomethyl phenyl or 4- butyl phenyl, R4For C3-C18Alkyl.In preferred situation, the third catalyst is second
Acyl acetone lanthanum, acetylacetone,2,4-pentanedione neodymium, isopropoxy neodymium, isopropoxy lanthanum, isopropoxy scandium, Lanthanum Stearate, stearic acid neodymium, chlorination
Lanthanum, three (2,6- di-t-butyl -4- methylphenoxy) one of lanthanums and their hydrate or a variety of.
In method of the present invention, the esterification condition in step (1) can be in conventional esterification condition
It properly selects.Under preferable case, the esterification reaction temperature is 180-220 DEG C.In the esterification reaction process, work as reaction
When the water of generation is greater than the 98% of theoretical production quantity, it can be determined that terminate for esterification.
In method of the present invention, in step (1), it is preferable that the absolute pressure under the first low vacuum is than first
Absolute pressure high 300-600Pa, more preferable 400-500Pa under high vacuum.Absolute pressure under preferable case, under the first low vacuum
Power is 500-600Pa, and the absolute pressure under the first high vacuum is 200Pa or less (such as 10-200Pa).
In method of the present invention, in step (1), the reaction condition of the precondensation may include: that temperature is
240-255 DEG C, the time is 0.5-2 hours.
In method of the present invention, in step (1), the reaction condition of the polycondensation may include: that temperature is
250-270 DEG C, the time is 2-3 hours.
In method of the present invention, in step (1), the component a and the molar ratio of the dosage of the component b are
1:0.8-6 preferably 1:0.8-3.
In method of the present invention, the esterification condition in step (2) can be in conventional esterification condition
It properly selects.Under preferable case, the esterification reaction temperature is 150-200 DEG C.In the esterification reaction process, work as reaction
When the water of generation is greater than the 98% of theoretical production quantity, it can be determined that terminate for esterification.
In method of the present invention, in step (2), the component c and the molar ratio of the dosage of the component b are
1:0.8-6 preferably 1:0.8-3.
In method of the present invention, in step (3), it is preferable that the polycondensation process includes: to make mixture
Material (i.e. the mixture of polymer P 1 and the reaction product of step (2) preparation) first carries out precondensation under the second low vacuum, then
Polycondensation is carried out under the second high vacuum, wherein the absolute pressure under the second low vacuum is greater than the absolute pressure under the second high vacuum.
In method of the present invention, it is preferable that the absolute pressure under the second low vacuum is than exhausted under the second high vacuum
300-600Pa high to pressure, more preferable 400-500Pa.Under preferable case, the absolute pressure under the second low vacuum is 500-
600Pa, the absolute pressure under the second high vacuum are 200Pa or less (such as 10-200Pa).
In method of the present invention, in step (3), the reaction condition of the precondensation may include: that temperature is
240-255 DEG C, the time is 0.5-2 hours.
In method of the present invention, in step (3), the reaction condition of the polycondensation may include: that temperature is
250-270 DEG C, the time is 2-3 hours.
A preferred embodiment of the invention, the preparation method packet of the linear random biodegradable copolymer ester
It includes:
(1) component a and component b are esterified in the presence of the first catalyst, the second catalyst and third catalyst
Reaction；The component a is at least one of aromatic acid and/or the acid anhydrides of aromatic acid；The component b is rouge
Fat race dihydric alcohol；The molar ratio of the additional amount of the additional amount and component b of component a is 1:0.8-6, preferably 1:0.8-3, until esterification
Reaction terminates, and starts to vacuumize, first precondensation is carried out at low vacuum (vacuum degree 600-300Pa), 240-260 DEG C, then into
Row high vacuum (vacuum degree is less than 200Pa) polycondensation reaction, reaction temperature is 250-270 DEG C, is reacted 2-3 hours, and reaction was completed, system
Polymer P 1 is obtained, crushing pelletizing is optionally carried out.
(2) in the presence of the first catalyst, the second catalyst and third catalyst, it is esterified component b and component c
Reaction, the component c are aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and cycloaliphatic diacid
At least one of acid anhydrides；The molar ratio of the additional amount of the additional amount and component b of component c is 1:0.8-6；To esterification knot
Beam.
(3) polymer P 1 is added in the reaction product of step (2) preparation, carries out polycondensation reaction, first preshrunk together
It is poly-, then carry out final polycondensation reaction 2-3 hours, until reaction terminates.
In method of the present invention, above-mentioned steps (1) and step (2), can be with any one elder generations without successive point
Carry out after another, can also both carry out simultaneously.
The present invention also provides the linear random biodegradable copolymer esters prepared by the above method.The copolyesters has
Lower melt index, specifically, the copolyesters are measured under 150 DEG C, 2.16kg load using ISO 1133-2005 method
Melt index be 3.5-5.2g/10min, using the molten of ISO 1133-2005 method measurement under 190 DEG C, 2.16kg load
Melting index is 10-20g/10min.
The invention will be further described by the following examples, but protection scope of the present invention is not limited only to this.
In the following Examples and Comparative Examples, Lanthanum Stearate is made according to the method for embodiment A5 in CN1807485A.
Embodiment 1
The metatitanic acid four of the terephthalic acid (TPA) of 285g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.1g, 0.14g triphenyl
Hydroxyl tin (being purchased from Beijing chemical reagents corporation) and the Lanthanum Stearate of 0.31g are heated with stirring to reflux in a nitrogen atmosphere, will
Temperature is adjusted to 220 DEG C, and when the water wait react generation is greater than the 98% of theoretical production quantity, the absolute pressure in reaction kettle is adjusted
To 550Pa, temperature of reaction kettle is 255 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to
260 DEG C, and obtain yellow polymer P11 to terminal within polycondensation 2 hours at this temperature and pressure.
The metatitanic acid of the 1,4- succinic acid of 202.6g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
Four butyl esters (be purchased from Beijing chemical reagents corporation), 0.2g Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.31g's is hard
Resin acid lanthanum, in a nitrogen atmosphere, heating stirring is to flowing back, and the temperature was then adjusted to 200 DEG C, the water of generation to be reacted is greater than theoretical raw
At amount 98% when, the polymer P 11 is added, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is
It 255 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and in the temperature and pressure
Obtain light yellow copolymer SP1 to terminal within polycondensation 2 hours under power.
Comparative example 1
The metatitanic acid four of the terephthalic acid (TPA) of 285g, the 1,4- butanediol of 200g, 0.245g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from company, Beijing Chemical Factory No. 3) of 0.1g and 0.14g
Fentin hydroxide (is purchased from Beijing chemical reagents corporation), in a nitrogen atmosphere, is heated with stirring to reflux, the temperature was then adjusted to
220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, be added thereto 202.6g 1, 4- succinic acid, 200
The Lanthanum Stearate of 1,4-butanediol and 0.62g continues heating stirring to reflux, the temperature was then adjusted to 200 DEG C, generation to be reacted
When water steams completely, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, and it is small to carry out precondensation 1
When, continue for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and polycondensation 7 hours at this temperature and pressure, obtains shallow
Yellow copolymer DP1.
Embodiment 2
The metatitanic acid four of the terephthalic acid (TPA) of 204g, the 1,4- butanediol of 144g, 0.174g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.071g, 0.099g three
Phenyl hydroxyl tin (being purchased from Beijing chemical reagents corporation) and the Lanthanum Stearate of 0.22g are heated with stirring to back in a nitrogen atmosphere
Stream, the temperature was then adjusted to 220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, by the absolute pressure in reaction kettle
Power is adjusted to 550Pa, and temperature of reaction kettle is 255 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature
260 DEG C are adjusted to, and obtains yellow polymer P21 to terminal within polycondensation 3 hours at this temperature and pressure.
Four fourth of metatitanic acid of the 1,4- succinic acid of 269g, the 1,4- butanediol of 266g, 0.3g is added into the reaction kettle of 2.5L
The stearic acid of Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.4g of ester (being purchased from Beijing chemical reagents corporation), 0.13g
Lanthanum, in a nitrogen atmosphere, heating stirring is to flowing back, and the temperature was then adjusted to 200 DEG C, the water of generation to be reacted is greater than theoretical production quantity
98% when, the polymer P 21 is added, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C,
It carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and contracts at this temperature and pressure
Poly- 3 hours to terminal, obtains light yellow copolymer SP2.
Comparative example 2
The metatitanic acid four of the terephthalic acid (TPA) of 204g, the 1,4- butanediol of 144g, 0.174g are added into the reaction kettle of 2.5L
The Dibutyltin oxide (being purchased from company, Beijing Chemical Factory No. 3) and 0.099g of butyl ester (being purchased from Beijing chemical reagents corporation), 0.071g
Fentin hydroxide (be purchased from Beijing chemical reagents corporation), in a nitrogen atmosphere, be heated with stirring to reflux, the temperature was then adjusted to
220 DEG C, when the water wait react generation is greater than the 98% of theoretical production quantity, the 1, 4- succinic acid of 269g, 266g are added thereto
The Lanthanum Stearate of 1,4-butanediol and 0.62g continues heating stirring to reflux, the temperature was then adjusted to 200 DEG C, generation to be reacted
When water steams completely, the absolute pressure in reaction kettle is adjusted to 550Pa, temperature of reaction kettle is 255 DEG C, and it is small to carry out precondensation 1
When, continue for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and polycondensation 7 hours at this temperature and pressure, obtains shallow
Yellow copolymer DP2.
Embodiment 3
The metatitanic acid four of the terephthalic acid (TPA) of 466g, the 1,4- butanediol of 303g, 0.245g are added into the reaction kettle of 2.5L
Butyl ester (be purchased from Beijing chemical reagents corporation), the Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) of 0.1g, 0.14g triphenyl
Hydroxyl tin (being purchased from Beijing chemical reagents corporation) and the Lanthanum Stearate of 0.31g are heated with stirring to reflux in a nitrogen atmosphere, will
Temperature is adjusted to 220 DEG C, and when the water wait react generation is greater than the 98% of theoretical production quantity, the absolute pressure in reaction kettle is adjusted
To 600Pa, temperature of reaction kettle is 250 DEG C, carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 100Pa, temperature is adjusted to
260 DEG C, and obtain yellow polymer P31 to terminal within polycondensation 2 hours at this temperature and pressure.
The metatitanic acid four of the 1,4- succinic acid of 82.8g, the 1,4- butanediol of 76g, 0.245g are added into the reaction kettle of 2.5L
The tristearin of Dibutyltin oxide (being purchased from Beijing Chemical Factory No. 3) and 0.31g of butyl ester (being purchased from Beijing chemical reagents corporation), 0.2g
Sour lanthanum, in a nitrogen atmosphere, heating stirring is to flowing back, and the temperature was then adjusted to 200 DEG C, the water of generation to be reacted is greater than theoretical generate
Amount 98% when, the polymer P 31 is added, the absolute pressure in reaction kettle is adjusted to 600Pa, temperature of reaction kettle 255
DEG C, it carries out precondensation 1 hour, continues for vacuum degree to be adjusted to 150Pa, temperature is adjusted to 260 DEG C, and at this temperature and pressure
Obtain light yellow copolymer SP3 to terminal within polycondensation 2 hours.
Test case
The number-average molecular weight of copolymer SP1-SP3 and DP1-DP2 are detected according to gel permeation chromatography (GPC) method and are again divided equally
Son amount；
The molecular weight distribution index of copolymer is detected and calculated according to GPC method；
The glass transition temperature of copolymer is detected according to differential scanning calorimeter (DSC) measuring method；
The tensile mechanical properties of copolymer SP1-SP3 and DP1-DP2 are detected as being broken according to the method for ASTM D638-03
Elongation and fracture tensile strength；
The measurement of melt index: using American science instrument manufacturing company CS-127 type fusion index instrument measurement copolymer
Melt flow rate (MFR) (MI), under 190 DEG C of (or 150 DEG C), 2.16kg loads, using " the thermoplastic of ISO 1133-2005
The measurement of melt mass flow rate and melt volume-flow rate " standard is measured.
Its testing result is as shown in table 1 below.
Table 1
The copolyesters prepared according to the method described in the present invention it can be seen from the data of upper table 1 has lower melting
Index, and molecular weight with higher, tensile mechanical properties are preferable.
Claims (11)
1. a kind of linear random biodegradable copolymer ester, the copolyesters have aliphatic ester structural unit shown in formula (1) and
Aromatic ester structural unit shown in formula (2),
Wherein, R1' and R3' identical or different, and it is each independently selected from alkylidene；R2' selected from being made of alkylidene and cycloalkylidene
Group；R4' it is arlydene；
The melt index that the copolyesters uses ISO 1133-2005 method to measure under 150 DEG C, 2.16kg load is 3.5-
5.2g/10min, the melt index for using ISO 1133-2005 method to measure under 190 DEG C, 2.16kg load is 10-20g/
10min。
2. copolyesters according to claim 1, wherein R1' and R3' identical, and it is selected from the alkylidene of C2-C6；R2' it is C2-
The alkylidene of C6；R4' the arlydene for being C6-C12.
3. a kind of preparation method of linear random biodegradable copolymer ester, this method comprises:
(1) component a and component b is made to carry out esterification in the presence of the first catalyst, the second catalyst and third catalyst,
Terminate to esterification, start to vacuumize, first carries out precondensation under the first low vacuum, then contract under the first high vacuum
Poly- reaction, is made polymer P 1, wherein the absolute pressure under the first low vacuum is greater than the absolute pressure under the first high vacuum；
(2) component b and component c is made to carry out esterification in the presence of the first catalyst, the second catalyst and third catalyst,
Terminate to esterification；
(3) polymer P 1 prepared by step (1) is mixed with reaction product prepared by step (2) and carries out polycondensation reaction；
Wherein, the component a is at least one of aromatic acid and the acid anhydrides of aromatic acid；The component b is
Aliphatic dihydroxy alcohol；The component c is aliphatic dibasic acid, the acid anhydrides of aliphatic dibasic acid, cycloaliphatic diacid and alicyclic
At least one of acid anhydrides of binary acid；
First catalyst is oxide, M (OR selected from M1)nWith M (- OOCR2)nAt least one of compound or they
Mixture, wherein M is titanium, antimony or zinc, and n is the valence state of M, R1For C1-C10Alkyl, R2For C1-C30Alkyl；
Second catalyst is at least one organo-tin compound；
The third catalyst is that at least one chemical formula is RE (R3)3Compound, wherein RE is thulium, R3For
Selected from halogen, alkoxy, aryloxy group, levulinic ketone group and R4At least one of COO- group, R4For C1-C30Alkyl.
4. according to the method described in claim 3, wherein, the esterification reaction temperature in step (1) is 180-220 DEG C, step (2)
In esterification reaction temperature be 150-200 DEG C.
5. according to the method described in claim 3, wherein, in step (1), the absolute pressure under the first low vacuum is 500-
600Pa, the absolute pressure under the first high vacuum are 200Pa or less.
6. the method according to claim 3 or 5, wherein in step (1), the reaction condition of the precondensation includes: temperature
Degree is 240-255 DEG C, and the time is 0.5-2 hours；The reaction condition of the polycondensation includes: that temperature is 250-270 DEG C, time 2-
3 hours.
7. the method according to any one of claim 3-5, wherein in step (3), the polycondensation process packet
It includes: so that mixed material is first carried out precondensation under the second low vacuum, polycondensation is then carried out under the second high vacuum, wherein second
Absolute pressure under low vacuum is greater than the absolute pressure under the second high vacuum.
8. according to the method described in claim 7, wherein, the absolute pressure under the second low vacuum is 500-600Pa, the second Gao Zhen
Absolute pressure under empty is 200Pa or less.
9. according to the method described in claim 7, wherein, in step (3), the reaction condition of the precondensation includes: temperature
It is 240-255 DEG C, the time is 0.5-2 hours；The reaction condition of the polycondensation includes: that temperature is 250-270 DEG C, time 2-3
Hour.
10. the method according to any one of claim 3-9, wherein the component a is the aromatic dicarboxylic of C8-C14
At least one of the acid anhydrides of aromatic acid of acid and C8-C14；The component b is the aliphatic dihydroxy alcohol of C2-C6；Institute
State at least one of aliphatic dibasic acid and the acid anhydrides of aliphatic dibasic acid of C3-C7 that component c is C3-C7.
11. the linear random biodegradable copolymer ester of the preparation of the method as described in any one of claim 3-10.
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