CN102140165B - Biodegradable copolyester and preparation method thereof - Google Patents
Biodegradable copolyester and preparation method thereof Download PDFInfo
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- CN102140165B CN102140165B CN 201019114006 CN201019114006A CN102140165B CN 102140165 B CN102140165 B CN 102140165B CN 201019114006 CN201019114006 CN 201019114006 CN 201019114006 A CN201019114006 A CN 201019114006A CN 102140165 B CN102140165 B CN 102140165B
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 100
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 84
- -1 phosphorus compound Chemical class 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 11
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 34
- 230000032050 esterification Effects 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 10
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-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
- 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 5
- 238000000034 method Methods 0.000 claims description 5
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 229920000562 Poly(ethylene adipate) Polymers 0.000 claims description 3
- 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 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 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 claims description 3
- 239000002002 slurry Substances 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
- 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 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-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
- 239000002994 raw material Substances 0.000 abstract description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 12
- 235000011037 adipic acid Nutrition 0.000 abstract 6
- 239000001361 adipic acid Substances 0.000 abstract 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 11
- 229920001707 polybutylene terephthalate Polymers 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DMCTVRQBJMBEDT-UHFFFAOYSA-N phenol;1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl.OC1=CC=CC=C1 DMCTVRQBJMBEDT-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
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Abstract
The invention relates to a biodegradable copolyester and a preparation method thereof; carrying out esterification reaction on purified terephthalic acid, adipic acid, 1, 4-butanediol and ethylene glycol at the temperature of 150-220 ℃ under normal pressure, wherein the molar ratio of the purified terephthalic acid to the adipic acid is 3: 7-8: 2; the molar ratio of the ethylene glycol to the 1, 4-butanediol is 1: 9-9: 1, and the ratio of the total molar number of the purified terephthalic acid and the adipic acid to the total molar number of the ethylene glycol and the 1, 4-butanediol is 1: 1.0-1.8; performing polycondensation reaction at 10-150 Pa to obtain copolyester, wherein the addition amount of the titanium compound is 200-1200 ppm of the total weight of terephthalic acid and adipic acid; the adding amount of the antimony compound is 100-600 ppm of the total weight of the terephthalic acid and the adipic acid; the adding amount of the phosphorus compound is 50-400 ppm of the total weight of the terephthalic acid and the adipic acid; the raw material price is low, the reaction temperature is low, the pressure is low, and the product intrinsic viscosity is high.
Description
Technical field:
The present invention relates to a kind of biodegradable fat/aromatic copolyester and preparation method thereof, relate in more detail aromatic binary carboxylic acid, aliphatic dicarboxylic acid and aliphatic dihydroxy alcohol direct esterification and copolycondensation and prepare biodegradable fat/aromatic copolyester and preparation method thereof.
Background technology:
Aliphatic polyester is a kind of polymkeric substance of totally biodegradable, and it can be decomposed into the mineralising inorganic salt of carbonic acid gas, water and contained element thereof and new biomass under microbial process.At present, there have been many kinds to enter batch production or suitability for industrialized production.But this material cost is high, and product price is high, the bottleneck that these have all become the restriction aliphatic polyester to further develop.Thermoplasticity aromatic polyester thermal characteristics is stable, good mechanical performance, be convenient to processing, cheap, since industrialization, has developed into the broad-spectrum resin of a class.But the aromatic polyester biological degradability is very poor, can not use as degradable material separately.Therefore the aliphatic-aromatic copolyester (CPEs) that obtains in conjunction with the degradation characteristic of the excellence use of aromatic polyester and processing characteristics and aliphatic polyester is the focus of current degradable material development.
The US Patent No. 5889135 of Germany BASF AG discloses a kind of fat/aromatic copolyester, it is with aliphatic acid and 1,4-butyleneglycol (1,4-BD) under the effect of tin compound, carry out esterification, and then with dimethyl terephthalate (DMT) (DMT) and 1, (Isosorbide-5-Nitrae-BD) carry out transesterification reaction under the titanium compound effect, esterification and ester exchange offspring carry out copolycondensation to the 4-butyleneglycol together.The Chinese patent CN101016373A of University Of Nanchang has reported the method for aromatic polyester and aliphatic polyester synthesizing degradable copolyester by reactively blending, and it is to utilize existing aromatic polyester and aliphatic polyester to generate degradable aliphatic/aromatic copolyester by melting state transesterification reaction.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of composite catalyst catalyzes and synthesizes biodegradable polybutylene terephthalate/adipate butanediol/terephthalate/adipate glycol copolyesters (PBATE), adopt this kind composite catalyst that esterification is carried out under the cold condition of normal pressure and 150～220 ℃, polymerization reaction time shortens, and polymerization obtain polybutylene terephthalate/adipate butanediol/terephthalate/adipate glycol copolyesters (PBATE) limiting viscosity is high.
Biodegradable polybutylene terephthalate/adipate butanediol/terephthalate provided by the invention/adipate glycol copolyesters (PBATE), to be arranged with line style random copolymerization by mutual-phenenyl two acid bromide two alcohol ester, tetramethylene adipate, ethylene glycol terephthalate and ethylene glycol adipate(EGA) to consist of, the molecular fraction of each composition respectively is 28～78%, 8～58%, 2～42%, 4～45%, the limiting viscosity of this copolyesters is 0.7～1.6dL/g, 90～150 ℃ of fusing points.
Biodegradable polybutylene terephthalate/adipate butanediol/terephthalate provided by the invention/the limiting viscosity of adipate glycol copolyesters (PBATE) is to make molten Ji with phenol tetrachloroethane, uses dark type viscometer 25 ℃ of lower detections of temperature; Each composition is to be solvent by deuterochloroform, characterizes again combination with Brucker AV 300 type nuclear magnetic resonance analyser measured results
1The HNMR spectrum can obtain the molar content of Related Component in the material.
The present invention catalyzes and synthesizes polybutylene terephthalate/adipate butanediol/terephthalate/adipate glycol copolymerization (PBATE) take titanium compound and antimony compounds as composite catalyst, and method may further comprise the steps:
(1) esterification
With pure terephthalic acid (PTA), hexanodioic acid (AA), 1,4-butyleneglycol (1,4-BD) and ethylene glycol (EG) directly adds or the mode that is prepared into slurry joins in the reactor together, under normal pressure, carry out esterification under 150～220 ℃ of temperature, deviate from water byproduct, generate mutual-phenenyl two acid bromide two alcohol ester, tetramethylene adipate, ethylene glycol terephthalate, ethylene glycol adipate(EGA) and oligopolymer thereof, when total esterification yield 〉=95%, esterification finishes; Pure terephthalic acid (PTA) is 3: 7～8: 2 with the mol ratio of hexanodioic acid (AA); Ethylene glycol (EG) and 1,4-butyleneglycol (1, mol ratio 4-BD) is 1: 9～9: 1, total mole number and the ethylene glycol (EG) and 1 of pure terephthalic acid (PTA) and hexanodioic acid (AA), (ratio of the total mole number of Isosorbide-5-Nitrae-BD) is 1: 1.0～1.8 to the 4-butyleneglycol.
(2) polycondensation
Reactor was decompressed to 10～150Pa in 60 minutes, constantly distillate by product 1 in the process, 4-butyleneglycol and ethylene glycol, the reaction final temperature is controlled at 265～280 ℃, then make reactor return to normal pressure with rare gas element, obtain polymer melt, polymer melt is carried out the Cast Strip pelletizing, obtain limiting viscosity in polybutylene terephthalate/adipate butanediol/terephthalate of 0.7～1.6dL/g/adipate glycol copolyesters (PBATE) section, 60～120 minutes vacuum polycondensation time.
When step (1) reinforced or add the composite catalyst of titanium compound and antimony compounds before the decompression operation of step (2), before the decompression operation of step (2), add phosphorus compound; Described composite catalyst adds in step (1) partly or entirely, the surplus of adding step (1) part or whole in step (2).
The add-on of described titanium compound is that being preferably 300～1000ppm is benchmark take the content of titanium compound in terephthalic acid (PTA) and hexanodioic acid (AA) gross weight as 200～1200ppm.
The add-on of described antimony compounds is that being preferably 150～400ppm is benchmark take the content of antimony compounds in terephthalic acid (PTA) and hexanodioic acid (AA) gross weight as 100～600ppm.
The add-on of described phosphorus compound is that being preferably 200～300ppm is benchmark take the content of phosphorus compound in terephthalic acid (PTA) and hexanodioic acid (AA) gross weight as 50～400ppm.
Described titanium compound is titanium ethylene glycolate, metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate.
Described antimony compounds is antimony acetate, antimonous oxide or antimony glycol.
Described phosphorus compound is trimethyl phosphite 99, triethyl phosphate, triphenylphosphate, triphenyl phosphite, phosphorous acid or phosphoric acid.
The present invention is take terephthalic acid (PTA), hexanodioic acid (AA), ethylene glycol (EG) and BDO (Isosorbide-5-Nitrae-BD) as basic raw material, prepared the high PBATE product of limiting viscosity.The raw material that main innovate point of the present invention is to use market to be easy to get and price is low is as the raw material of biodegradable copolyesters, the PBATE product performance viscosity of preparing by building-up reactions is high, and a kind of novel composite catalyst is used for PBATE synthetic esterification and polycondensation, thereby esterification is carried out under normal pressure, and esterification reaction temperature is lower, synthesising reacting time is shortened simultaneously, and speed of response is improved.Meanwhile, compare with traditional catalyzer metatitanic acid four butyl esters, catalytic activity is high, has overcome the shortcoming that esterification generally can not be carried out under normal pressure.
Description of drawings
The copolyether ester that Fig. 1 is corresponding with table 1 molecular structure
1H-NMR.
Embodiment
The following examples are to set forth rather than limit category of the present invention.Except as otherwise noted, all umber and percentage ratio all are that gross weight take PTA and AA is as benchmark among the embodiment.
Embodiment 1:
In a 5L stainless steel cauldron that the outlet of nitrogen inlet, condensation product and agitator be housed, add 820g pure terephthalic acid (PTA), 180g hexanodioic acid (AA), 525g1,4-butyleneglycol (1,4-BD) with 40g ethylene glycol (EG), 0.2g tetrabutyl titanate (200ppm that is equivalent to PTA and AA gross weight), 0.6g antimony acetate (600ppm that is equivalent to PTA and AA gross weight).Keep normal pressure in the still, constant speed stirs, and begins to deviate from water during temperature rise to 150 ℃ in the reactor, continue to heat up and the control reactor in temperature be not higher than 220 ℃, when the amount that distillates water byproduct in the question response still reached theoretical aquifer yield, esterification finished.Continuation adds 0.05g trimethyl phosphite 99 (50ppm that is equivalent to PTA and AA gross weight) in still, vacuumize, pressure in the polymeric kettle was reduced to below the 150Pa in 60 minutes, reaction is 85 minutes under this pressure, the reaction final temperature is controlled at 280 ℃, then make reactive system return to normal pressure with nitrogen, polymer melt obtains white polybutylene terephthalate/adipate butanediol/terephthalate/adipate glycol copolyesters (PBATE) section after Cast Strip and pelletizing.Limiting viscosity is 0.823dl/g, 150 ℃ of fusing points.
Embodiment 2:
In a 5L stainless steel cauldron that the outlet of nitrogen inlet, condensation product and agitator be housed, add 630g pure terephthalic acid (PTA), 370g hexanodioic acid (AA), 549g1,4-butyleneglycol (1,4-BD) with 94g ethylene glycol (EG), 0.2g metatitanic acid orthocarbonate or titanium isopropylate (200ppm that is equivalent to PTA and AA gross weight) and 0.3g antimonous oxide (300ppm that is equivalent to PTA and AA gross weight).Keep normal pressure in the still, constant speed stirs, and begins to deviate from water during temperature rise to 150 ℃ in the reactor, continue to heat up and the control reactor in temperature be not higher than 220 ℃, when the amount that distillates water byproduct in the question response still reached theoretical aquifer yield, esterification finished.Continuation adds 0.3g metatitanic acid orthocarbonate (300ppm that is equivalent to PTA and AA gross weight) in still, 0.1g antimonous oxide (100ppm that is equivalent to PTA and AA gross weight) and 0.15g triethyl phosphate (150ppm that is equivalent to PTA and AA gross weight), vacuumize, pressure in the polymeric kettle was reduced to below the 150Pa in 60 minutes, reaction is 65 minutes under this pressure, the reaction final temperature is controlled at 275 ℃, then make reactive system return to normal pressure with nitrogen, polymer melt obtains white after Cast Strip and pelletizing limiting viscosity is 0.723dl/g, polybutylene terephthalate/adipate butanediol/terephthalate that fusing point is 90 ℃/adipate glycol copolyesters (PBATE) section.
Embodiment 3:
In a 5L stainless steel cauldron that the outlet of nitrogen inlet, condensation product and agitator be housed, add 333g pure terephthalic acid (PTA), 468g hexanodioic acid (AA), 322g1,4-butyleneglycol (1,4-BD) with 40g ethylene glycol (EG), 0.3g metatitanic acid tetramethyl ester (300ppm that is equivalent to PTA and AA gross weight) and 0.3g antimony glycol (300ppm that is equivalent to PTA and AA gross weight).Keep normal pressure in the still, constant speed stirs, and begins to deviate from water during temperature rise to 150 ℃ in the reactor, continue to heat up and the control reactor in temperature be not higher than 220 ℃, when the amount that distillates water byproduct in the question response still reached theoretical aquifer yield, esterification finished.Continuation adds 0.5g metatitanic acid tetramethyl ester (500ppm that is equivalent to PTA and AA gross weight) and 0.2g triphenylphosphate or triphenyl phosphite (200ppm that is equivalent to PTA and AA gross weight) in still, vacuumize, pressure in the polymeric kettle was reduced to below the 150Pa in 60 minutes, reaction is 90 minutes under this pressure, the reaction final temperature is controlled at 272 ℃, then make reactive system return to normal pressure with nitrogen, polymer melt obtains white after Cast Strip and pelletizing limiting viscosity is 0.924dl/g, polybutylene terephthalate/adipate butanediol/terephthalate that fusing point is 132 ℃/adipate glycol copolyesters (PBATE) section.
Embodiment 4:
In a 5L stainless steel cauldron that the outlet of nitrogen inlet, condensation product and agitator be housed, add 431g pure terephthalic acid (PTA), 569g hexanodioic acid (AA), 281g1,4-butyleneglycol (1,4-BD) with 258g ethylene glycol (EG), add the composite catalyst slurries of 58.8g preparation, wherein contain the tetraethyl titanate of the 1000ppm that is equivalent to PTA and AA gross weight and the antimony acetate of 200ppm.Keep normal pressure in the still, constant speed stirs, and begins to deviate from water during temperature rise to 150 ℃ in the reactor, continue to heat up and the control reactor in temperature be not higher than 220 ℃, when the amount that distillates water byproduct in the question response still reached theoretical aquifer yield, esterification finished.Continuation adds 0.3g phosphorous acid (300ppm that is equivalent to PTA and AA gross weight) in still, vacuumize, pressure in the polymeric kettle was reduced to below the 150Pa in 60 minutes, reaction is 100 minutes under this pressure, the reaction final temperature is controlled at 270 ℃, then make reactive system return to normal pressure with nitrogen, polymer melt obtains white after Cast Strip and pelletizing limiting viscosity is 1.242dl/g, polybutylene terephthalate/adipate butanediol/terephthalate that fusing point is 120 ℃/adipate glycol copolyesters (PBATE) section.
Embodiment 5:
In a 5L stainless steel cauldron that the outlet of nitrogen inlet, condensation product and agitator be housed, add 328g pure terephthalic acid (PTA), 672g hexanodioic acid (AA) and 1069g1,4-butyleneglycol (1,4-BD), 1.2g titanium ethylene glycolate (1200ppm that is equivalent to PTA and AA gross weight), 0.1g antimony acetate (100ppm that is equivalent to PTA and AA gross weight).Keep normal pressure in the still, constant speed stirs, and begins to deviate from water during temperature rise to 150 ℃ in the reactor, continue to heat up and the control reactor in temperature be not higher than 220 ℃, when the amount that distillates water byproduct in the question response still reached theoretical aquifer yield, esterification finished.Continuation adds the phosphoric acid of 0.4g (400ppm that is equivalent to PTA and AA gross weight) in the still, vacuumize, pressure in the polymeric kettle was reduced to below the 150Pa in 60 minutes, reaction is 120 minutes under this pressure, the reaction final temperature is controlled at 265 ℃, then make reactive system return to normal pressure with nitrogen, polymer melt obtains white after Cast Strip and pelletizing limiting viscosity is 1.565dl/g, polybutylene terephthalate/adipate butanediol/terephthalate that fusing point is 118 ℃/adipate glycol copolyesters (PBATE) section.
The copolyether ester that Fig. 1 is corresponding with table 1 molecular structural formula
1H-NMR.
Table 1 molecular structural formula table
Claims (7)
1. the preparation method of a biodegradable copolyesters is characterized in that:
(1) esterification
With pure terephthalic acid, hexanodioic acid, 1,4-butyleneglycol and ethylene glycol directly add or are prepared into slurry and joins together in the reactor, under normal pressure, carry out esterification under 150～220 ℃ of temperature, deviate from water byproduct, generate mutual-phenenyl two acid bromide two alcohol ester, tetramethylene adipate, ethylene glycol terephthalate, ethylene glycol adipate(EGA) and oligopolymer thereof, when total esterification yield 〉=95%, esterification finishes; The mol ratio of pure terephthalic acid and hexanodioic acid is 3:7～8:2; The mol ratio of ethylene glycol and BDO is 1:9～9:1, and the total mole number of pure terephthalic acid and hexanodioic acid is 1:1.0～1.8 with the ratio of the total mole number of ethylene glycol and BDO;
(2) polycondensation
Reactor was decompressed to 10～150Pa in 60 minutes, constantly distillate by product 1 in the process, 4-butyleneglycol and ethylene glycol, the reaction final temperature is controlled at 265～280 ℃, then make reactor return to normal pressure with rare gas element, obtain polymer melt, polymer melt is carried out the Cast Strip pelletizing, obtain limiting viscosity at the polymer chips of 0.7～1.6dL/g, 60～120 minutes vacuum polycondensation time;
When step (1) reinforced, add the composite catalyst of titanium compound and antimony compounds, before the decompression operation of step (2), add phosphorus compound; Described composite catalyst adds in step (1) all;
The add-on of described titanium compound is 200～1200ppm of terephthalic acid and hexanodioic acid gross weight;
The add-on of described antimony compounds is 100～600ppm of terephthalic acid and hexanodioic acid gross weight;
The add-on of described phosphorus compound is 50～400ppm of terephthalic acid and hexanodioic acid gross weight.
2. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: the add-on of described titanium compound is 300～1000ppm of terephthalic acid and hexanodioic acid gross weight.
3. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: the add-on of described antimony compounds is 150～400ppm of terephthalic acid and hexanodioic acid gross weight.
4. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: the add-on of described phosphorus compound is 200～300ppm of terephthalic acid and hexanodioic acid gross weight.
5. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: described titanium compound is titanium ethylene glycolate, metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate.
6. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: described antimony compounds is antimony acetate, antimonous oxide or antimony glycol.
7. the preparation method of biodegradable copolyesters according to claim 1, it is characterized in that: described phosphorus compound is trimethyl phosphite 99, triethyl phosphate, triphenylphosphate, triphenyl phosphite, phosphorous acid or phosphoric acid.
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| WO2016108768A1 (en) * | 2014-12-30 | 2016-07-07 | Ptt Global Chemical Public Company Limited | Biodegradable copolyester composition |
| CN106400177B (en) * | 2016-08-31 | 2019-03-05 | 浙江聚兴化纤有限公司 | A kind of manufacturing method of comfort copolyester fiber |
| CN109251537A (en) * | 2018-08-29 | 2019-01-22 | 佛山市禅城区诺高环保科技有限公司 | A kind of environment-friendlyplasticizer plasticizer |
| CN109762143A (en) * | 2019-01-29 | 2019-05-17 | 中国科学院理化技术研究所 | Hydrolyzable copolyesters and its preparation method and application |
| CN114479030B (en) * | 2020-11-11 | 2024-03-26 | 中国石油化工股份有限公司 | PBT copolyester with high glass transition temperature and low melting point and application thereof |
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| CN1377380A (en) * | 1999-08-06 | 2002-10-30 | 伊斯曼化学公司 | Polyesters having a controlled melting point and fibers formed therefrom |
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| JP2008001855A (en) * | 2006-06-26 | 2008-01-10 | Toyobo Co Ltd | Polyester and use thereof |
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| CN1377380A (en) * | 1999-08-06 | 2002-10-30 | 伊斯曼化学公司 | Polyesters having a controlled melting point and fibers formed therefrom |
| US6713595B2 (en) * | 1999-12-11 | 2004-03-30 | Ire Chemical Ltd. | Copolyester resin composition and a process of preparation thereof |
| JP2008001855A (en) * | 2006-06-26 | 2008-01-10 | Toyobo Co Ltd | Polyester and use thereof |
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