CN110734541B - Bio-based copolyester and preparation method thereof - Google Patents
Bio-based copolyester and preparation method thereof Download PDFInfo
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- CN110734541B CN110734541B CN201910854377.6A CN201910854377A CN110734541B CN 110734541 B CN110734541 B CN 110734541B CN 201910854377 A CN201910854377 A CN 201910854377A CN 110734541 B CN110734541 B CN 110734541B
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Abstract
The invention relates to a bio-based copolyester and a preparation method thereof, wherein the structural formula of the bio-based copolyester is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
the glass transition temperature of the bio-based copolyester is 90-122 ℃, the bio-based copolyester has the characteristics of excellent heat resistance, better mechanical property, high transparency and the like, can meet the manufacturing requirements in the fields of baby feeding bottles, children toys, water cups, kitchen electrical products, food packaging, electronic and electric products, optics, decorative materials, automobile manufacturing and the like, and also has special application in the field of light bulletproof glass.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to bio-based copolyester and a preparation method thereof.
Background
Polyesters are obtained by polycondensation of polybasic acids and polyhydric alcohols, and include bisphenol a polycarbonate (BPA-PC), polyethylene terephthalate (PET), polyethylene furan dicarboxylate (PEF), and the like. Among them, BPA-PC has a glass transition temperature (Tg) of more than 100 ℃, strong impact resistance and high transparency, but bisphenol A is slowly released in the use process, so that metabolism disorder is caused, infant dysplasia, cancer and the like are induced, and the European Union and China prohibit the use of BPA-PC in the fields of infant food packaging and contact, so that the mainstream suppliers of water cups and kitchen electric products are in health consideration and do not use BPA-PC any more. PET and PEF have the characteristics of good mechanical property, good barrier property, high transparency and the like, but the Tg of the PET and the PEF is low, the thermal stability is poor, and the PET and the PEF are not suitable for hot drink bottles.
Disclosure of Invention
Based on the above, in order to overcome the above problems, a bio-based copolyester and a preparation method thereof are provided; the bio-based copolyester is obtained by melt polycondensation of 2, 5-furandicarboxylic acid or an esterified product thereof, bis [4- (2-hydroxyethoxy) phenyl ] sulfone and dihydric alcohol, has the glass transition temperature of 90-122 ℃, has the characteristics of excellent heat resistance, strong transparency, good mechanical property and the like, and can be used for manufacturing baby feeding bottles, water cups, kitchen electrical products, food packages, optical devices, decorative materials, automobile structural parts and the like.
A bio-based copolyester having a structural formula as shown in the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
further, the glass transition temperature of the bio-based copolyester is 90-122 ℃.
A method of preparing a bio-based copolyester, comprising:
(1) mixing 2, 5-furandicarboxylic acid or an esterified product thereof, bis [4- (2-hydroxyethoxy) phenyl ] sulfone, dihydric alcohol and an esterification catalyst, and carrying out an esterification reaction to obtain a first intermediate product, wherein the structural formula of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is shown as the following formula (2):
(2) performing polycondensation reaction on the first intermediate product to obtain the bio-based copolyester, wherein the structural formula of the bio-based copolyester is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
further, the molar ratio of the 2, 5-furandicarboxylic acid or an esterified product thereof to the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is 1: (0.1-0.9).
Further, the molar ratio of the sum of the used amounts of the dihydric alcohol and the bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the 2, 5-furandicarboxylic acid or the esterified product thereof is (1.1-2.2): 1.
further, the dihydric alcohol comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol and monoethylene glycol.
Further, the temperature of the esterification reaction in the step (1) is 160-220 ℃, and the reaction time is 2-6 hours.
Further, the polycondensation reaction in the step (2) is carried out in a vacuum environment, the temperature is 220-300 ℃, and the reaction time is 2-6 hours.
Further, the vacuum degree of the vacuum environment is not higher than 300 Pa.
Further, in the step (2), at least one of a polycondensation reaction catalyst, a stabilizer and an antioxidant is added.
2, 5-furandicarboxylic acid (2,5-FDCA) has high rigidity, asymmetric horizontal axis and low space packing density, so that the invention adopts rigid bis [4- (2-hydroxyethoxy) phenyl ] sulfone to partially replace dihydric alcohol to copolymerize with 2, 5-furandicarboxylic acid or an esterified product thereof and the dihydric alcohol to obtain the bio-based copolyester shown in the formula (1). The glass transition temperature of the bio-based copolyester reaches 90-122 ℃, and the bio-based copolyester has the characteristics of excellent heat resistance, better mechanical property, high transparency and the like, can meet the manufacturing requirements in the fields of baby feeding bottles, children toys, water cups, kitchen electrical products, food packaging, electronic and electric products, optics, decorative materials, automobile manufacturing and the like, and also has special application in the field of light bulletproof glass.
Drawings
FIG. 1 is a drawing showing the preparation of bio-based copolyester of example 1 of the present invention1An H-NMR spectrum;
fig. 2 is a DSC profile of bio-based copolyester of example 1 of the present invention.
Detailed Description
The bio-based copolyester provided by the present invention will be further described below.
The invention utilizes 2, 5-furandicarboxylic acid or esterified product thereof, bis [4- (2-hydroxyethoxy) phenyl ] sulfone and dihydric alcohol to copolymerize and prepare the bio-based copolyester, the glass transition temperature of the bio-based copolyester reaches 90-122 ℃, and the bio-based copolyester has the characteristics of good heat resistance, strong stability, high transparency, excellent mechanical property, environmental protection and the like, and can be better applied to the fields of baby feeding bottles, water cups, kitchen electrical products, food packaging, optical devices, decorative materials, automobile manufacturing and the like.
The structural formula of the bio-based copolyester provided by the invention is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
specifically, the glass transition temperature of the bio-based copolyester reaches 90-122 ℃, so that the bio-based copolyester has the characteristics of excellent heat resistance, better mechanical property, high transparency and the like. Furthermore, by adjusting the structural formula
and-R-, the glass transition temperature of the bio-based copolyester of the invention can be adjusted.
Preferably, when
And the molar ratio of the structural units of-R-is (40-90): (10-60), the glass transition temperature of the bio-based copolyester can reach 100-122 DEG C
The molar ratio of (a) to (b) is increased.
Therefore, the bio-based copolyester can meet the manufacturing requirements in the fields of baby feeding bottles, children toys, water cups, kitchen electrical products, food packaging, electronic and electric appliances, optics, decorative materials, automobile manufacturing and the like, and also has special application in the field of light bulletproof glass.
The invention also provides a preparation method of the bio-based copolyester, which comprises the following steps:
(1) mixing 2, 5-furandicarboxylic acid or an esterified product thereof, bis [4- (2-hydroxyethoxy) phenyl ] sulfone, dihydric alcohol and an esterification catalyst, and carrying out an esterification reaction to obtain a first intermediate product, wherein the structural formula of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is shown as the following formula (2):
(2) performing polycondensation reaction on the first intermediate product to obtain the bio-based copolyester, wherein the structural formula of the bio-based copolyester is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
in the step (1), the 2, 5-furandicarboxylic acid is a furan derivative with stable properties, has two carboxyl groups, is similar to the structure of terephthalic acid, and is a cyclic conjugated system. The difference between the two is that 2, 5-furandicarboxylic acid is prepared by hydrolyzing and oxidizing starch or saccharide in nature, while terephthalic acid is mainly obtained by depending on petroleum. Therefore, in order to reduce the consumption of non-renewable energy sources and simultaneously reduce the emission of greenhouse gases, 2, 5-furandicarboxylic acid can be used for industrially producing copolyester well instead of terephthalic acid.
Wherein the esterified 2, 5-furandicarboxylic acid includes dimethyl 2, 5-furandicarboxylate. In view of the better reactivity of dimethyl 2, 5-furandicarboxylate, dimethyl 2, 5-furandicarboxylate is preferably used in the present invention.
In addition, PET based on terephthalic acid monomer has Tg of about 70 ℃, melting temperature of about 260 ℃ and processing temperature of about 285 ℃, so when rigid molecules are introduced to prepare high Tg copolyester based on the above, the introduced rigid segments increase the melting temperature of the copolyester, and thus the processing temperature needs to be raised to 300 ℃ or higher. However, when the processing temperature is raised to above 300 ℃, thermal decomposition of the copolyester is accelerated, resulting in insufficient molecular weight and deepening of color of the copolyester.
Whereas PEF based on 2, 5-furandicarboxylic acid monomer has a Tg of about 87 deg.C, but a melting temperature of about 217 deg.C. Therefore, a high Tg copolyester can be prepared by introducing a small amount of bis [4- (2-hydroxyethoxy) phenyl ] sulfone. And because the melting temperature is low, the processing temperature of the copolyester is improved but does not exceed 300 ℃ after the rigid chain segment of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is introduced, so that the preparation of the copolyester is more controllable and the transparency is better.
When the usage amount of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is too low, the Tg of the bio-based copolyester is slightly improved, but when the usage amount is too high, the prepared bio-based copolyester is more brittle due to the higher rigidity of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone, and the practical requirement cannot be met. Therefore, the molar ratio of 2, 5-furandicarboxylic acid or an esterified product thereof to the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is preferably 1: (0.1 to 0.9), more preferably 1: (0.4-0.9).
Specifically, the dihydric alcohol comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol and monoethylene glycol. Preferably, the diol is at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, and neopentyl glycol.
Considering that the molar ratio of the diol to the 2, 5-furandicarboxylic acid or the ester thereof is too high, the diol may undergo self-polycondensation reaction at high temperature, so that the proportion of by-products in the first intermediate product is increased, which is not favorable for the synthesis of the target product. And the molar ratio of the dihydric alcohol to the 2, 5-furandicarboxylic acid or the esterified product thereof is too low, so that the esterification reaction rate is reduced, and the reaction time is prolonged. Therefore, under the condition of fully exerting the advantages of the raw material molar ratio reaction, the byproduct is more effectively controlled, the invention regulates and controls the esterification reaction rate by controlling the molar ratio of the total amount of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone and the dihydric alcohol to the 2, 5-furandicarboxylic acid or the esterified product thereof, and improves the yield of the first intermediate product. Preferably, the molar ratio of the total amount of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone and the dihydric alcohol to the 2, 5-furandicarboxylic acid or the esterified product thereof is (1.1-2.2): 1, more preferably (1.5 to 1.7): 1.
specifically, the esterification catalyst comprises at least one of zinc acetate, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony, antimony acetate and dibutyltin oxide. Proper catalyst can increase the reaction speed and reduce the esterification time, but too high catalyst dosage can also accelerate the occurrence of side reaction. Therefore, the amount of the esterification catalyst is 0.05 to 0.5%, preferably 0.2 to 0.4% of the molar amount of 2, 5-furandicarboxylic acid or an esterified product thereof, in view of the rate of the esterification reaction.
Considering that the esterification reaction is an endothermic reaction, the temperature of the esterification reaction needs to be reasonably controlled. The reasonable reaction temperature can not only improve the solubility of the whole system, but also promote the esterification reaction and improve the esterification rate. Therefore, the esterification reaction in step (1) is carried out in an inert gas atmosphere at a reaction temperature of 160 to 220 ℃ and preferably 185 to 210 ℃. The reaction time is 2 to 6 hours, preferably 4.5 to 6 hours.
In the step (2), the temperature of the polycondensation reaction is 220-300 ℃, preferably 230-255 ℃, and the reaction time is 2-6 hours, preferably 5-6 hours. Because the melting temperature of the polyester obtained by the reaction of the 2, 5-furandicarboxylic acid and the dihydric alcohol is low, the processing temperature is still lower than 300 ℃ after rigid bis [4- (2-hydroxyethoxy) phenyl ] sulfone is introduced, and the preparation of the copolyester is facilitated.
Specifically, the polycondensation reaction is carried out in a vacuum environment. Wherein, in the polycondensation stage, the high vacuum degree is favorable for discharging the by-product generated in the polycondensation, thereby obtaining the polyester product with high viscosity. However, in the polycondensation reaction, too high a vacuum degree causes the low-viscosity copolymer to be drawn out, clogging the pipe, and the requirement for equipment is higher, so that the production cost is increased. Therefore, in order to ensure the quality of the copolyester product, the vacuum degree of the polycondensation reaction can be gradually and slowly reduced to below 300 Pa. Preferably, the degree of vacuum is reduced to 100Pa or less.
Specifically, during the polycondensation reaction, a polycondensation reaction catalyst is added into the first intermediate product, wherein the polycondensation reaction catalyst comprises at least one of antimony trioxide, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony, antimony acetate and dibutyltin oxide. Preferably, the amount of the polycondensation catalyst is 0.05 to 0.5 percent, preferably 0.2 to 0.4 percent, based on the molar amount of the 2, 5-furandicarboxylic acid or the esterified product thereof.
It is understood that when the esterification catalyst is at least one of isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony, antimony acetate, dibutyl tin oxide, the esterification catalyst may also be used as a polycondensation catalyst. In this case, the first intermediate product may be directly subjected to the polycondensation reaction of step (2). However, it is considered that the esterification catalyst is partially deactivated after the esterification reaction. Therefore, in the case where the esterification catalyst and the polycondensation catalyst are the same, a part of the polycondensation catalyst may be added additionally to the first intermediate product before the polycondensation reaction in step (2) is carried out.
Specifically, during the polycondensation reaction, a stabilizer is added, and the stabilizer can reduce the oxidative breakage of ester bonds, aliphatic chains, carbon-carbon bonds and the like under oxygen and prevent the occurrence of thermal decomposition. The stabilizer comprises at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate, and the dosage of the stabilizer is 0.01 to 0.5 percent of the molar weight of the 2, 5-furandicarboxylic acid or the esterified product thereof, and the more preferable dosage is 0.15 to 0.35 percent.
Specifically, during the polycondensation reaction, an antioxidant can be added, and the antioxidant can capture oxygen free radicals and eliminate trace oxygen, so that the occurrence of thermal decomposition reaction and oxidation side reaction is reduced. The antioxidant comprises at least one of antioxidant-1010, antioxidant-1076 and antioxidant-168, and the dosage of the antioxidant is 0.05 to 0.5 percent of the molar weight of the 2, 5-furandicarboxylic acid or the esterified substance thereof, and the more preferable dosage is 0.15 to 0.35 percent.
Hereinafter, the bio-based copolyester and the preparation method thereof will be further described by the following specific examples.
In the examples, NMR spectra1H-NMR was measured on a Bruker 400AVANCE III Spectrometer type instrument at 400MHz, CF3COOD。
In the examples, the molecular weight of all polymers was measured using Agilent PL-GPC220, columns were two PLgels 5 μm Mixed-D300 x 7.5mm in series. The mobile phase is chloroform, the testing temperature is 40 ℃, and the sample dissolving solvent is o-chlorophenol: chloroform-1: 1(v/v), the sample concentration is 1mg/mL, the flow rate is 1mL/min, and the standard is PS (3070-.
In the examples, thermal analysis was carried out using differential scanning calorimetry (Mettler Toledo DSC) at a temperature rise rate of 10 ℃/min in N2The atmosphere is carried out, and the temperature range is-10 ℃ to 300 ℃.
Example 1:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.125mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.275mol of 1, 4-butanediol were charged into the polymerization reactor, followed by 0.15% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. Reacting for 4 hours at 180 ℃ under an inert atmosphere to obtain a first intermediate product.
To the first intermediate product, 0.12% of triphenyl phosphate based on the molar mass of dimethyl 2, 5-furandicarboxylate and 0.1% of antioxidant-1010 based on the theoretical yield of the polymer were added, the vacuum degree was gradually reduced to below 100Pa, the temperature was gradually raised to 230 ℃, and the reaction was carried out for 4.5 hours to obtain a bio-based copolyester.
The relative number average molecular weight of the bio-based copolyester is 29300g/mol, and the relative weight average molecular weight is 49500 g/mol. Of the biobased copolyester1The H-NMR is shown in FIG. 1. Through testing, the bis [4- (2-hydroxyethoxy) phenyl]The molar ratio of sulfone structural units to 1, 4-butanediol structural units is 50: 50, the DSC curve of the copolyester is shown in FIG. 2, and the glass transition temperature of the copolyester is 95 ℃. The test proves that the tensile strength of the bio-based copolyester is 83.8MPa, and the tensile modulus is 2265 MPa.
Example 2:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.1625mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.2375mol of 1, 3-propanediol were charged into the polymerization reactor, followed by 0.2% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 185 ℃ for 4.5 hours under an inert atmosphere to obtain a first intermediate product.
To the first intermediate product, 0.15% of triphenyl phosphate based on the molar mass of dimethyl 2, 5-furandicarboxylate and 0.15% of antioxidant-1010 based on the theoretical yield of the polymer were added, the vacuum degree was gradually reduced to below 100Pa, the temperature was gradually raised to 235 ℃ and the reaction was carried out for 5.0 hours to obtain a bio-based copolyester.
Through detection, the relative number average molecular weight of the high-temperature resistant bio-based copolyester is 28400g/mol, the relative weight average molecular weight is 47200g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 3-propylene glycol is 65: the glass transition temperature of the copolyester was 106 ℃. The test proves that the tensile strength of the bio-based copolyester is 85.7MPa, and the tensile modulus is 2552 MPa.
Example 3:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.1625mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.2375mol of 1, 4-butanediol were charged into the polymerization reactor, followed by 0.25% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 185 ℃ for 4.5 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.2 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.2 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 235 ℃, and reacting for 5.0 hours to obtain the bio-based copolyester.
Through detection, the relative number average molecular weight of the high-temperature resistant bio-based copolyester is 27900g/mol, the relative weight average molecular weight is 46800g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 4-butanediol is 64: 36, the glass transition temperature of the copolyester was 105 ℃. The test proves that the tensile strength of the bio-based copolyester is 84.6MPa, and the tensile modulus is 2417 MPa.
Example 4:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.2mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.2mol of ethylene glycol were charged into a polymerization reactor, followed by 0.25% of tetrabutyl titanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 190 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.2 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.2 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 250 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
Through detection, the relative number average molecular weight of the high-temperature resistant bio-based copolyester is 28500g/mol, the relative weight average molecular weight is 48300g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of ethylene glycol is 80: the glass transition temperature of the copolyester was 121 ℃. The test shows that the tensile strength of the bio-based copolyester is 86.2MPa, and the tensile modulus is 2503 MPa.
Example 5:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.2mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.2mol of 1, 4-butanediol were charged into the polymerization reactor, followed by 0.25% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 200 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.2 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.2 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 240 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
Through detection, the relative number average molecular weight of the high-temperature-resistant bio-based copolyester is 29300g/mol, the relative weight average molecular weight is 48900g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 4-butanediol is 80: the glass transition temperature of the copolyester was 117 ℃. The test shows that the tensile strength of the bio-based copolyester is 85.7MPa, and the tensile modulus is 2430 MPa.
Example 6:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.1mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.3mol of 1, 6-hexanediol were charged into a polymerization reactor, followed by 0.2% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 190 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.15 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.15 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 230 ℃, and reacting for 5.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 24700g/mol, the relative weight average molecular weight is 45300g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 6-hexanediol is 40: the glass transition temperature of the copolyester was 90 ℃. Tests show that the tensile strength of the bio-based copolyester is 80.5MPa, and the tensile modulus is 2130 MPa.
Example 7:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.15mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.25mol of 1, 6-hexanediol were charged into the polymerization reactor, followed by 0.2% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 190 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.22 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.25 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 230 ℃, and reacting for 5.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 23700g/mol, the relative weight average molecular weight is 44700g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 6-hexanediol is 60: 40, the glass transition temperature of the copolyester was 103 ℃. The test proves that the tensile strength of the bio-based copolyester is 82.3MPa, and the tensile modulus is 2204 MPa.
Example 8:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.2mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.2mol of 1, 10-decanediol were charged into the polymerization reactor, followed by 0.23% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 180 ℃ for 5.0 hours under an inert atmosphere to obtain a first intermediate product.
To the first intermediate product, 0.21% of triphenyl phosphate based on the molar mass of dimethyl 2, 5-furandicarboxylate and 0.23% of antioxidant-1010 based on the theoretical yield of the polymer were added, the vacuum degree was gradually reduced to below 100Pa, the temperature was gradually raised to 225 ℃, and the reaction was carried out for 4.0 hours to obtain a bio-based copolyester.
Through detection, the relative number average molecular weight of the bio-based copolyester is 22300g/mol, the relative weight average molecular weight is 43900g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 10-decanediol is 80: the glass transition temperature of the copolyester was 92 ℃. The test proves that the tensile strength of the bio-based copolyester is 79.5MPa, and the tensile modulus is 2053 MPa.
Example 9:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.22mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.18mol of 1, 10-decanediol were charged into the polymerization reactor, followed by 0.3% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 185 ℃ for 5.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.25 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.3 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 230 ℃, and reacting for 5.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester 23100g/mol and the relative weight average molecular weight of 42800g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 10-decanediol is 88: 12, the glass transition temperature of the copolyester was 104 ℃. The test proves that the tensile strength of the bio-based copolyester is 82.1MPa, and the tensile modulus is 2201 MPa.
Example 10:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.1mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.3mol of 1, 4-cyclohexanedimethanol were added to the polymerization reactor, followed by 0.35% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 210 ℃ for 5.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.25 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.3 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 250 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 24700g/mol, the relative weight average molecular weight is 43600g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 4-cyclohexanedimethanol is 40: 60, the glass transition temperature of the copolyester was 116 ℃. The test proves that the tensile strength of the bio-based copolyester is 87.2MPa, and the tensile modulus is 2312 MPa.
Example 11:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.15mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.25mol of 1, 4-cyclohexanedimethanol were added to the polymerization reactor, followed by 0.4% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 210 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
To the first intermediate product, 0.28% of triphenyl phosphate based on the molar mass of dimethyl 2, 5-furandicarboxylate and 0.32% of antioxidant-1010 based on the theoretical yield of the polymer were added, the vacuum degree was gradually reduced to below 100Pa, the temperature was gradually raised to 255 ℃, and the reaction was carried out for 6.0 hours to obtain bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester 23100g/mol and the relative weight average molecular weight of 42500g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 4-cyclohexanedimethanol is 60: 40, the glass transition temperature of the copolyester was 122 ℃. The test proves that the tensile strength of the bio-based copolyester is 87.5MPa, and the tensile modulus is 2432 MPa.
Example 12:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.1mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.3mol of neopentyl glycol were charged into a polymerization reactor, followed by 0.32% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 190 ℃ for 5.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.23 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.25 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 240 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 21200g/mol, the relative weight average molecular weight is 41100g/mol, and the molar ratio of the structural unit of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of the neopentyl glycol is 40: the glass transition temperature of the copolyester was 103 ℃. The test proves that the tensile strength of the bio-based copolyester is 83.5MPa, and the tensile modulus is 2227 MPa.
Example 13:
0.25mol of dimethyl 2, 5-furandicarboxylate, 0.15mol of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 0.25mol of neopentyl glycol were charged into a polymerization reactor, followed by 0.35% of tetrabutyl titanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 190 ℃ for 6.0 hours under an inert atmosphere to obtain a first intermediate product.
To the first intermediate product, 0.25% of triphenyl phosphate based on the molar mass of dimethyl 2, 5-furandicarboxylate and 0.28% of antioxidant-1010 based on the theoretical yield of the polymer were added, the vacuum degree was gradually reduced to below 100Pa, the temperature was gradually raised to 240 ℃, and the reaction was carried out for 6.0 hours to obtain bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 23700g/mol, the relative weight average molecular weight is 44500g/mol, and the molar ratio of the structural unit of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of the neopentyl glycol is 60: 40, the glass transition temperature of the copolyester was 120 ℃. The test proves that the tensile strength of the bio-based copolyester is 83.8MPa, and the tensile modulus is 2234 MPa.
Comparative example 1:
46.0g (0.25mol) of dimethyl 2, 5-furandicarboxylate, 0.4mol of ethylene glycol were charged into the polymerization reactor, followed by 0.15% of tetrabutyltitanate based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 180 ℃ for 4.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.12 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.1 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 240 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
The relative number average molecular weight of the bio-based copolyester is 27900g/mol, the relative weight average molecular weight is 48100g/mol, and the glass transition temperature of the copolyester is 87 ℃. The test shows that the tensile strength of the bio-based copolyester is 70.9MPa, and the tensile modulus is 1734 MPa.
As can be seen from the comparative analysis of comparative example 1 and other examples, in comparative example 1, copolymerization without adding bis [4- (2-hydroxyethoxy) phenyl ] sulfone can obtain a bio-based copolyester with poor molecular chain rigidity, and the glass transition temperature of the bio-based copolyester material is only 87 ℃. Meanwhile, the copolyester material has poor mechanical properties and low tensile strength and tensile modulus.
Comparative example 2:
46.0g (0.25mol) of dimethyl 2, 5-furandicarboxylate, 6.8g (0.02mol) of bis [4- (2-hydroxyethoxy) phenyl ] sulfone and 29.3g (0.325mol) of 1, 4-butanediol were charged into a polymerization reactor, followed by 0.15% of tetrabutyltitanate, based on the molar amount of dimethyl 2, 5-furandicarboxylate. The reaction was carried out at 180 ℃ for 4.0 hours under an inert atmosphere to obtain a first intermediate product.
And adding 0.12 percent of triphenyl phosphate based on the molar weight of dimethyl 2, 5-furandicarboxylate and 0.1 percent of antioxidant-1010 based on the theoretical yield of the polymer into the first intermediate product, gradually reducing the vacuum degree to be below 100Pa, gradually raising the temperature to 220 ℃, and reacting for 6.0 hours to obtain the bio-based copolyester.
According to detection, the relative number average molecular weight of the bio-based copolyester is 28300g/mol, the relative weight average molecular weight is 47500g/mol, and the molar ratio of the structural unit of bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the structural unit of 1, 4-butanediol is 30: 70, the glass transition temperature of the copolyester is 63 ℃. Through detection, the tensile strength of the bio-based copolyester is 71.3MPa, and the tensile modulus is 1767 MPa.
As can be seen from comparative example 2, comparative example 2 has a lower content of added bis [4- (2-hydroxyethoxy) phenyl ] sulfone, and therefore, the molecular chain of the obtained bio-based copolyester has insufficient rigidity, and the glass transition temperature of the bio-based copolyester material is only 63 ℃. Meanwhile, the copolyester material has poor mechanical properties and low tensile strength and tensile modulus.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A bio-based copolyester, wherein the structural formula of the bio-based copolyester is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
the glass transition temperature of the bio-based copolyester is 90-122 ℃.
2. A method of preparing the bio-based copolyester of claim 1, comprising:
(1) mixing 2, 5-furandicarboxylic acid or an esterified product thereof, bis [4- (2-hydroxyethoxy) phenyl ] sulfone, dihydric alcohol and an esterification catalyst, and carrying out an esterification reaction to obtain a first intermediate product, wherein the structural formula of the bis [4- (2-hydroxyethoxy) phenyl ] sulfone is shown as the following formula (2):
(2) performing polycondensation reaction on the first intermediate product to obtain the bio-based copolyester, wherein the structural formula of the bio-based copolyester is shown as the following formula (1):
wherein x and y are both integers of 1-20, z is an integer of 20-100, and-R-comprises at least one of the following structural formulas:
3. the method of claim 2, wherein the molar ratio of 2, 5-furandicarboxylic acid or an esterified product thereof to bis [4- (2-hydroxyethoxy) phenyl ] sulfone is 1: (0.1-0.9).
4. The method for preparing bio-based copolyester according to claim 3, wherein the molar ratio of the sum of the amounts of the diol and the bis [4- (2-hydroxyethoxy) phenyl ] sulfone to the 2, 5-furandicarboxylic acid or the esterified product thereof is (1.1-2.2): 1.
5. the method of claim 2, wherein the diol comprises at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol, and monoethylene glycol.
6. The preparation method of bio-based copolyester according to claim 2, wherein the esterification reaction temperature in step (1) is 160 ℃ to 220 ℃ and the reaction time is 2 hours to 6 hours.
7. The method for preparing bio-based copolyester according to claim 2, wherein the polycondensation reaction in step (2) is performed in a vacuum environment at 220 ℃ to 300 ℃ for 2 hours to 6 hours.
8. The method for preparing bio-based copolyester according to claim 7, wherein vacuum degree of the vacuum environment is not higher than 300 Pa.
9. The method for preparing bio-based copolyester according to claim 2, wherein at least one of polycondensation catalyst, stabilizer and antioxidant is further added in the step (2).
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