CN104327260A - Preparation method of biodegradable recycled polyester - Google Patents
Preparation method of biodegradable recycled polyester Download PDFInfo
- Publication number
- CN104327260A CN104327260A CN201410609018.1A CN201410609018A CN104327260A CN 104327260 A CN104327260 A CN 104327260A CN 201410609018 A CN201410609018 A CN 201410609018A CN 104327260 A CN104327260 A CN 104327260A
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- China
- Prior art keywords
- reaction
- ethylene glycol
- depolymerization
- preparation
- temperature
- Prior art date
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- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 442
- -1 diol titanium alkali metal Chemical class 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 188
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 60
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 60
- 239000002253 acid Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 55
- 238000006136 alcoholysis reaction Methods 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 43
- 238000001704 evaporation Methods 0.000 claims description 36
- 230000008020 evaporation Effects 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 36
- 238000012691 depolymerization reaction Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006068 polycondensation reaction Methods 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 15
- 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 13
- ZWEDFZVJMFBOGV-UHFFFAOYSA-N C(=O)C1=C(O)C(O)=C(C(C)C)C2=CC(C)=C(C(O)=C12)C1=C(O)C2=C(C=O)C(O)=C(O)C(C(C)C)=C2C=C1C.C(C)O Chemical compound C(=O)C1=C(O)C(O)=C(C(C)C)C2=CC(C)=C(C(O)=C12)C1=C(O)C2=C(C=O)C(O)=C(O)C(C(C)C)=C2C=C1C.C(C)O ZWEDFZVJMFBOGV-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-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
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 150000001457 metallic cations Chemical class 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- GIDJXAQRKDSAND-UHFFFAOYSA-J [Ge+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [Ge+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GIDJXAQRKDSAND-UHFFFAOYSA-J 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 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 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 230000008929 regeneration Effects 0.000 abstract description 15
- 238000011069 regeneration method Methods 0.000 abstract description 15
- 150000002148 esters Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 230000018109 developmental process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 124
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- NWJKPSLXLQLUTC-UHFFFAOYSA-N ethane-1,2-diol;sodium Chemical compound [Na].OCCO NWJKPSLXLQLUTC-UHFFFAOYSA-N 0.000 description 16
- AQVNXGRBASVGRC-UHFFFAOYSA-N [Li].OCCO Chemical compound [Li].OCCO AQVNXGRBASVGRC-UHFFFAOYSA-N 0.000 description 13
- 229910052701 rubidium Inorganic materials 0.000 description 13
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- ZVDJKPHNSCMPGU-UHFFFAOYSA-N potassium;propane-1,2-diol Chemical compound [K].CC(O)CO ZVDJKPHNSCMPGU-UHFFFAOYSA-N 0.000 description 12
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 12
- 239000003086 colorant Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- ZSXFZANQMJQBTQ-UHFFFAOYSA-N ethane-1,2-diol;potassium Chemical compound [K].OCCO ZSXFZANQMJQBTQ-UHFFFAOYSA-N 0.000 description 8
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 8
- 229940058015 1,3-butylene glycol Drugs 0.000 description 6
- 235000019437 butane-1,3-diol Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012634 fragment Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 229960003511 macrogol Drugs 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 0 C(*O1)O[Tl]112(O*CO1)O*CO2 Chemical compound C(*O1)O[Tl]112(O*CO1)O*CO2 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate tribasic Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a preparation method of biodegradable recycled polyester. The preparation method is applied to the field of chemical regeneration of waste polyester and polyester differential development. In the preparation method, a diol titanium alkali metal coordination compound soluble in glycol is taken as a catalyst to catalyze glycol depolymerization of a waste polyester material and a copolycondensation process of a depolymerization product and aliphatic diacid polyether ester so as to generate crystalline biodegradable recycled polyester which is good in color and luster. The catalyst adopted in the method has relatively high catalytic activity on both glycol depolymerization of the polyester and a copolymerization process of the depolymerization product, and can be applied to re-copolymerization without being removed from the depolymerization product, thus the separation and purification cost of the depolymerization product can be greatly lowered, the production efficiency is improved, and continuous differential chemical regeneration of PET becomes possible.
Description
Technical field
The invention belongs to the chemical regeneration technical field of polyester, relate to a kind of preparation method of biodegradable recycled polyester, particularly relate to binary titanium alkoxide alkali metal coordination compound that a kind of employing is dissolvable in water ethylene glycol prepares biodegradable recycled polyester for the ethylene glycol depolymerization of catalyst, polyester and depolymerization product copolymerization method as catalyzer.
Background technology
Polyethylene terephthalate (polyethylene terephthalate, PET, be called for short polyester) be a kind of semi-crystalline thermoplastic macromolecule material of excellent performance, be widely used in the fields such as chemical fibre, packaging, medicine, electric mechanical, 2010, global polyester ultimate production reached 5,610 ten thousand tons.While PET industry develop rapidly, the process problem of waste and old polyester goods is comed one after another, and in society, the huge storage of waste polyester goods not only brings huge pressure to ecotope, causes the serious waste of fossil resources simultaneously.Therefore; the regeneration of waste polyester goods is reclaimed and not only can turn waste into wealth; alleviate the pressure of the Nonrenewable resources shortage such as oil; waste and old polyester is regenerated as Biodegradable polyester to be significant to the protection of ecotope and the Sustainable development etc. of PET industry, be also the focus of current PET industry development simultaneously.
In conjunction with the physicochemical characteristic of polyester, its way of recycling is mainly divided into physics to regenerate and chemical regeneration two kinds.Physics method of reproduction is based on the thermoplasticity of polyester, by the method for carrying out melting granulation again after the removal of impurities of waste and old polyester goods, cleaning, pulverizing drying being realized the regeneration of polyester, although physics regeneration has, cost is low, the simple feature of technology, but the degradation that only can realize polyester reclaims, and recovered frequency is limited, enclosed circulation can not be realized.The reversibility of chemical regeneration based on polyester polycondensation reaction and the nucleophilic reaction mechanism of transesterification reaction, polyester is made to be depolymerized to polymerization single polymerization monomer or intermediate by the attack of small molecules depolymerizing agent to macromolecular chain, after separating-purifying, carry out repolymerization realize regeneration, main depolymerization method has hydrolysis, methyl alcohol solution and ethylene glycol solution three kinds, wherein hydrolysis reaction needs acid or the alkali of high density, methyl alcohol solution reaction needed high temperature and high pressure environment, therefore high to equipment requirements, industrialization difficulty is large; By contrast, it is gentleer that ethylene glycol solution has reaction conditions, and can utilize existing polyester production facility, technical process is short, is easy to realize continuous prodution, the feature that easier functionalization regeneration etc. are outstanding and enjoy industry to favor.Simultaneously; the degraded under field conditions (factors) of PET polyester is very slowly; a large amount of not recoverable Polyester wastes is also to the huge pressure that ecotope brings; therefore the exploitation of degradable polyester is the differential important branch of polyester, so it is the exploitation route taking into account economic benefit and environment protection that waste PET polyester chemistry is regenerated as degradable polyester.
The ethylene glycol solution of PET reacts the heterogeneous reaction of normal pressure or the low pressure of normally carrying out at 180-220 DEG C.Because temperature of reaction is higher, in order to prevent the reaction times long generation causing the side reactions such as the decomposition of polymer degradation, depolymerization product and glycol ether generation, usually need to add alcoholysis catalysts accelerated reaction.At present, the alcoholysis catalysts known the most take zinc acetate as the metallic salt of representative, although the alcoholysis catalytic efficiency of zinc acetate is high, but zinc acetate also exists serious defect as depolymerization catalyst, first its consumption is higher, be generally the 0.5-1.5% of PET quality, and be difficult to after depolymerization remove from product, the zine ion simultaneously remaining in high-content in depolymerization product can accelerate because it comprehends to the catalytic machine of ketonic oxygen coordination side reactions such as causing in repolymerization process thermal destruction, molecular weight is increased limited, the viscosity of recycled polyester is low, poor quality.Patent of invention CN 102584594 A CoCl
4 2-/ NiCl
4 2-the method of the ionic liquid-catalyzed alcoholysis polyethylene terephthalate of type, the method of patent of invention CN 102731310 A the first transition metal ion liquid catalyst alcoholysis ethylene glycol terephthalate, and CN200810101969.2 is used in the polyester alcoholysis catalysts announced in the catalyzer of alcoholysis polyethylene terephthalate, although have reaction conditions gentleness, speed of response is fast, transformation efficiency is high, catalytic selectivity is high, the advantages such as catalyzer can be recycled, but the defect that existence one is very important simultaneously, be exactly in the catalyzer of this type of ionic liquid halogen group element content very high, if fail catalyzer to remove from depolymerization product, then can cause macromolecular decomposition because producing hydrogen halide in repolymerization process, have a strong impact on the quality of repolymerization goods, and catalyzer removal thoroughly from depolymerization product significantly will be increased production cost, lose more than gain.Patent of invention CN200810126347.5SO
4 2-/ MO
2type solid super acid catalyst degraded polyethylene terephthalate prepares a kind of SO disclosed in BHET
4 2-/ MO
2although it is easily separated that type solid acid catalyst has product, catalytic selectivity is high, the feature easily recycled, and because it is heterogeneous catalyst, in catalytic reaction, mass transfer process is complicated, causes catalytic efficiency lower.
Summary of the invention
The object of this invention is to provide a kind of preparation method of biodegradable recycled polyester, be intended to solve the published alcoholysis catalysts that uses in the current polyesterols solution differential chemical regeneration process residual disadvantageous effect to producing in polymerization process again in alcoholysis product, and the problem causing catalytic efficiency low due to the heterogeneous property of catalyzer in depolymerization liquid.The preparation method of biodegradable recycled polyester provided by the invention is adopted just to can be used for copolymerization again without the need to being removed from depolymerization product by catalyzer, greatly can save depolymerization product separating-purifying cost, ensure that carrying out smoothly and the quality of biodegradable recycled polyester, for the differential chemical regeneration of PET serialization provides possibility of repolymerization process.
The alcoholysis of PET polyester and this Liang Zhong reacting quintessence of polycondensation are all realize molecule chain break with the dimolecular reaction mechanism of acyl-oxygen cleavage and increase, but because the factor difference such as reactant nature and reaction conditions of alcoholysis reaction and polycondensation is larger, have not yet to see a kind of catalyzer can all realize reaction efficiently and directionally in two simultaneously catalysis under reaction conditions, depolymerization catalyst often has a negative impact to polycondensation process, as serious thermal destruction catalysis etc. simultaneously.Therefore need in PET polyester chemistry regenerative process at present the catalyzer removing that alcoholysis process used to ensure depolymerization product the carrying out smoothly of polymerization process again, this process significantly will add cost of withdrawing deposit, and make PET polyester chemical regeneration and chemistry functional regeneration Difficulty thereof.The present invention is by adopting bimetal matching structure design, catalyzer is made to combine two kinds of catalytic mechanisms of the dimolecular reaction of acyl-oxygen cleavage, i.e. ligand exchange mechanism and metal alkoxide mechanism, this catalyzer all can be shown efficiently and the catalytic activity of orientation in the alcoholysis and polycondensation two kinds reaction of PET, and side reaction is few, the catalyzer of this bimetal fit structure provided by the invention is ate complex, suitable and the rational transition metal titanium of outer shell electron distribution of preferred electronegativity is as the central atom of acid group coordination ion, make part with di-alcohols structure and promote homogeneity and ligand exchange activity, adopt basic metal race as positively charged ion on the one hand for promoting the ligancy of catalytic center titanium atom, part is made more easily deformation to occur, thus strengthen the catalytic activity of titanium in alcoholysis and polycondensation process, on the other hand, basic metal race positively charged ion can realize auxiliary acceleration by the mode forming metal alkoxide to alcoholysis reaction, all high reactivity can be shown to PET depolymerization and copolycondensation to reach this catalyzer, without the need to being removed after depolymerization, therefore biodegradable recycled polyester preparation method provided by the invention can effectively solve foregoing problem.
The preparation method of a kind of biodegradable recycled polyester of the present invention, comprises the following steps:
1) ethylene glycol depolymerization is carried out to PET polyester:
1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, forms depolymerization solution;
1.2) depolymerization solution is mixed with PET polyester and stirred carry out depolymerization reaction, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the reaction times is 30min-8h;
The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:
Wherein, M
+being IA race metallic cation, is Li
+, Na
+, K
+or Rb
+;
R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4;
This kind of structure design has following advantage:
A)-O-R '-O-structure can make this Titanium series catalyst have solubility in depolymerizing agent ethylene glycol, to guarantee that depolymehzation process is for homogeneous catalysis, promotes catalytic efficiency;
B) M
+the introducing of IA race metallic cation can effectively avoid Ti with-(-O-R '-O-)-
3the catalytic activity that the chain-like structure that structure autohemagglutination forms one dimension prolongation causes reduces;
C) M
+the introducing of IA race metallic cation can make the ligancy of Ti atom in catalyzer improve, thus cause the stability of catalyst space structure to reduce, there is ligand exchange reaction due to coordination in the ester bond more easily and in depolymerizing agent and polyester, thus causes macromole chain rupture.Meanwhile, the coordination of Ti and ester bond can increase the Electron Affinities of carbonyl carbon in macromolecular chain, and M
+can have an effect with the hydroxyl in depolymerizing agent ethylene glycol and the nucleophilicity of hydroxyl oxygen, therefore Ti and M can be increased
+the mutual promoting action of both makes at the easier attack polyester macromolecule of ethylene glycol and acyl-oxygen bond rupture occurs, i.e. the alcoholysis of PET, therefore has very high alcoholysis catalytic activity;
D) high in temperature of reaction, reactant is mainly in the polycondensation process of polyester oligomer, and the titanium ethylene glycolate acid group part of this catalyzer can make still have efficient catalytic activity in its polycondensation process by ligand exchange effect.
2) to decolouring and the purification of depolymerization product, step is as follows:
2.1) in step 1) to add containing quality of activated carbon mark in gained solution be the ethylene glycol dispersion liquid of 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirs decolouring 1-5h;
2.2) gac of impurity and decolouring is then removed after filtration;
2.3) repeating step 2.1) and 2.2) 2-5 time, also namely decolouring and filtration procedure carry out 2-5 time repeatedly, obtain the ethylene glycol solution of the depolymerizing substance after removal of impurities decolouring;
2.4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190-210 DEG C and pressure is 0.5-0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
3) copolymerization of depolymerization product, concrete step is as follows:
3.1) preparation of modification by copolymerization carboxylate: by binary of fatty acids, ethylene glycol, polyethers three with etc. amount mixing, and to add a certain amount of titanium ethylene glycolate alkali metal complex be catalyzer, be 170-180 DEG C in temperature of reaction, pressure is carry out esterification 3-4h under 1atm, distillates the water generated in reaction process in time simultaneously, protect with rare gas element in reaction process, reaction terminates rear acquisition aliphatic dibasic acid polyether ester compound;
3.2) by step 3.1) and step 2) the aliphatic dibasic acid polyether ester compound that obtains and purification and the depolymerization product after decolouring, polycondensation catalyst and thermo-stabilizer, be 1atm at 200-220 DEG C and pressure, under protection of inert gas, be uniformly mixed by certain mass ratio;
3.3) then, temperature of reaction is increased to 230-250 DEG C, continue reaction 60-120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa;
3.4) then, temperature of reaction is increased to 265-290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120-180min, namely obtain biodegradable recycled polyester.
As preferred technical scheme:
The preparation method of a kind of biodegradable recycled polyester as above, in described depolymerization solution, the consumption of described binary titanium alkoxide alkali metal coordination compound is the 0.1%-1% of quality of glycol; The molar mass of PET polyester calculates with 192g/mol; The preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, too much ethylene glycol can cause the side reaction generating glycol ether to occur, the very few productive rate that will reduce depolymerization speed and monomer, the preferred 180-210 DEG C of depolymerization reaction temperature, temperature of reaction is too low can reduce depolymerization rate, too high, can cause the generation of side reaction; Stir during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under protection of inert gas.
The preparation method of a kind of biodegradable recycled polyester as above, described binary titanium alkoxide alkali metal coordination compound is obtained by following steps:
A) by general formula be Ti (OR)
4titanium compound under 50-150 DEG C and nitrogen protection condition, be dibasic alcohol the HO-R '-OH Homogeneous phase mixing of 2-4 with carbonatoms; Wherein, the saturated hydrocarbon chains structure of R to be carbonatoms be 2-4, R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4; In conjunction with building-up reactions activity, catalytic activity, raw material stability and price factor, Ti (OR)
4preferred tetrabutyl titanate, titanium isopropylate; The preferred ethylene glycol of dibasic alcohol, 1,2-PD;
B) add IA race metal hydroxides MOH, continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180-250 DEG C;
C) in reaction process, backflow dibasic alcohol also gets rid of the lower boiling monohydroxy-alcohol R-OH and water that react and generate, and the reaction times is 2-5 hour, and reaction terminates rear fast by the dibasic alcohol evaporation acquisition white completely in system or micro-yellow solid;
D) utilized by above-mentioned solid ethanol-Gossypol recrystallized from chloroform repeatedly to obtain colourless or light yellow crystal and be described binary titanium alkoxide alkali metal coordination compound.
The preparation method of a kind of biodegradable recycled polyester as above, Ti (OR)
4be 1:20-100 with the mol ratio of HO-R '-OH; MOH and Ti (OR)
4mol ratio be 2.01-2.05:1; Step c) in, describedly refer to that, at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm fast, in 0.5-5min by dibasic alcohol evaporation in system completely.
The preparation method of a kind of biodegradable recycled polyester as above, described PET polyester is any type of goods made by polyethylene terephthalate and waste and old product by composition.
The preparation method of a kind of biodegradable recycled polyester as above, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the add-on of the ethylene glycol solution containing gac is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.
The preparation method of a kind of biodegradable recycled polyester as above, step 3.1) in, described binary of fatty acids is 1,6-hexanodioic acid, one or more in 1,10-sebacic acid; The polyoxyethylene glycol of described polyethers to be molecular weight be 400-2000; The add-on of described titanium ethylene glycolate alkali metal complex is 100-200ppm, and stir speed (S.S.) is 50-100rpm; Step 3.2) in, described presses certain mass than mixing, and namely the mass ratio of depolymerization product and aliphatic dibasic acid polyether ester compound is 8:2-1:2; Described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyzer, antimony glycol, antimony acetate, antimonous oxide, Germanium tetraacetate, germanium dioxide, titanium isopropylate, tetra-n-butyl titanate, titanium ethylene glycolate; The add-on of described polycondensation catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring; Described thermo-stabilizer is one or more in trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate; The add-on of described thermo-stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.
The preparation method of a kind of biodegradable recycled polyester as above, step 3.2) in, be uniformly mixed and refer to that mixing speed is that 50-80 turns/min, be uniformly mixed 30-60min; Step 3.3) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure changing down of 1kPa, and need during reaction to stir, mixing speed is that 50-80 turns/min; Step 3.4) in, continuing at the uniform velocity to reduce pressure to the air pressure changing down of 20Pa is 100Pa-1kPa/min, and continues when reacting to stir, and mixing speed is that 80-120 turns/min.
Beneficial effect:
(1) preparation method of a kind of biodegradable recycled polyester of the present invention belongs to the high-valued regeneration to waste and old polyester, has good economic worth and the value of environmental protection;
(2) catalyzer that adopts of the preparation method of a kind of biodegradable recycled polyester of the present invention, both can the ethylene glycol depolymerization reaction of the PET of catalysis efficiently, also can the copolyreaction again of its depolymerization product of catalysis efficiently.The zinc acetate can avoiding generally adopting at present, zinc-containing metal salt, containing the ionic liquid class catalyst alcoholysis of haloid element to the disadvantageous effect that repolymerization produces; Therefore the preparation method of this biodegradable recycled polyester is adopted just to can be used for copolymerization again without the need to being removed from depolymerization product by catalyzer, greatly can save depolymerization product separating-purifying cost, ensure that carrying out smoothly and the quality of biodegradable recycled polyester of repolymerization process, for the differential chemistry of PET serialization provides possibility, there is good application prospect;
(2) biodegradable recycled polyester preparation method provided by the present invention is adopted, the catalytic efficiency adopting mass transfer process complicated in solid heterogeneous catalyst alcoholysis and polymerization process to cause can be overcome low, because the binary titanium alkoxide basic metal composite salt catalyzer adopted has good solubility in ethylene glycol;
(3) the binary titanium alkoxide basic metal composite salt catalyzer used in recycled polyester preparation method provided by the present invention containing heavy metal, is not nontoxic or lower toxicity, and therefore prepared low-melting point polyester is safe and reliable;
(4) process for synthetic catalyst used in recycled polyester preparation method provided by the present invention is relatively simple, and reaction conditions is gentle, and reaction process is easy to control, and has good popularizing application prospect.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
First carry out producing of ethylene glycol lithium titanate, it comprises the following steps:
A) by tetraethyl titanate under 50 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetraethyl titanate and ethylene glycol is 1:100;
B) add lithium hydroxide, the mol ratio of lithium hydroxide and tetraethyl titanate is 2.05:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water reacting and generate, reaction times is 3 hours, after reaction terminates at temperature is 190 DEG C, reaction system pressure is under 0.5atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol lithium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate obtained above, the consumption of ethylene glycol lithium titanate is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste PET polyester bottles fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the reaction times is 3h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 1.5 times of depolymerization solution quality, at temperature is 150 DEG C, after atmospheric pressure reflux stirs decolouring 5h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190 DEG C and pressure is 0.5atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, Macrogol 4000 three with etc. amount mixing, and the ethylene glycol lithium titanate adding 100ppm is catalyzer, is 170 DEG C in temperature of reaction, pressure is carry out esterification 4h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 8:2 mixing step 4) and step 5) product that obtains, and add 100ppm ethylene glycol lithium titanate as polycondensation catalyst and 50ppm tripotassium phosphate ester heat stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 250 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 265 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.203dl/g fusing point: 220.7 DEG C of colours: L:79.31, b:6.53
Embodiment 2
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 150 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:50;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.03:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, the dibasic alcohol evaporation in system is obtained white solid completely in 1min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste pure polyester fabric fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the reaction times is 1h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 220 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1,6-hexanodioic acid, ethylene glycol, poly(oxyethylene glycol) 400 three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 200ppm, is 180 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound;
6) in mass ratio for 7:3 mixing step 4) and step 5) product that obtains, 500ppm triphenylphosphate thermo-stabilizer, and at 200 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 230 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 275 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.35dl/g fusing point: 170.3 DEG C of colours: L:73.34, b:12.67
Embodiment 3
First carry out producing of propylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 100 DEG C and nitrogen protection condition, with 1,2-PD Homogeneous phase mixing, the mol ratio of titanium isopropylate and 1,2-PD is 1:80;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 200 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 4 hours, and after reaction terminates at temperature is 200 DEG C, reaction system pressure is under 0.7atm, in in 1min by the ethylene glycol evaporation in system completely, dibasic alcohol evaporation in system is obtained faint yellow solid completely, utilizes ethanol-Gossypol recrystallized from chloroform to obtain clear crystal three times to this solid, be i.e. obtained propylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate obtained above, the consumption of propylene glycol potassium titanate is 0.5% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 600 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 1atm, and the reaction times is 8h
3) in step 2) add containing quality of activated carbon mark in gained solution be 4% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 4 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 200 DEG C and pressure is 0.6atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) sebacic acid tetraethylene-glycol carboxylate preparation: by 1,10-sebacic acid, ethylene glycol, Macrogol 2000 three with etc. amount mixing, and the propylene glycol potassium titanate adding 100ppm is catalyzer, is 175 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition sebacic acid tetraethylene-glycol carboxylate;
6) in mass ratio for 6:4 mixing step 4) and step 5) product that obtains, and add 200ppm propylene glycol potassium titanate as polycondensation catalyst and 500ppm tetra-sodium thermo-stabilizer, and at 200 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 250 DEG C, continue reaction 100min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 285 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 170min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.69dl/g fusing point: 130.7 DEG C of colours: L:73.25, b:12.39
Embodiment 4
First carry out producing of butyleneglycol metatitanic acid rubidium, it comprises the following steps:
A) by metatitanic acid tetra-tert ester under 50 DEG C and nitrogen protection condition, with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butyleneglycol mol ratios are 1:20;
B) add rubidium hydroxide, the mol ratio of rubidium hydroxide and metatitanic acid tetra-tert ester is 2.01:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 250 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling trimethyl carbinol and water that react and generate, and the reaction times is 5 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, in in 5min by the 1,3 butylene glycol evaporation in system completely, the dibasic alcohol evaporation in system is obtained yellow solid completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain light yellow crystal three times to this solid, i.e. obtained butyleneglycol metatitanic acid rubidium;
The structural formula of described alcoholysis catalysts butyleneglycol metatitanic acid rubidium is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts butyleneglycol metatitanic acid rubidium obtained above, the consumption of butyleneglycol metatitanic acid rubidium is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with PET polyester film and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2.5atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.9% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 0.5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, Polyethylene Glycol-600 three with etc. amount mixing, and the butyleneglycol metatitanic acid rubidium adding 120ppm is catalyzer, is 175 DEG C in temperature of reaction, pressure is carry out esterification 2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 1:2 mixing step 4) and step 5) product that obtains, and add 50ppm butyleneglycol metatitanic acid rubidium as polycondensation catalyst and 300ppm diphenyl phosphite thermo-stabilizer, and at 210 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 235 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.65dl/g fusing point: 115.6 DEG C of colours: L:70.76, b:17.32
Embodiment 5
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 150 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:60;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.01:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 205 DEG C, reaction system pressure is under 0.6atm, the dibasic alcohol evaporation in system is obtained white solid completely in 2min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste polyester bottle chip and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 50 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 230 DEG C, and reaction system pressure is 2.5atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 3% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 3 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of sebacic acid glycol ether carboxylate: by 1,10-sebacic acid, ethylene glycol, Macrogol 2000 three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 100ppm, is 170 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition sebacic acid glycol ether carboxylate;
6) in mass ratio for 8:2 mixing step 4) and step 5) product that obtains, 500ppm ammonium phosphate thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 80min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 285 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.79dl/g fusing point: 156.1 DEG C of colours: L:76.57, b:11.32
Embodiment 6
First carry out producing of ethylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 120 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of titanium isopropylate and ethylene glycol is 1:60;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 220 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 2 hours, after reaction terminates at temperature is 205 DEG C, reaction system pressure is under 0.6atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol potassium titanate is:
Then carry out a kind of preparation method of biodegradable recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol potassium titanate obtained above, the consumption of ethylene glycol potassium titanate is 0.1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution is mixed and the depolymerization reaction carried out under protection of inert gas with knitting containing the polyester cotton blending washing 85%, stir simultaneously, stir speed (S.S.) is 200 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 50:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 200 DEG C, and reaction system pressure is 1.5atm, and the reaction times is 1h;
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 3 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1,6-hexanodioic acid, ethylene glycol, Macrogol 2000 three with etc. amount mixing, and adding the ethylene glycol potassium titanate catalyst of 100ppm, is 178 DEG C in temperature of reaction, pressure is carry out esterification 3.2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound;
6) in mass ratio for 5:2 mixing step 4) and step 5) product that obtains, 100ppm ethylene glycol potassium titanate as polycondensation catalyst, 500ppm primary ammonium phosphate as thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 100min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 275 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 150min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.62dl/g fusing point: 165.2 DEG C of colours: L:75.32, b:11.39
Embodiment 7
First carry out producing of ethylene glycol lithium titanate, it comprises the following steps:
A) by tetraethyl titanate under 60 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetraethyl titanate and ethylene glycol is 1:80;
B) add lithium hydroxide, the mol ratio of lithium hydroxide and tetraethyl titanate is 2.05:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling second alcohol and water reacting and generate, reaction times is 3 hours, after reaction terminates at temperature is 190 DEG C, reaction system pressure is under 0.5atm, the dibasic alcohol evaporation in system is obtained white solid completely in 0.5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol lithium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol lithium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol lithium titanate obtained above, the consumption of ethylene glycol lithium titanate is 0.8% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste PET polyester bottles fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1500 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 20:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 190 DEG C, and reaction system pressure is 1atm, and the reaction times is 3h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 1.5 times of depolymerization solution quality, at temperature is 150 DEG C, after atmospheric pressure reflux stirs decolouring 5h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 190 DEG C and pressure is 0.5atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, Macrogol 4000 three with etc. amount mixing, and the ethylene glycol lithium titanate adding 100ppm is catalyzer, is 170 DEG C in temperature of reaction, pressure is carry out esterification 4h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 7:3 mixing step 4) and step 5) product that obtains, 50ppm dimethyl phosphate, 50ppm diphenyl phosphate are as thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 250 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 265 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.303dl/g fusing point: 170.7 DEG C of colours: L:79.31, b:6.53
Embodiment 8
First carry out producing of ethylene glycol sodium titanate, it comprises the following steps:
A) by tetra-n-butyl titanate under 120 DEG C and nitrogen protection condition, with ethylene glycol Homogeneous phase mixing, the mol ratio of tetra-n-butyl titanate and ethylene glycol is 1:60;
B) add sodium hydroxide, the mol ratio of sodium hydroxide and tetra-n-butyl titanate is 2.03:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 210 DEG C;
C) in reaction process, backflow ethylene glycol also gets rid of the lower boiling propyl carbinol and water that react and generate, reaction times is 2 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.8atm, the dibasic alcohol evaporation in system is obtained white solid completely in 5min by the ethylene glycol evaporation in system completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain clear crystal three times to this solid, i.e. obtained ethylene glycol sodium titanate;
The structural formula of described alcoholysis catalysts ethylene glycol sodium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts ethylene glycol sodium titanate obtained above, the consumption of ethylene glycol sodium titanate is 0.1% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with waste pure polyester fabric fragment and carry out the depolymerization reaction under protection of inert gas; stir simultaneously; stir speed (S.S.) is 1000 turns/min; the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 10:1; the molar mass of PET polyester calculates with 192g/mol; depolymerization reaction temperature is 180 DEG C, and reaction system pressure is 1atm, and the reaction times is 1h.
3) in step 2) add containing quality of activated carbon mark in gained solution be 5% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 5 times of depolymerization solution quality, at temperature is 220 DEG C, after atmospheric pressure reflux stirs decolouring 1h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid Triethylene Glycol compound: by 1,6-hexanodioic acid, ethylene glycol, poly(oxyethylene glycol) 400 three with etc. amount mixing, and adding the ethylene glycol metatitanic acid sodium catalyst of 200ppm, is 180 DEG C in temperature of reaction, pressure is carry out esterification 3h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid Triethylene Glycol compound;
6) in mass ratio for 3:1 mixing step 4) and step 5) product that obtains, add 50ppm ethylene glycol sodium titanate as polycondensation catalyst and 100ppm diphenyl phosphate as thermo-stabilizer, and at 200 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 230 DEG C, continue reaction 60min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 275 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.35dl/g fusing point: 150.3 DEG C of colours: L:73.34, b:12.67
Embodiment 9
First carry out producing of propylene glycol potassium titanate, it comprises the following steps:
A) by titanium isopropylate under 100 DEG C and nitrogen protection condition, with 1,2-PD Homogeneous phase mixing, the mol ratio of titanium isopropylate and 1,2-PD is 1:80;
B) add potassium hydroxide, the mol ratio of potassium hydroxide and titanium isopropylate is 2.02:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 200 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling isopropyl alcohol and water reacting and generate, reaction times is 4 hours, and after reaction terminates at temperature is 200 DEG C, reaction system pressure is under 0.7atm, in in 1min by the ethylene glycol evaporation in system completely, dibasic alcohol evaporation in system is obtained faint yellow solid completely, utilizes ethanol-Gossypol recrystallized from chloroform to obtain clear crystal three times to this solid, be i.e. obtained propylene glycol potassium titanate;
The structural formula of described alcoholysis catalysts propylene glycol potassium titanate is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts propylene glycol potassium titanate obtained above, the consumption of propylene glycol potassium titanate is 0.4% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with containing the polyester cotton fragment washing 65% and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 30:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 160 DEG C, and reaction system pressure is 2.5atm, and the reaction times is 8h;
3) in step 2) add containing quality of activated carbon mark in gained solution be 4% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 4 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 5 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 200 DEG C and pressure is 0.6atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid glycol ether carboxylate: by 1,6-hexanodioic acid, ethylene glycol, Polyethylene Glycol-600 three with etc. amount mixing, and the butyleneglycol metatitanic acid rubidium adding 150ppm is catalyzer, is 175 DEG C in temperature of reaction, pressure is carry out esterification 3.5h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid glycol ether carboxylate;
6) in mass ratio for 1:2 mixing step 4) and step 5) product that obtains, and add 10ppm germanium dioxide, 50ppm Germanium tetraacetate and 30pp antimony glycol as polycondensation catalyst and 200ppm ammonium phosphite as thermo-stabilizer, and at 210 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 235 DEG C, continue reaction 120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 180min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.65dl/g fusing point: 115.6 DEG C of colours: L:70.76, b:17.32
Embodiment 10
First carry out producing of butyleneglycol metatitanic acid rubidium, it comprises the following steps:
A) by metatitanic acid tetra-tert ester under 50 DEG C and nitrogen protection condition, with 1,3 butylene glycol Homogeneous phase mixing, metatitanic acid tetra-tert ester and 1,3 butyleneglycol mol ratios are 1:20;
B) add rubidium hydroxide, the mol ratio of rubidium hydroxide and metatitanic acid tetra-tert ester is 2.01:1, and continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 250 DEG C;
C) in reaction process, backflow 1,2-propylene glycol also gets rid of the lower boiling trimethyl carbinol and water that react and generate, and the reaction times is 5 hours, after reaction terminates at temperature is 210 DEG C, reaction system pressure is under 0.5atm, in in 5min by the 1,3 butylene glycol evaporation in system completely, the dibasic alcohol evaporation in system is obtained yellow solid completely, ethanol-Gossypol recrystallized from chloroform is utilized to obtain light yellow crystal three times to this solid, i.e. obtained butyleneglycol metatitanic acid rubidium;
The structural formula of described alcoholysis catalysts butyleneglycol metatitanic acid rubidium is:
Then carry out a kind of preparation method of recycled polyester, comprise the following steps:
1) be dissolved in depolymerizing agent ethylene glycol by alcoholysis catalysts butyleneglycol metatitanic acid rubidium obtained above, the consumption of butyleneglycol metatitanic acid rubidium is 0.2% of quality of glycol, forms depolymerization solution;
2) depolymerization solution mixed with PET polyester film and carry out the depolymerization reaction under protection of inert gas, stir simultaneously, stir speed (S.S.) is 600 turns/min, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 16:1, the molar mass of PET polyester calculates with 192g/mol, depolymerization reaction temperature is 240 DEG C, and reaction system pressure is 2atm, and the reaction times is 30min;
3) in step 2) add containing quality of activated carbon mark in gained solution be 0.9% ethylene glycol dispersion liquid, the add-on of gac ethylene glycol dispersion liquid is 0.5 times of depolymerization solution quality, at temperature is 200 DEG C, after atmospheric pressure reflux stirs decolouring 2h, remove the gac of impurity and decolouring after filtration, decolouring and filtration procedure carry out 2 times repeatedly;
4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured, under temperature is 210 DEG C and pressure is 0.8atm condition, by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring;
5) preparation of hexanodioic acid four contracting triethylene glycol carboxylate: by 1,6-hexanodioic acid, ethylene glycol, Macrogol 2000 three with etc. amount mixing, and adding the ethylene glycol potassium titanate catalyst of 100ppm, is 178 DEG C in temperature of reaction, pressure is carry out esterification 3.2h under 1atm, distillate the water generated in reaction process in time simultaneously, protect in reaction process with rare gas element, reaction terminates the preparation of rear acquisition hexanodioic acid four contracting triethylene glycol carboxylate;
6) in mass ratio for 5:4 mixing step 4) and step 5) product that obtains, 100ppm titanium ethylene glycolate, 50ppm titanium isopropylate, 20ppm antimonous oxide, 10ppm antimony glycol as polycondensation catalyst and 50ppm ammonium phosphite, 70ppm phosphoric acid, 80ppm phosphorous acid, 90ppm ortho phosphorous acid, 100ppm tetra-sodium, 200ppm triphenyl phosphite as thermo-stabilizer, and at 220 DEG C, pressure 1atm, is uniformly mixed under protection of inert gas condition; Then, temperature of reaction is increased to 240 DEG C, continue reaction 100min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa; Then, temperature of reaction is increased to 275 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 150min, namely obtain biodegradable recycled polyester.
The main performance index of gained biodegradable recycled polyester section obtains as follows according to GB/T 14190-2008 testing standard:
Limiting viscosity: 1.62dl/g fusing point: 100.7 DEG C of colours: L:75.32, b:11.39.
Claims (10)
1. a preparation method for biodegradable recycled polyester, is characterized in that, comprises the following steps:
1) ethylene glycol depolymerization is carried out to PET polyester:
1.1) alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is dissolved in depolymerizing agent ethylene glycol, forms depolymerization solution;
1.2) depolymerization solution is mixed with PET polyester and stirred carry out depolymerization reaction, the mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester is 4-50:1, and depolymerization reaction temperature is 160-240 DEG C, and reaction system pressure is 1-2.5atm, and the reaction times is 30min-8h;
The structural formula of described alcoholysis catalysts binary titanium alkoxide alkali metal coordination compound is:
Wherein, M
+being IA race metallic cation, is Li
+, Na
+, K
+or Rb
+;
R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4;
2) to decolouring and the purification of depolymerization product, step is as follows:
2.1) in step 1) to add containing quality of activated carbon mark in gained solution be the ethylene glycol dispersion liquid of 0.5-5%, at temperature is 150-220 DEG C, atmospheric pressure reflux stirs decolouring 1-5h;
2.2) then after filtration remove impurity and decolouring gac;
2.3) repeating step 2.1) and 2.2) 2-5 time, also namely decolouring and filtration procedure carry out 2-5 time repeatedly, obtain the ethylene glycol solution of the depolymerizing substance after removal of impurities decolouring;
2.4) ethylene glycol solution of the depolymerizing substance after removal of impurities being decoloured by the ethylene glycol evaporation in solution completely, obtains the depolymerization product of purifying and after decolouring under temperature is 190-210 DEG C and pressure is 0.5-0.8atm condition;
3) copolymerization of depolymerization product, concrete step is as follows:
3.1) preparation of modification by copolymerization carboxylate: by binary of fatty acids, ethylene glycol, polyethers three with etc. amount mixing, and to add a certain amount of titanium ethylene glycolate alkali metal complex be catalyzer, be 170-180 DEG C in temperature of reaction, pressure is stir under 1atm to carry out esterification 3-4h, distillates the water generated in reaction process in time simultaneously, protect with rare gas element in reaction process, reaction terminates rear acquisition aliphatic dibasic acid polyether ester compound;
3.2) by step 3.1) and step 2) the aliphatic dibasic acid polyether ester compound that obtains and purification and the depolymerization product after decolouring; polycondensation catalyst and thermo-stabilizer; be 1atm at 200-220 DEG C and pressure, under protection of inert gas, be uniformly mixed by certain mass ratio.
3.3) then, temperature of reaction is increased to 230-250 DEG C, continue reaction 60-120min, simultaneously this period, the system internal pressure of making at the uniform velocity is reduced to 1kPa.
3.4) then, temperature of reaction is increased to 265-290 DEG C, after the system internal pressure of making is reduced to 20Pa, continues reaction 120-180min, namely obtain biodegradable recycled polyester.
2. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, in described depolymerization solution, the consumption of described binary titanium alkoxide alkali metal coordination compound is the 0.1%-1% of quality of glycol; The molar mass of PET polyester calculates with 192g/mol; The preferred 8-20:1 of mol ratio of depolymerizing agent ethylene glycol consumption and PET polyester, the preferred 180-210 DEG C of depolymerization reaction temperature; Stir during described depolymerization reaction, stir speed (S.S.) is that 50-1500 turns/min; Described depolymerization reaction carries out under protection of inert gas.
3. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, described binary titanium alkoxide alkali metal coordination compound is obtained by following steps:
A) by general formula be Ti (OR)
4titanium compound under 50-150 DEG C and nitrogen protection condition, be dibasic alcohol the HO-R '-OH Homogeneous phase mixing of 2-4 with carbonatoms; Wherein, the saturated hydrocarbon chains structure of R to be carbonatoms be 2-4, R ' for carbonatoms be the saturated hydrocarbon chains structure of 2-4 or the saturated hydrocarbon chains structure containing diether linkage structure;
B) add IA race metal hydroxides MOH, continuing stirring until reaction system is after the liquid of transparent and homogeneous, raises temperature of reaction to 180-250 DEG C;
C) in reaction process, backflow dibasic alcohol also gets rid of the lower boiling monohydroxy-alcohol R-OH and water that react and generate, and the reaction times is 2-5 hour, and reaction terminates rear fast by complete for the dibasic alcohol evaporation in system, obtains white or micro-yellow solid;
D) utilized by above-mentioned solid ethanol-Gossypol recrystallized from chloroform repeatedly to obtain colourless or light yellow crystal and be described binary titanium alkoxide alkali metal coordination compound.
4. the preparation method of a kind of biodegradable recycled polyester according to claim 3, is characterized in that, Ti (OR)
4be 1:20-100 with the mol ratio of HO-R '-OH; MOH and Ti (OR)
4mol ratio be 2.01-2.05:1; Step c) in, describedly refer to that, at temperature is 190-210 DEG C, reaction system pressure is under 0.5-0.8atm fast, in 0.5-5min by dibasic alcohol evaporation in system completely.
5. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, described PET polyester is any type of goods made by polyethylene terephthalate and waste and old product by composition.
6. the preparation method of a kind of biodegradable recycled polyester according to claim 1, it is characterized in that, the decolouring of described depolymerization product and the step of purification, step 2.1) in, the add-on of the ethylene glycol solution containing gac is 0.5-5 times of depolymerizing substance ethylene glycol solution quality.
7. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, step 3.1) in, described binary of fatty acids is 1,6-hexanodioic acid, one or more in 1,10-sebacic acid; Described polyethers is molecular weight is 400-4000 polyoxyethylene glycol.
8. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, step 3.1) in, the add-on of described titanium ethylene glycolate alkali metal complex is 100-200ppm, and stir speed (S.S.) is 50-100rpm; Step 3.2) in, described certain mass of pressing is than mixing, and namely the mass ratio of depolymerization product and aliphatic dibasic acid polyether ester compound is 8:2-1:2.
9. the preparation method of a kind of biodegradable recycled polyester according to claim 1, it is characterized in that, step 3.2) in, described polycondensation catalyst is one or more in binary titanium alkoxide alkali metal coordination compound catalyzer, antimony glycol, antimony acetate, antimonous oxide, Germanium tetraacetate, germanium dioxide, titanium isopropylate, tetra-n-butyl titanate, titanium ethylene glycolate; The add-on of described polycondensation catalyst is the 0-200ppm of the depolymerization product quality after purifying and decolouring; Described thermo-stabilizer is one or more in trimethyl phosphite 99, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, primary ammonium phosphate, phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate; The add-on of described thermo-stabilizer is the 50ppm-500ppm of the depolymerization product quality after purifying and decolouring.
10. the preparation method of a kind of biodegradable recycled polyester according to claim 1, is characterized in that, step 3.1) in, be uniformly mixed and refer to that mixing speed is that 50-80 turns/min, be uniformly mixed 30-60min; Step 3.2) in, at the uniform velocity reduction pressure is 0.5kPa-10kPa/min to the air pressure changing down of 1kPa, and need during reaction to stir, mixing speed is that 50-80 turns/min; Step 3.3) in, continuing at the uniform velocity to reduce pressure to the air pressure changing down of 20Pa is 100Pa-1kPa/min, and continues when reacting to stir, and mixing speed is that 80-120 turns/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459635A (en) * | 2017-07-20 | 2017-12-12 | 东华大学 | A kind of biodegradable recycled polyester and preparation method thereof |
| WO2018018107A1 (en) * | 2016-07-28 | 2018-02-01 | Figueiró Alexandre De Andrade | Process for manufacturing and decorating a laminate floor based on the use of recycled polyethylene terephthalate, and the product obtained |
| CN112646135A (en) * | 2020-12-10 | 2021-04-13 | 北京服装学院 | Method for continuously preparing spinnable colorless regenerated polyester from colored waste polyester textiles |
| CN112708947A (en) * | 2020-12-14 | 2021-04-27 | 浙江理工大学 | Preparation method of self-crimping fiber with recycled polyester as raw material |
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| CN114031756A (en) * | 2021-10-13 | 2022-02-11 | 国高材高分子材料产业创新中心有限公司 | Method for preparing recycled polyester by closed-loop recycling waste polyester with typical green low-carbon characteristics |
| WO2023231524A1 (en) * | 2022-06-02 | 2023-12-07 | 四川大学 | Catalyst for polyester depolymerization or cyclic ester synthesis, preparation method therefor and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584594A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Method for catalyzing alcoholysis performed on polyethylene glycol terephthalate (PET) by using CoCl42-/NiCl42-type ionic liquid |
| CN102731310A (en) * | 2011-04-12 | 2012-10-17 | 中国科学院过程工程研究所 | Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid |
| CN103436990A (en) * | 2013-08-16 | 2013-12-11 | 盛虹集团有限公司 | Recycled polyester sea-island fiber and preparation method thereof |
| CN103965509A (en) * | 2014-04-29 | 2014-08-06 | 江南大学 | Method for recycling and utilizing waste liquid generated in degrading polyester using glycol |
-
2014
- 2014-11-03 CN CN201410609018.1A patent/CN104327260B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584594A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Method for catalyzing alcoholysis performed on polyethylene glycol terephthalate (PET) by using CoCl42-/NiCl42-type ionic liquid |
| CN102731310A (en) * | 2011-04-12 | 2012-10-17 | 中国科学院过程工程研究所 | Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid |
| CN103436990A (en) * | 2013-08-16 | 2013-12-11 | 盛虹集团有限公司 | Recycled polyester sea-island fiber and preparation method thereof |
| CN103965509A (en) * | 2014-04-29 | 2014-08-06 | 江南大学 | Method for recycling and utilizing waste liquid generated in degrading polyester using glycol |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018018107A1 (en) * | 2016-07-28 | 2018-02-01 | Figueiró Alexandre De Andrade | Process for manufacturing and decorating a laminate floor based on the use of recycled polyethylene terephthalate, and the product obtained |
| CN107459635A (en) * | 2017-07-20 | 2017-12-12 | 东华大学 | A kind of biodegradable recycled polyester and preparation method thereof |
| CN112646135A (en) * | 2020-12-10 | 2021-04-13 | 北京服装学院 | Method for continuously preparing spinnable colorless regenerated polyester from colored waste polyester textiles |
| CN112708947A (en) * | 2020-12-14 | 2021-04-27 | 浙江理工大学 | Preparation method of self-crimping fiber with recycled polyester as raw material |
| CN113150375A (en) * | 2021-03-29 | 2021-07-23 | 中国科学院青岛生物能源与过程研究所 | Method for recycling polylactic acid material under catalysis of zinc catalyst |
| CN114031756A (en) * | 2021-10-13 | 2022-02-11 | 国高材高分子材料产业创新中心有限公司 | Method for preparing recycled polyester by closed-loop recycling waste polyester with typical green low-carbon characteristics |
| CN114031756B (en) * | 2021-10-13 | 2022-08-26 | 国高材高分子材料产业创新中心有限公司 | Method for preparing recycled polyester by closed-loop recycling waste polyester with typical green low-carbon characteristics |
| WO2023060768A1 (en) | 2021-10-13 | 2023-04-20 | 国高材高分子材料产业创新中心有限公司 | Method for preparing regenerated polyester by means of closed-loop recovery of waste polyester with typical green and low-carbon characteristics |
| WO2023231524A1 (en) * | 2022-06-02 | 2023-12-07 | 四川大学 | Catalyst for polyester depolymerization or cyclic ester synthesis, preparation method therefor and use thereof |
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Denomination of invention: A method for preparing biodegradable regenerated polyester Effective date of registration: 20231213 Granted publication date: 20160406 Pledgee: China Construction Bank Shuyang sub branch Pledgor: Keze New Materials Co.,Ltd. Registration number: Y2023980070909 |