CN102190782B - A kind of copolyester compound and preparation method - Google Patents
A kind of copolyester compound and preparation method Download PDFInfo
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- CN102190782B CN102190782B CN201010148857.XA CN201010148857A CN102190782B CN 102190782 B CN102190782 B CN 102190782B CN 201010148857 A CN201010148857 A CN 201010148857A CN 102190782 B CN102190782 B CN 102190782B
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Abstract
The invention provides a kind of copolyester compound and preparation method thereof, this copolyester compound is formed by the glycol of biogenetic derivation, the diacid of biogenetic derivation and aromatic diacid copolymerization, its fusing point Tm >=220 DEG C.This copolyesters chemical combination be the diacid of aromatic diacid and biogenetic derivation is carried out with the glycol of biogenetic derivation respectively esterification again polycondensation synthesize.This copolyester compound fusing point is high, applied range.
Description
Technical field
The invention belongs to polymeric material field, particularly relate to a kind of copolyesters of biogenetic derivation raw material.
Background technology
Polyester is as a base polymer, be used widely, its Application Areas is very wide, in recent years since, along with going from bad to worse of environment for human survival, people more and more pay close attention to development environment friendly material and use renewable starting material, oil is as Nonrenewable resources, along with a large amount of use is fewer and feweri, how substituting and to reduce use oil as starting material, is that people face one of important research problem.
Patent CN200810018622.1 provides a kind of method preparing half biogenetic derivation polyester, its acid starting material terephthalic acid or dimethyl terephthalate (DMT) are petroleum resources, its raw polyol ethylene glycol is biogenetic derivation, the performance of the polyethylene terephthalate of preparation and the polyethylene terephthalate of complete petroleum resources is very nearly the same, but it is 30% weight is biogenetic derivation, all the other 70% are petroleum resources, and biogenetic derivation composition proportion is lower.
Patent US200910124763 provides a kind of method preparing complete biogenetic derivation polyester, and its acid starting material FDCA or FDCA dimethyl ester are prepared by biology, and its raw polyol ethylene glycol, propylene glycol or butyleneglycol are by biogenetic derivation.But a fly in the ointment is that its fusing point is lower, thus limits its use range.
Summary of the invention
The object of the present invention is to provide the copolyester compound that a kind of biogenetic derivation raw material proportion is higher, and this copolyester compound fusing point is high, applied range.
Copolyester compound of the present invention is formed by the glycol of biogenetic derivation, the diacid of biogenetic derivation and aromatic diacid copolymerization, its fusing point Tm >=220 DEG C; The general structure of this copolyester compound is as follows, and wherein B is the biological diol structure unit of dehydrogenation, and A is the aromatic diacid structural unit of dehydroxylation, and x is the integer of 50 ~ 200.
The ethylene glycol of the preferred biogenetic derivation of glycol of said biogenetic derivation, the 1,3-PD of biogenetic derivation or the BDO of biogenetic derivation.Carbon source in biomaterial is transferred in dibasic alcohol by the preparation method of biogenetic derivation glycol.Farm crop are a kind of renewable resourcess, can by the CO in air
2pass through photosynthesis, be converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. to store in farm crop fruit and stalk thereof, the present invention utilizes the stalk of corn, wheat, sugarcane and farm crop, obtains the raw material dibasic alcohol of polyester through biological fermentation and/or the chemical industry course of processing.Biomaterial of the present invention is the stalk of corn, sugarcane, wheat and farm crop.Dibasic alcohol is obtained through biological and/or chemical process.The biomaterial used is the stalk of corn, sugarcane, wheat and farm crop.Butyleneglycol is obtained through biological and/or chemical process.Such as corn is through bioprocess separating starch, and obtain the sugar of 5 carbon and 6 carbon through processing, these sugars can prepare multicomponent binary alcohol through the technique of hydrogenation catalyst, after purifies and separates general procedure, just can obtain raw material dibasic alcohol of the present invention.
The FDCA of the preferred biogenetic derivation of diacid of said biogenetic derivation or the FDCA dimethyl ester of biogenetic derivation.Described FDCA or FDCA dimethyl ester are originated by biomass cellulose and are obtained.By Mierocrystalline cellulose first obtained fructose, fructose Dehydration obtains hydroxymethylfurfural (HMF), and hydroxymethylfurfural obtains furandicarboxylic acid through reaction process such as peroxidation, is prepared into FDCA dimethyl ester by furandicarboxylic acid.The preferred terephthalic acid of said aromatic diacid, dimethyl terephthalate (DMT), NDA or NDA dimethyl ester.
During copolymerization, the mol ratio of the diacid of aromatic diacid and biogenetic derivation is preferably 1: 0.05 ~ 1: 20.
During copolymerization, the mol ratio of the total mole number of the diacid of aromatic diacid and biogenetic derivation and the glycol of biogenetic derivation is preferably 1: 1 ~ 1: 8.
The preparation method of copolyester compound of the present invention, specifically comprise Esterification Stage and polymerization stage, first the glycol of aromatic diacid and biogenetic derivation is carried out esterification, obtain the first prepolymer, again the glycol of the diacid of biogenetic derivation and biogenetic derivation is carried out esterification, obtain the second prepolymer, then the first prepolymer and the second prepolymer are carried out polycondensation and obtain copolyester compound; Esterification reaction temperature is 140 ~ 230 DEG C; Polycondensation temperature is 210 ~ 280 DEG C.
Esterification reaction temperature is preferably 150 ~ 170 DEG C.In esterification reaction process, aromatic diacid and furandicarboxylic acid stir respectively while slowly heat together with glycol, catalyzer or catalyst mixture, the terminal of esterification is that reaction mixture becomes transparent, and the reaction mixture in this period is small molecules prepolymer.The preferred 230-260 DEG C of polymeric reaction temperature, polycondensation process preferably carries out under vacuo, owing to having the by product glycol of generation in polycondensation reaction system, removes the speed of response that by product improves polycondensation under vacuo.
In the preparation method of copolyester compound of the present invention, aromatic diacid is preferably terephthalic acid, dimethyl terephthalate (DMT), 2,6-naphthalic acid or 2,6-naphthalene diformic acid dimethyl ester, the diacid of biogenetic derivation is preferably FDCA or 2,5-furandicarboxylic acid dimethyl ester, during copolymerization, the mol ratio of the diacid of aromatic diacid and biogenetic derivation is preferably 1: 0.05 ~ 1: 20, and within the scope of this, reaction is comparatively steady and the time of having reacted required is shorter.The mol ratio of the total mole number of the diacid of aromatic diacid and biogenetic derivation and the glycol of biogenetic derivation is preferably 1: 1 ~ 1: 8, and within the scope of this, reaction is comparatively steady and the time of having reacted required is shorter.
In the preparation method of copolyester compound of the present invention, catalyzer is described.When diacid and glycol synthetic macromolecular compound, even if also can react because the self-catalysis of diacid does not add catalyzer.But as the diacid of reactant, its concentration along with the carrying out of reaction can step-down gradually, catalytic effect is deteriorated, and therefore adds catalyzer better.Catalyzer in esterification reaction process can be the organometallic compound such as metal acid compound and salt, tin, zinc, titanium, catalyzer in polycondensation process can be acetate, the carbonate of zinc, manganese, magnesium etc., or the organometallic compounds such as the metal oxide of zinc, manganese, magnesium etc. and tin, zinc, titanium, but be combined esterification and the preferred titanium compound of polycondensation, catalyzer of the present invention is titanium compound.Concrete be enumerated as tetrabutyl titanate, sec.-propyl titanic acid ester, propyl titanate or propenyl titanic acid ester.
Stablizer phosphorus compound is also used in the present invention, can be trivalent or phosphoric organic compound and inorganic phosphorous compound, that can simply enumerate has trimethyl phosphite 99, triphenylphosphate, phosphoric acid etc., can be the commercially available trivalent of phosphorus system and the antioxidant of pentavalent, as commercially available PEP36, AP1500, AX-71.Do not enumerate more specifically at this.
Except using above-described catalyzer and stablizer in the present invention, nano titanium oxide can also be added, its particle diameter of nano titanium oxide is that 20-40nm. adds 0.05-1%, the titanium dioxide of preferable particle size 20 nanometer, addition 0.1%, appropriate titanium dioxide add the effect that can reach delustring.
The present invention can also add the weighting material that other can not reduce polyester property, and as polynite, mica etc., do not enumerate more specifically at this, appropriate polynite or mica add the thermal change type temperature that can improve polymkeric substance, expand its range of application.The glycol of biogenetic derivation, the diacid of biogenetic derivation and aromatic diacid copolymerization are prepared copolyester compound by the present invention, its fusing point is made to keep higher on the one hand, itself and PBT, PTT is made to have similar fusing point, expand its range of application, make biogenetic derivation composition proportion in copolyesters higher as far as possible on the other hand, namely improve its bioid degree.
The following describes fusing point test method of the present invention and evaluation method.
DSC tests:
Constant temperature 3 minutes after differential scan calorimeter DSC (TA, Q100) is warmed up to 280 DEG C from 40 DEG C with 16 DEG C/min, eliminates thermal history; Then rapid cool to room temperature, then constant temperature 3 minutes after being warmed up to 280 DEG C from 40 DEG C with 16 DEG C/min, then cool to 40 DEG C with 16 DEG C/min, terminate.Second time obtains second-order transition temperature in heating up and is designated as Tg, and cold crystallization temperature Tcc and melt temperature are fusing point Tm.
Embodiment
Further illustrate the present invention by following examples, the concrete numerical value of each embodiment and comparative example is in table one.
Embodiment 1
At the temperature of 250 DEG C, the biogenetic derivation ethylene glycol (great achievement group product) of the terephthalic acid of 166 weight parts and 75 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
Be to weigh the first prepolymer and the second prepolymer at 5: 95 to calculate furandicarboxylic acid group and terephthalic acid group ratio in product copolyester compound, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 DEG C through 1.5 hours, and when described reaction completes, the temperature in flask is 290 DEG C, and resulting pressure is about 130Pa, obtains copolyester compound, and its structural formula is as follows:
Embodiment 2
At the temperature of 250 DEG C, the biogenetic derivation ethylene glycol (great achievement group product) of the terephthalic acid of 166 weight parts and 75 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
Be to weigh the first prepolymer and the second prepolymer at 8: 92 to calculate furandicarboxylic acid group and terephthalic acid group ratio in product copolyester compound, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 DEG C through 1.5 hours, and when described reaction completes, the temperature in flask is 290 DEG C, resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 3
At the temperature of 250 DEG C, the biogenetic derivation ethylene glycol (great achievement group product) of the terephthalic acid of 166 weight parts and 75 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
Be to weigh the first prepolymer and the second prepolymer at 10: 90 to calculate furandicarboxylic acid group and terephthalic acid group ratio in product copolyester compound, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 DEG C through 1.5 hours, and when described reaction completes, the temperature in flask is 290 DEG C, resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 4
At the temperature of 250 DEG C, the biogenetic derivation ethylene glycol (great achievement group product) of the terephthalic acid of 166 weight parts and 75 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
Be to weigh the first prepolymer and the second prepolymer at 12: 88 to calculate furandicarboxylic acid group and terephthalic acid group ratio in product copolyester compound, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 DEG C through 1.5 hours, and when described reaction completes, the temperature in flask is 290 DEG C, resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 5
At the temperature of 250 DEG C, the biogenetic derivation ethylene glycol (great achievement group product) of the NDA of 166 weight parts and 75 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
By the first prepolymer and the second prepolymer to calculate furandicarboxylic acid group and 2 in product copolyester compound, 6-naphthalic acid group ratio is to weigh at 10: 90, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 DEG C through 1.5 hours, and when described reaction completes, the temperature in flask is 290 DEG C, and resulting pressure is about 130Pa, obtains copolyester compound, and structural formula is as follows:
Embodiment 6
At the temperature of 250 DEG C, the biogenetic derivation butyleneglycol (great achievement group product) of the terephthalic acid of 166 weight parts and 108 weight parts is carried out direct esterification reaction, obtains the first prepolymer.
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation butyleneglycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 307 weight parts carries out esterification (ES reaction), obtains the second prepolymer.
Be to weigh the first prepolymer and the second prepolymer at 10: 90 to calculate furandicarboxylic acid group and terephthalic acid group ratio in product copolyester compound, the low prepolymer claimed two kinds mixes, drop in polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, the homo(io)thermism in flask is 250 DEG C, and resulting pressure is about 130Pa, obtains copolyester compound, and structural formula is as follows:
Comparative example 1
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 212 weight parts carries out esterification (ES reaction), be placed on and be furnished with in the polymerization flask of rectifying tower, tetrabutyl titanate (the AR of esterifying catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, react under nitrogen protection, when reaction mixture becomes transparent, when rectifying tower tower top temperature drops to 50 DEG C, above-mentioned reaction completes, obtain micromolecular prepolymer.
The polycondensation stage, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm, under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 240 DEG C through 1.5 hours, when described reaction completes, temperature in flask is 240 DEG C, resulting pressure is about 130Pa, obtain poly-2, 5-furandicarboxylic acid glycol ester.
Comparative example 2
At the temperature of 250 DEG C, direct esterification reaction is carried out with the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol (great achievement group product) of 75 weight parts, gained reaction product is placed in the polymerization four-hole boiling flask being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 5ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 30ppm, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature was warming up to 290 DEG C through one and a half hours, when described reaction completes, temperature in flask is 290 DEG C, resulting pressure is about 200Pa, obtain polymkeric substance ethylene glycol terephthalate.
Comparative example 3
At the temperature of 250 DEG C, with 2 of 166 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 6-naphthalic acid and 75 weight parts carries out direct esterification reaction, gained reaction product is placed in the polymerization four-hole boiling flask being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 5ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 30ppm, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature was warming up to 290 DEG C through one and a half hours, when described reaction completes, temperature in flask is 290 DEG C, resulting pressure is about 200Pa, obtain polymer poly 2, 6-(ethylene naphthalate).
Comparative example 4
At the temperature of 220 DEG C, direct esterification reaction is carried out with the terephthalic acid of 166 weight parts and the biogenetic derivation butyleneglycol (great achievement group product) of 108 weight parts, gained reaction product is placed in the polymerization four-hole boiling flask being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 5ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 30ppm, under atmospheric pressure be decompressed to about 300Pa through one hour, homo(io)thermism is 250 DEG C, resulting pressure is about 200Pa, obtain polymer poly mutual-phenenyl two acid bromide two alcohol ester.
Comparative example 5
At the temperature of 160 DEG C, by 2 of 89 weight parts, the biogenetic derivation butyleneglycol (great achievement group product) of 5-furandicarboxylic acid (high and new technology industrial development zone, Mianyang Gao Te Science and Technology Ltd. product) and 307 weight parts carries out esterification (ES reaction), be placed on and be furnished with in the polymerization flask of rectifying tower, tetrabutyl titanate (the AR of esterifying catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, react under nitrogen protection, when reaction mixture becomes transparent, when rectifying tower tower top temperature drops to 50 DEG C, above-mentioned reaction completes, obtain micromolecular prepolymer.
The polycondensation stage, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition be in Ti element relative to copolyester compound total amount for 100ppm, tripotassium phosphate ester cpds (AR, Shanghai Run Jie chemical reagent company limited product) addition be in phosphoric relative to copolyester compound total amount for 100ppm, under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 220 DEG C through 1.5 hours, when described reaction completes, temperature in flask is 220 DEG C, resulting pressure is about 130Pa, obtain poly-2, 5-furandicarboxylic acid butanediol ester.
Table one:
| Project | Furandicarboxylic acid/terephthalic acid (or NDA) (mol ratio) | Tm/℃ | Tc/℃ | Tg/℃ |
| Embodiment 1 | 5∶95 | 243.24 | 179.16 | 82.06 |
| Embodiment 2 | 8∶92 | 236.28 | 170.99 | 80.98 |
| Embodiment 3 | 10∶90 | 226.74 | - | 81.28 |
| Embodiment 4 | 12∶88 | 222.87 | - | 80.9 |
| Embodiment 5 | 10∶90 | 245.23 | - | 82.15 |
| Embodiment 6 | 10∶90 | 208 | 145 | 42 |
| Comparative example 1 | 100∶0 | 209 | 168 | 87 |
| Comparative example 2 | 0∶100 | 254 | 177.15 | 78 |
| Comparative example 3 | 0∶100 | 270 | 190 | 120 |
| Comparative example 4 | 0∶100 | 221 | 170 | 50 |
| Comparative example 5 | 100∶0 | 169 | 100 | 40 |
Claims (5)
1. a copolyester compound, is characterized in that: this copolyester compound is formed by the glycol of biogenetic derivation, the diacid of biogenetic derivation and aromatic diacid copolymerization, its fusing point Tm >=220 DEG C; The general structure of this copolyester compound is as follows, and wherein B is the biological diol structure unit of dehydrogenation, and A is the aromatic diacid structural unit of dehydroxylation, and x is the integer of 50 ~ 200; Said aromatic diacid is terephthalic acid or NDA, and the mol ratio of the diacid of aromatic diacid and biogenetic derivation is 1:0.05 ~ 1:20
。
2. copolyester compound according to claim 1, is characterized in that: the glycol of said biogenetic derivation is the ethylene glycol of biogenetic derivation, 1,3-PD or BDO.
3. copolyester compound according to claim 1, is characterized in that: the diacid of said biogenetic derivation is the FDCA of biogenetic derivation.
4. copolyester compound according to claim 1, is characterized in that: during copolymerization, the mol ratio of the total mole number of the diacid of aromatic diacid and biogenetic derivation and the glycol of biogenetic derivation is 1:1 ~ 1:8.
5. the preparation method of copolyester compound described in a claim 1, it is characterized in that: first the glycol of aromatic diacid and biogenetic derivation is carried out esterification, obtain the first prepolymer, again the glycol of the diacid of biogenetic derivation and biogenetic derivation is carried out esterification, obtain the second prepolymer, then the first prepolymer and the second prepolymer are carried out polycondensation and obtain copolyester compound; Esterification reaction temperature is 140 ~ 230 DEG C; Polycondensation temperature is 210 ~ 280 DEG C.
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| WO2018041818A1 (en) * | 2016-09-01 | 2018-03-08 | ROSOLEN-DELARUE, Katell | Process for producing a bio-based polyethylene terephthalate (pet) polymer, entirely from bio-based materials |
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| US4876327A (en) * | 1987-05-13 | 1989-10-24 | Stamicarbon B.V. | Aromatic polyester |
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| WO2017098296A1 (en) * | 2015-12-11 | 2017-06-15 | SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrégé "S.A.E.M.E" | Pet polymer with an anti-crystallization comonomer that can be bio-sourced |
| WO2018041818A1 (en) * | 2016-09-01 | 2018-03-08 | ROSOLEN-DELARUE, Katell | Process for producing a bio-based polyethylene terephthalate (pet) polymer, entirely from bio-based materials |
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