CN102140165B - Biodegradable copolyester and preparation method thereof - Google Patents

Biodegradable copolyester and preparation method thereof Download PDF

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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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terephthalic acid
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ethylene glycol
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CN102140165A (en
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史君
王晓慧
陈颖
李连斌
付志峰
李振忠
吴佩华
胡亚文
邹妍
温国防
刘智全
刘冬
李彦钧
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Petrochina Co Ltd
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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

A kind of biodegradable copolyesters and preparation method thereof
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
Figure GSA00000019331900081

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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CN103087305B (en) * 2011-11-07 2015-11-18 上海杰事杰新材料(集团)股份有限公司 A kind of Biodegradable aromatic-aliphatic copolyester and preparation method thereof
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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