CN102190782A - Copolyester compound and method for preparing same - Google Patents
Copolyester compound and method for preparing same Download PDFInfo
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Abstract
The invention provides a copolyester compound and a method for preparing the same. The copolyester compound is prepared through copolymerization of biologically sourced diol, biologically sourced diacid and aromatic diacid, and the melting point Tm of the copolyester compound is more than or equal to 220 DEG C. In the preparation method, the aromatic diacid and the biologically sourced diacid are respectively esterified with the biologically sourced diol, and the obtained products are subjected to condensation polymerization to obtain the copolyester compound. The copolyester compound has the advantages of high melting point and wide scope of application.
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 uses are fewer and feweri, how to substitute and reduce and use oil as starting material, be that people face one of important research problem.
Patent CN200810018622.1 provides a kind of method for preparing thing source polyester in half a lifetime, its acid starting material terephthalic acid or dimethyl terephthalate (DMT) are the oil sources, its raw polyol ethylene glycol is biogenetic derivation, the polyethylene terephthalate of preparation is very nearly the same with the performance of the polyethylene terephthalate in complete oil source, but it is 30% weight is biogenetic derivation, all the other 70% are oil sources, and it is lower that biogenetic derivation is formed proportion.
Patent US200910124763 provides a kind of method for preparing complete biogenetic derivation polyester, its acid starting material 2, and 5-furans dioctyl phthalate or 2,5-furans dioctyl phthalate dimethyl ester is 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, thereby has limited its use range.
Summary of the invention
The object of the present invention is to provide the higher copolyester compound of a kind of biogenetic derivation raw material proportion, and this copolyester compound fusing point height, applied range.
Copolyester compound of the present invention is to be formed by the diacid of the glycol of biogenetic derivation, biogenetic derivation and aromatic diacid copolymerization, its fusing point Tm 〉=220 ℃; 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 50～200 integer.
1 of the ethylene glycol of the preferred biogenetic derivation of glycol of said biogenetic derivation, biogenetic derivation, 1 of ammediol or biogenetic derivation, 4-butyleneglycol.The preparation method of biogenetic derivation glycol transfers to carbon source in the biomaterial in the dibasic alcohol.Farm crop are a kind of renewable resourcess, can be with airborne CO
2Pass through photosynthesis, being converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. stores in farm crop fruit and stalk thereof, the present invention utilizes the stalk of corn, wheat, sugarcane and farm crop, and the process biological fermentation and/or the chemical industry course of processing make the raw material dibasic alcohol of polyester.Biomaterial of the present invention is the stalk of corn, sugarcane, wheat and farm crop.Obtain dibasic alcohol through biology and/or chemical process.Employed biomaterial is the stalk of corn, sugarcane, wheat and farm crop.Obtain butyleneglycol through biology and/or chemical process.For example corn is through the bioprocess separating starch, and through processing the sugar that obtains 5 carbon and 6 carbon, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalysts, after the purifies and separates general procedure, just can obtain raw material dibasic alcohol of the present invention.
2 of the preferred biogenetic derivation of diacid of said biogenetic derivation, 2 of 5-furans dioctyl phthalate or biogenetic derivation, 5-furans dioctyl phthalate dimethyl ester.Described 2,5-furans dioctyl phthalate or 2,5-furans dioctyl phthalate dimethyl ester is obtained by the biomass cellulose source.Make fructose earlier by Mierocrystalline cellulose, the fructose dehydration makes hydroxymethylfurfural (HMF), and hydroxymethylfurfural makes the furans dioctyl phthalate through reaction process such as peroxidation, is prepared into 2 by the furans dioctyl phthalate, 5-furans dioctyl phthalate dimethyl ester.The preferred terephthalic acid of said aromatic diacid, dimethyl terephthalate (DMT), 2,6-naphthalic acid or 2,6-naphthalene diformic acid dimethyl ester.
During copolymerization the mol ratio of the diacid of aromatic diacid and biogenetic derivation be preferably 1: 0.05～1: 20.
During copolymerization the mol ratio of the glycol of the total mole number of the diacid of aromatic diacid and biogenetic derivation and biogenetic derivation be preferably 1: 1～1: 8.
The preparation method of copolyester compound of the present invention, specifically comprise Esterification Stage and polymerization stage, glycol with aromatic diacid and biogenetic derivation carries out esterification earlier, obtain first prepolymer, again the diacid of biogenetic derivation and the glycol of biogenetic derivation are carried out esterification, obtain second prepolymer, then first prepolymer and second prepolymer are carried out polycondensation and obtain copolyester compound; Esterification reaction temperature is 140～230 ℃; The polycondensation temperature is 210～280 ℃.
Esterification reaction temperature is preferably 150～170 ℃.Aromatic diacid and furans dioctyl phthalate heat while stirring slowly with glycol, catalyzer or catalyst mixture respectively in the esterification reaction process, it is transparent that the terminal point of esterification is that reaction mixture becomes, and the reaction mixture in this period is the small molecules prepolymer.The preferred 230-260 of polymeric reaction temperature ℃, polycondensation process is preferably under the vacuum and carries out, owing to have the by product glycol of generation in the polycondensation reaction system, removes the speed of response that by product improves polycondensation under vacuum.
Among the preparation method of copolyester compound of the present invention, aromatic diacid is terephthalic acid, dimethyl terephthalate (DMT), 2 preferably, 6-naphthalic acid or 2,6-naphthalene diformic acid dimethyl ester, the diacid of biogenetic derivation preferably 2,5-furans dioctyl phthalate or 2,5-furans dioctyl phthalate dimethyl ester, during copolymerization the mol ratio of the diacid of aromatic diacid and biogenetic derivation be preferably 1: 0.05～1: 20, in this scope, reaction steadily and reaction to finish the needed time 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, in this scope, reaction steadily and reaction to finish the needed time shorter.
Among the preparation method of copolyester compound of the present invention, catalyzer is described.When diacid and glycol synthetic macromolecular compound, though since the self-catalysis of diacid do not add catalyzer and can react yet.But as the diacid of reactant, its concentration is along with the carrying out step-down gradually of reaction, the catalytic effect variation, and it is better therefore to add catalyzer.Catalyzer in the esterification reaction process can be organometallic compounds such as metal acidulants and salt, tin, zinc, titanium, catalyzer in the polycondensation process can be acetate, the carbonate of zinc, manganese, magnesium etc., perhaps organometallic compounds such as the metal oxide of zinc, manganese, magnesium etc. and tin, zinc, titanium, but double esterification and the preferred titanium compound of polycondensation of closing, catalyzer of the present invention is a titanium compound.Concrete be enumerated as tetrabutyl titanate, sec.-propyl titanic acid ester, propyl group titanic acid ester or propenyl titanic acid ester.
Also use the stablizer phosphorus compound among the present invention, can be trivalent or phosphoric organic compound and inorganic phosphorous compound, that can simply enumerate has trimethyl phosphite 99, a triphenylphosphate, phosphoric acid etc., can be the trivalent of commercially available phosphorus system and the antioxidant of pentavalent, as commercially available PEP36, AP1500, AX-71.Do not enumerate more specifically at this.
Among the present invention except using above-described catalyzer and stablizer, can also add nano titanium oxide, its particle diameter of nano titanium oxide is that 20-40nm. adds 0.05-1%, the titanium dioxide of preferable particle size 20 nanometers, addition 0.1%, the adding of an amount of titanium dioxide can reach the effect of delustring.
The present invention can also add other weighting materials that can not reduce the polyester performance, if you would take off soil, and mica etc. are not enumerated more specifically at this, and an amount of polynite or micaceous add the thermal change type temperature that can improve polymkeric substance, enlarge its range of application.The present invention is with the glycol of biogenetic derivation, the diacid and the aromatic diacid copolymerization copolyester compound of biogenetic derivation, make its fusing point keep higher on the one hand, make it have similar fusing point to PBT, PTT, enlarge its range of application, make in the copolyesters biogenetic derivation composition proportion higher as far as possible on the other hand, promptly improve its bioid degree.
The following describes fusing point test method of the present invention and evaluation method.
The DSC test:
Differential scanning calorimeter DSC (TA, Q100) be warmed up to 280 ℃ from 40 ℃ with 16 ℃/min after constant temperature 3 minutes, eliminate thermal history; Rapid cool to room temperature then, be warmed up to 280 ℃ from 40 ℃ with 16 ℃/min again after constant temperature 3 minutes, cool to 40 ℃ with 16 ℃/min again, finish.Obtain second-order transition temperature in heating up for the second time and be designated as Tg, cold crystallization temperature Tcc and melt temperature are fusing point Tm.
Embodiment
Further specify the present invention with following embodiment, the concrete numerical value of each embodiment and comparative example sees Table one.
Embodiment 1
Under 250 ℃ temperature, the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol of 75 weight parts (great achievement group product) are carried out the direct esterification reaction, obtain first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
Is to weigh at 5: 95 first prepolymer and second prepolymer to calculate in the product copolyester compound furans dioctyl phthalate group and terephthalic acid group ratio, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 130Pa, obtains copolyester compound, and its structural formula is as follows:
Embodiment 2
Under 250 ℃ temperature, the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol of 75 weight parts (great achievement group product) are carried out the direct esterification reaction, obtain first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
Is to weigh at 8: 92 first prepolymer and second prepolymer to calculate in the product copolyester compound furans dioctyl phthalate group and terephthalic acid group ratio, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 3
Under 250 ℃ temperature, the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol of 75 weight parts (great achievement group product) are carried out the direct esterification reaction, obtain first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
Is to weigh at 10: 90 first prepolymer and second prepolymer to calculate in the product copolyester compound furans dioctyl phthalate group and terephthalic acid group ratio, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 4
Under 250 ℃ temperature, the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol of 75 weight parts (great achievement group product) are carried out the direct esterification reaction, obtain first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
Is to weigh at 12: 88 first prepolymer and second prepolymer to calculate in the product copolyester compound furans dioctyl phthalate group and terephthalic acid group ratio, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 130Pa, obtains copolyester compound (structural formula is with embodiment 1).
Embodiment 5
Under 250 ℃ temperature, with 2 of 166 weight parts, the biogenetic derivation ethylene glycol of 6-naphthalic acid and 75 weight parts (great achievement group product) carries out the direct esterification reaction, obtains first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
With first prepolymer and second prepolymer to calculate furans dioctyl phthalate group and 2 in the product copolyester compound, 6-naphthalic acid group ratio is to weigh at 10: 90, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 290 ℃ through 1.5 hours, and when described reaction was finished, the temperature in the flask was 290 ℃, and resulting pressure is about 130Pa, obtains copolyester compound, and structural formula is as follows:
Embodiment 6
Under 250 ℃ temperature, the terephthalic acid of 166 weight parts and the biogenetic derivation butyleneglycol of 108 weight parts (great achievement group product) are carried out the direct esterification reaction, obtain first prepolymer.
Under 160 ℃ temperature, with 2 of 89 weight parts, the biogenetic derivation butyleneglycol (great achievement group product) of 5-furans dioctyl phthalate (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 second prepolymer.
Is to weigh at 10: 90 first prepolymer and second prepolymer to calculate in the product copolyester compound furans dioctyl phthalate group and terephthalic acid group ratio, with two kinds claim low prepolymer mix, drop in the polymerization test tube, tetrabutyl titanate (the AR of polymerizing catalyst in addition, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, the addition of tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) is to be 100ppm in phosphoric with respect to the copolyester compound total amount.Under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, the homo(io)thermism in the flask is 250 ℃, and resulting pressure is about 130Pa, obtains copolyester compound, and structural formula is as follows:
Comparative example 1
Under 160 ℃ temperature; with 2 of 89 weight parts; the biogenetic derivation ethylene glycol (great achievement group product) of 5-furans dioctyl phthalate (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 in the polymerization flask of being furnished with rectifying tower; tetrabutyl titanate (the AR of esterifying catalyst; Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount; under nitrogen protection, react; when reaction mixture becomes transparent; when the rectifying tower tower top temperature drops to 50 ℃; above-mentioned reaction is finished, and obtains micromolecular prepolymer.
The polycondensation stage, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) addition be to be 100ppm with respect to the copolyester compound total amount in phosphoric, under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 240 ℃ through 1.5 hours, when described reaction is finished, temperature in the flask is 240 ℃, resulting pressure is about 130Pa, obtains gathering 2,5-furans dioctyl phthalate glycol ester.
Comparative example 2
Under 250 ℃ temperature, carry out the direct esterification reaction with the terephthalic acid of 166 weight parts and the biogenetic derivation ethylene glycol of 75 weight parts (great achievement group product), the gained reaction product is placed the polymerization four-hole boiling flask of being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 5ppm in the Ti element with respect to the copolyester compound total amount, tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) addition be to be 30ppm with respect to the copolyester compound total amount in phosphoric, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature was warming up to 290 ℃ through one and a half hours, when described reaction is finished, temperature in the flask is 290 ℃, resulting pressure is about 200Pa, obtains the polymkeric substance ethylene glycol terephthalate.
Comparative example 3
Under 250 ℃ temperature, with 2 of 166 weight parts, the biogenetic derivation ethylene glycol of 6-naphthalic acid and 75 weight parts (great achievement group product) carries out the direct esterification reaction, the gained reaction product is placed the polymerization four-hole boiling flask of being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 5ppm in the Ti element with respect to the copolyester compound total amount, tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) addition be to be 30ppm with respect to the copolyester compound total amount in phosphoric, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature was warming up to 290 ℃ through one and a half hours, when described reaction is finished, temperature in the flask is 290 ℃, resulting pressure is about 200Pa, obtain the polymkeric substance polyethylene glycol 2.
Comparative example 4
Under 220 ℃ temperature, carry out the direct esterification reaction with the terephthalic acid of 166 weight parts and the biogenetic derivation butyleneglycol of 108 weight parts (great achievement group product), the gained reaction product is placed the polymerization four-hole boiling flask of being furnished with rectifying tower, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 5ppm in the Ti element with respect to the copolyester compound total amount, tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) addition be to be 30ppm with respect to the copolyester compound total amount in phosphoric, under atmospheric pressure be decompressed to about 300Pa through one hour, homo(io)thermism is 250 ℃, resulting pressure is about 200Pa, obtains the polymer poly mutual-phenenyl two acid bromide two alcohol ester.
Comparative example 5
Under 160 ℃ temperature; with 2 of 89 weight parts; the biogenetic derivation butyleneglycol (great achievement group product) of 5-furans dioctyl phthalate (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 in the polymerization flask of being furnished with rectifying tower; tetrabutyl titanate (the AR of esterifying catalyst; Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount; under nitrogen protection, react; when reaction mixture becomes transparent; when the rectifying tower tower top temperature drops to 50 ℃; above-mentioned reaction is finished, and obtains micromolecular prepolymer.
The polycondensation stage, tetrabutyl titanate (the AR of polymerizing catalyst, Shishewei Chemical Co., Ltd., Shanghai's product) addition is to be 100ppm in the Ti element with respect to the copolyester compound total amount, tripotassium phosphate ester cpds (AR, prompt chemical reagent company limited product is moistened in Shanghai) addition be to be 100ppm with respect to the copolyester compound total amount in phosphoric, under atmospheric pressure be decompressed to about 300Pa through 1.5 hours, temperature was warming up to 220 ℃ through 1.5 hours, when described reaction is finished, temperature in the flask is 220 ℃, resulting pressure is about 130Pa, obtains gathering 2,5-furans dioctyl phthalate butanediol ester.
Table one:
| Project | Furans dioctyl phthalate/terephthalic acid (or 2, the 6-naphthalic acid) (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 (7)
1. copolyester compound, it is characterized in that: this copolyester compound forms its fusing point Tm 〉=220 ℃ by the glycol of biogenetic derivation, the diacid and the aromatic diacid copolymerization of biogenetic derivation; 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 50～200 integer.
2. copolyester compound according to claim 1 is characterized in that: the glycol of said biogenetic derivation is the ethylene glycol, 1 of biogenetic derivation, ammediol or 1,4-butyleneglycol.
3. copolyester compound according to claim 1 is characterized in that: the diacid of said biogenetic derivation is 2 of a biogenetic derivation, 5-furans dioctyl phthalate or 2,5-furans dioctyl phthalate dimethyl ester.
4. copolyester compound according to claim 1 is characterized in that: said aromatic diacid is terephthalic acid, dimethyl terephthalate (DMT), 2,6-naphthalic acid or 2,6-naphthalene diformic acid dimethyl ester.
5. copolyester compound according to claim 1 is characterized in that: the mol ratio of the diacid of aromatic diacid and biogenetic derivation is 1: 0.05～1: 20 during copolymerization.
6. copolyester compound according to claim 1 is characterized in that: the mol ratio of the glycol of the total mole number of the diacid of aromatic diacid and biogenetic derivation and biogenetic derivation is 1: 1～1: 8 during copolymerization.
7. the preparation method of the described copolyester compound of claim 1, it is characterized in that: the glycol with aromatic diacid and biogenetic derivation carries out esterification earlier, obtain first prepolymer, again the diacid of biogenetic derivation and the glycol of biogenetic derivation are carried out esterification, obtain second prepolymer, then first prepolymer and second prepolymer are carried out polycondensation and obtain copolyester compound; Esterification reaction temperature is 140～230 ℃; The polycondensation temperature is 210～280 ℃.
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| CN113292708A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | Bio-based copolyester and preparation method and application thereof |
| CN113493561A (en) * | 2020-03-20 | 2021-10-12 | 中国科学院大连化学物理研究所 | 2, 6-naphthalenedicarboxylic acid based copolyester material and preparation method thereof |
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