CN109503817B - Biodegradable poly (ethylene succinate-co-ethylene oxalate) ester and preparation method thereof - Google Patents
Biodegradable poly (ethylene succinate-co-ethylene oxalate) ester and preparation method thereof Download PDFInfo
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Abstract
本发明提供了一种生物降解性聚（丁二酸乙二醇‑co‑草酸乙二醇）酯及其制备方法，所述制备方法是采用廉价的生物基材料——草酸、丁二酸与乙二醇为原料，在较高的酯化温度（180~200℃）下发生酯化反应，得到较多具有端基草酸乙二醇酯羟基的聚体，然后在220~230℃发生熔融缩聚，制备得到高分子量的生物降解性聚（丁二酸乙二醇‑co‑草酸乙二醇）酯，同时得到了0.05~0.3g/mL的草酸水溶液，其可以作为副产品直接使用，或者除去水继续作为原料使用。本发明的制备方法不仅提高了缩聚反应的速率，使聚合反应时间大幅度缩短，而且得到了高分子量的聚酯，产物的特性粘数高，色泽好，结晶速率快，提高了共聚酯的加工成型性能，有利于材料的生产。The present invention provides a biodegradable poly(ethylene succinate-co-ethylene glycol oxalate) ester and a preparation method thereof. The preparation method adopts inexpensive bio-based materials - oxalic acid, succinic acid and Ethylene glycol is used as raw material, and esterification reaction occurs at higher esterification temperature (180~200℃) to obtain more polymers with terminal ethylene glycol oxalate hydroxyl groups, and then melt polycondensation occurs at 220~230℃ , to prepare high molecular weight biodegradable poly(ethylene glycol succinate-co-ethylene glycol oxalate) ester, and at the same time obtain 0.05~0.3g/mL oxalic acid aqueous solution, which can be used directly as a by-product, or remove water Continue to use as raw material. The preparation method of the invention not only improves the rate of the polycondensation reaction, greatly shortens the polymerization reaction time, but also obtains a high molecular weight polyester, the product has high intrinsic viscosity, good color and lustre, and the crystallization rate is fast, and the copolyester is improved. The processing and forming properties are beneficial to the production of materials.
Description
Technical Field
The invention relates to biodegradable copolyester and a preparation method thereof, in particular to biodegradable poly (ethylene succinate-co-ethylene oxalate) ester and a preparation method thereof.
Background
Polyethylene succinate (PES) is a semi-crystalline aliphatic polyester, has a glass transition temperature of about-10 ℃ and a melting point of about 102 ℃, is a polymer with a higher melting point in the aliphatic polyester, is second only to polybutylene succinate (PBS), and has a biodegradation rate higher than that of the PBS. PES with high molecular weight has mechanical strength similar to that of low-density polyethylene and polypropylene, and can be used directly instead of general-purpose plastics. PES has low price, high melting point, good biodegradability and great development potential.
The PES synthesis method mainly comprises a solution polycondensation method, a polycondensation chain extension method and a direct polycondensation method.
The solution polycondensation method can synthesize PES with higher relative molecular weight, but the reaction speed is slow, the solvent needs to be recovered, the production cost is high, and the practical application is difficult to obtain. Sunjie et al synthesized PES with high relative molecular weight by solution polymerization using decalin as solvent,M n =49000，M w =127000, but the polycondensation reaction time was 12-14 hours.
The polycondensation chain extension method is a method capable of synthesizing PES with high relative molecular mass in a short time under mild operation conditions. CN101628972 discloses a preparation method of polyethylene glycol succinate, which takes succinic acid and ethylene glycol as raw materials, adds a high boiling point solvent, finally removes the solvent to obtain an oligomer, and then takes diisocyanate, binary acyl chloride or binary anhydride as a chain extender to prepare polyester with the number average molecular weight of more than 20 ten thousand. However, since the chain extender (such as diisocyanate) used has high toxicity, the amount of the chain extender needs to be strictly controlled in order to reduce the residue in the product, and the purification process is complicated, which causes inconvenience in actual production.
The direct polycondensation method is simpler in equipment and process, but requires Sb2O3With GeO2As a catalyst. Sb2O3Easy decomposition and more addition amount, thereby enabling the product to have darker color; GeO2Expensive and not suitable for industrialization.
As the synthesis method of PES is either too long in reaction time, complex in process or high in cost, the PES is not suitable for industrial scale production, and the high molecular weight PES product is not industrialized at present. In addition, the crystallization rate of PES products prepared by the existing method is too low, which is not beneficial to molding processing, and further limits the development of PES. Therefore, it is an object of the industry and academia to develop a method for rapidly preparing high molecular weight PES and to provide PES products with high crystallization rates without increasing costs.
Disclosure of Invention
The invention aims to provide biodegradable poly (ethylene succinate-co-ethylene oxalate) ester and a preparation method thereof, so as to shorten the polymerization reaction time and improve the crystallization rate and the processing and forming performance of products.
The purpose of the invention is realized as follows:
a biodegradable poly (ethylene succinate-co-ethylene oxalate) ester has a molecular chain structure shown in formula (I):
in the formula, x is the polymerization degree of the polyethylene glycol oxalate in the repeating structure, y is the polymerization degree of the polyethylene glycol succinate in the repeating structure, n represents the number of the repeating structure, nx = 0-2, and ny = 120-200;
the terminal group A and the terminal group B are both selected from any one of EOX and EBS, and the terminal group A and the terminal group B are the same or different;
EOX is
EBS is
，
And in the poly (ethylene succinate-co-ethylene oxalate) ester, the number ratio of two end groups
(ii) a The number average molecular weight of the ester is calculated according to the nuclear magnetic hydrogen spectrum after purificationM n = 1.7×104~3.0×104Intrinsic viscosity [ eta ]]>0.9。
The preparation method of the biodegradable poly (ethylene succinate-co-ethylene oxalate) ester comprises the following steps:
(1) adding a raw material, a catalyst and an antioxidant into a reaction kettle, wherein the raw material is a mixture of succinic acid, oxalic acid and ethylene glycol according to a molar ratio of 23: m: n, m is more than or equal to 2.40 and less than 5.34, and n =1.2(23+ m); the catalyst is a mixture of tetrabutyl titanate, zinc acetate and antimony trioxide, and the antioxidant is triphenyl phosphate;
(2) reacting under normal pressure under the protection of nitrogen, wherein the reaction temperature is 180-200 ℃;
(3) heating to 220-230 ℃, reducing the pressure to 50-100Pa, and continuing the reaction;
(4) after the reaction is finished, discharging under the protection of nitrogen, and cooling to room temperature to obtain the biodegradable poly (ethylene succinate-co-ethylene oxalate) ester.
In the step (1), the molar ratio of the succinic acid to the oxalic acid to the ethylene glycol is 23:3.9: 32.3.
In the step (1), the using amount of the tetrabutyl titanate is 0.5-1 wt%, and preferably 1 wt%; the amount of the triphenyl phosphate is 1-2 wt%, preferably 1.5 wt%; the mass ratio of tetrabutyl titanate, zinc acetate and antimony trioxide is preferably 1: 3: 1.
In the step (2), the reaction time is 3-4 h, preferably 3.5 h.
In the step (3), the reaction time is 3-6 h, preferably 4.5 h.
The invention adopts cheap bio-based materials, namely oxalic acid, succinic acid and ethylene glycol, as raw materials, and performs esterification reaction at a higher esterification temperature (180-200 ℃) to obtain a polymer with more terminal group ethylene glycol oxalate hydroxyl groups, and then performs melt polycondensation at 220-230 ℃, and limits the oxalic acid dosage within a specific range to prepare the modified copolyester with high molecular weight. Meanwhile, 0.05-0.3 g/mL of oxalic acid aqueous solution is obtained, and the oxalic acid aqueous solution can be directly used as a byproduct or can be continuously used as a raw material after water is removed.
The reaction mechanism of the invention is as follows:
esterification reaction is carried out to obtain the m-polymer P with the end group of the hydroxyl of the glycol oxalatemAnd n-mer P having terminal hydroxyl groups of ethylene succinaten，PmAnd PnThe ester exchange reaction is carried out, the oxygen atom on the hydroxyl 2 attacks the carbonyl carbon atom a or b on the oxalic acid group to form the (m + n) polymer Pm+nThe reaction formula is shown below.
The crystallization mechanism of the copolyester obtained by the invention is as follows:
during the gradual cooling of the highly oriented melt, different polyethylene glycol oxalate (PEOX) blocks (mainly blocks at the end positions) in the copolyester can spontaneously aggregate to generate phase separation and crystallize within the temperature range of 80-130 ℃; when the temperature continues to decrease and reaches the crystallization temperature interval of polyethylene succinate (PES) blocks (20-80 ℃), PEOX crystals as heterogeneous nuclei accelerate crystallization of PES, and the crystallization process is schematically shown in FIG. 7.
The preparation method of the invention not only improves the speed of polycondensation reaction and greatly shortens the time of polymerization reaction, but also obtains the polyester with high molecular weight, has high intrinsic viscosity and high crystallization speed of the product, improves the processing and forming performance of the copolyester, and is beneficial to the production and processing of materials.
In the preparation method, the dosage of the catalyst antimony trioxide is not more than 1 wt%, and the obtained product has good color.
Drawings
FIG. 1 is a photograph of an actual implementation of the copolyesters prepared in comparative example 1, example 1 and example 2, wherein the copolyester of comparative example 1 is on the left, the copolyester of example 1 is in the middle, and the copolyester of example 2 is on the right.
FIG. 2 is a drawing showing the preparation of copolyesters according to examples 1 and 21H NMR spectrum, in which A represents example 1 and B represents example 2.
FIG. 3 is a DSC temperature rise profile of the copolyester.
FIG. 4 is a cooling curve of the copolyester.
FIG. 5 is a plot of isothermal crystallization of copolyesters at 75 deg.C, where plot 0 represents comparative example, plot 1 represents example 1, plot 2 represents example 2, and plot 3 represents example 3.
FIG. 6 is a tensile curve of a copolyester, where curve 0 represents comparative example, curve 1 represents example 1, curve 2 represents example 2, and curve 3 represents example 3.
FIG. 7 is a schematic representation of the crystallization process of the copolyester.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
The raw materials used in the following examples were analytically pure, the purity was 99%, triphenyl phosphate and succinic acid were purchased from mclin corporation; ethylene glycol is purchased from Aladdin company, oxalic acid (containing two crystal waters) is purchased from Beichen Square reagent factory in Tianjin city; zinc acetate is purchased from the development center of Mi Europe chemical reagent in Tianjin; antimony trioxide was purchased from chemical reagent III, Tianjin.
Example 1
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 6.7g (0.053 mol) of oxalic acid (containing two crystal waters), 41.7g (0.673 mol) of ethylene glycol, 0.067g of tetrabutyl titanate serving as a catalyst, 0.200g of zinc acetate, 0.067g of antimony trioxide and 0.100g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2h under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ for reacting for 1h at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 1 h; finally, the temperature is increased to 230 ℃, the reaction is continued for 5h under the pressure of 50-100Pa, the discharge is protected by nitrogen, and the reaction product is cooled to room temperature with the yield of 94% (relative to the theoretical content of PES formed by adding succinic acid, the same applies below).
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 0.7mol percent; 2) a pale yellow solid in appearance; 3) intrinsic viscosity [ eta ]]= 1.05; 4) melting point 102 deg.C, crystallizing temperature 38 deg.C, and enthalpy change of crystallization 6J.g-1(ii) a 5) The tensile strength is 50 +/-2 MPa, and the elongation at break is 1380 +/-110%.
Example 2
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 10.3g (0.081 mol) of oxalic acid (containing two crystal waters), 43.8g (0.707 mol) of ethylene glycol, 0.070g of tetrabutyl titanate serving as a catalyst, 0.211g of zinc acetate, 0.070g of antimony trioxide and 0.105g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2h under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ for reacting for 1h at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 1 h; finally, the temperature is raised to 230 ℃, the reaction is continued for 4.5 hours under the pressure of 50-100Pa, the materials are discharged under the protection of nitrogen, and the reaction product is cooled to the room temperature, and the yield of the reaction product is 98 percent.
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 2.3mol percent; 2) a pale yellow solid in appearance; 3) intrinsic viscosity [ eta ]]= 1.15; 4) melting point 104 ℃, crystallization temperature 44 ℃, and crystallization enthalpy change 16J.g-1(ii) a 5) The tensile strength is 48 plus or minus 2MPa, and the elongation percentage at break is 1050 plus or minus 110.
Example 3
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 10.9g (0.086 mol) of oxalic acid (containing two crystal waters), 44.2g (0.713 mol) of ethylene glycol, 0.071g of tetrabutyl titanate serving as a catalyst, 0.214g of zinc acetate, 0.071g of antimony trioxide and 0.106g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2.5h under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ for reacting for 1h at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; finally, the temperature is raised to 230 ℃, the reaction is continued for 2.5 hours under the pressure of 50-100Pa, the materials are discharged under the protection of nitrogen, and the reaction product is cooled to the room temperature, and the yield of the reaction product is 98 percent.
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 3.3 mol percent; 2) a nitrogen yellow solid in appearance; 3) intrinsic viscosity of [. eta. ]]= 0.98; 4) melting point 105 deg.C, crystallization temperature 47 deg.C, and crystallization enthalpy change 45 J.g-1(ii) a 5) The tensile strength is 48 plus or minus 2MPa, and the elongation at break is 960 plus or minus 85 percent.
Example 4
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 11.4g (0.090 mol) of oxalic acid (containing two crystal waters), 44.5g (0.718 mol) of ethylene glycol, 0.071g of tetrabutyl titanate serving as a catalyst, 0.214g of zinc acetate, 0.071g of antimony trioxide and 0.107g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2.5h under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ for reacting for 1h at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; finally, the temperature is raised to 230 ℃, the reaction is continued for 2.5 hours under the pressure of 50-100Pa, the materials are discharged under the protection of nitrogen, and the reaction product is cooled to the room temperature, and the yield of the reaction product is 98 percent.
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 3.8 mol percent; 2) a nitrogen yellow solid in appearance; 3) intrinsic viscosity of [. eta. ]]= 0.96; 4) melting point 105 deg.C, crystallization temperature 47 deg.C and 60 deg.C, and crystallization enthalpy change 45 J.g-1(ii) a 5) The tensile strength is (48 +/-2) MPa, and the elongation at break is (1050 +/-110)%.
Example 5
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 12g (0.095 mol) of oxalic acid (containing two crystal waters), 44.9g (0.724 mol) of ethylene glycol, 0.072g of tetrabutyl titanate serving as a catalyst, 0.216g of zinc acetate, 0.072g of antimony trioxide and 0.108g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2.5h under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ for reacting for 1h at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; finally, the temperature is raised to 230 ℃, the reaction is continued for 2.5 hours under the pressure of 50-100Pa, the materials are discharged under the protection of nitrogen, and the reaction product is cooled to the room temperature, and the yield of the reaction product is 98 percent.
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 4.0 mol percent; 2) a nitrogen yellow solid in appearance; 3) intrinsic viscosity of [. eta. ]]= 0.94; 4) melting point 105 deg.C, crystallizing temperature 60 deg.C, and crystallization enthalpy change 35 J.g-1(ii) a 5) The tensile strength is 43 plus or minus 2MPa, and the elongation percentage at break is 1130 plus or minus 110 percent.
Example 6
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 15.0g (0.118 mol) of oxalic acid (containing two crystal water), 46.6g (0.751 mol) of ethylene glycol, 0.075g of tetrabutyl titanate serving as a catalyst, 0.225g of zinc acetate, 0.075g of antimony trioxide and 0.112g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 3 hours under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ and reacting for 1 hour at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; and finally, heating to 230 ℃, continuously reacting for 4 hours under the pressure of 50-100Pa, discharging under the protection of nitrogen, and cooling to room temperature, wherein the yield of the reactant is 102%.
The synthesized PES copolyester product has the following structure and properties: 1) the content of the terminal oxalic acid group is 4.3 mol percent; 2) a nitrogen yellow solid in appearance; 3) intrinsic viscosity of [. eta. ]]= 0.91; 4) melting point 101 deg.C, crystallization temperature 42 deg.C, and crystallization enthalpy change 16J.g-1(ii) a 5) The tensile strength is 34 plus or minus 1MPa, and the elongation percentage at break is 750 plus or minus 50.
Example 7
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 6.0g (0.0474 mol) of oxalic acid (containing two crystal waters), 41.3g (0.666 mol) of ethylene glycol, 0.066g of tetrabutyl titanate serving as a catalyst, 0.198g of zinc acetate, 0.066g of antimony trioxide and 0.099g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 3 hours under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ and reacting for 1 hour at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; and finally, heating to 230 ℃, continuously reacting for 6h under the pressure of 50-100Pa, discharging under the protection of nitrogen when the rod climbing (the phenomenon of judging the reaction is finished), and cooling to room temperature, wherein the color of the copolyester is dark yellow.
Example 8
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 17.0g (0.134 mol) of oxalic acid (containing two crystal water), 47.8g (0.771 mol) of ethylene glycol, 0.077g of tetrabutyl titanate serving as a catalyst, 0.231g of zinc acetate, 0.077g of antimony trioxide and 0.116g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 3 hours under normal pressure at a nitrogen flow rate of 20 mL/min, then heating to 200 ℃ and reacting for 1 hour at a nitrogen flow rate of 100-200 mL/min; then heating to 220 ℃, starting to reduce the pressure to 50-100Pa, and reacting for 2 h; and finally, heating to 230 ℃, continuously reacting for 6h under the pressure of 50-100Pa, discharging under the protection of nitrogen when the pole climbing (the phenomenon of judging the end of the reaction) is not reached, and cooling to room temperature, wherein the color of the copolyester is dark yellow, and the yield is 89%, and is low.
Comparative example 1
Adding 60.0g (0.508 mol) of succinic acid serving as a reaction raw material, 40.9g (0.660 mol) of ethylene glycol, 0.24g of antimony trioxide serving as a catalyst and 0.18g of triphenyl phosphate serving as an antioxidant into a reaction kettle; heating to 180 ℃ under the protection of nitrogen, starting stirring, reacting for 2h under normal pressure, then heating to 200 ℃ and reacting for 1h, wherein the nitrogen flow rate is 20 mL/min; and then heating to 230 ℃, starting to reduce the pressure to 50-100Pa, continuing to react for 5 hours, discharging under the protection of nitrogen, and cooling to room temperature, wherein the yield of the reactant is 96%.
The synthesized PES product has the following structure and properties: 1) a dark yellow solid in appearance; 2) intrinsic viscosity [ eta ]]= 0.92; 3) melting point of 103 deg.C, crystallization temperature of 40 deg.C, and crystallization enthalpy change of 3J.g-1(ii) a 4) The tensile strength is 44 +/-2 MPa, and the elongation at break is 850 +/-80%.
And carrying out structural characterization and performance test on the obtained product. Note: dissolving a sample used for measuring the intrinsic viscosity by using chloroform, precipitating by using a large amount of methanol, and repeating for many times to remove small molecules; none of the samples tested were purified.
And (3) nuclear magnetic hydrogen spectrum characterization: an AvIII model nuclear magnetic resonance spectrometer (600 MHz, Bruker BioSpin Co., Germany) was used with deuterated chloroform (CDCl)3) The nuclear magnetic hydrogen spectra of the copolyesters prepared in example 1 and example 2 were determined using TMS as an internal standard as a solvent (1H NMR), the results are shown in fig. 2.
From FIG. 2, the areas of hydrogen represented at d and c (b + c + e + f) are almost equal, and it can be concluded that the content of ethylene glycol in the polymer backbone is almost the same as the content of succinic acid, indicating that PES segments are almost all in the polymer backbone and oxalic acid units are almost not in the backbone, i.e., the PEOX segments are mostly at the terminal positions.
In addition, comparing the spectra of the products obtained in example 1 and example 2, as the amount of oxalic acid added increases (the amount of oxalic acid added in example 2 is greater than that in example 1), the area ratio of a to g representing hydrogen increases, i.e., the molar ratio of the terminal ethylene oxalate ester groups of the product to the terminal ethylene succinate ester groups increases, and the corresponding polycondensation reaction time decreases. When the added oxalic acid amount is lower than the lower boundary value or higher than the upper boundary value, the reaction time is prolonged, and no high molecular weight polymer can be obtained within 6 hours.
Determination of intrinsic viscosity [ η ]: intrinsic viscosity measurements were performed on the copolyesters prepared in examples 1 to 6 and comparative example 1 using an Ubbelohde viscometer (DC9V/0, Schott Co., Germany) at a chloroform solution concentration of 0.01 g/mL and a test temperature of (25. + -. 0.1) ℃ with the test results shown in Table 1.
Characterization of melt crystallization behavior: the melting and crystallization behavior of the copolyesters prepared in examples 1-6 and comparative example 1 was characterized using a Differential Scanning Calorimetry (DSC) instrument (Perkine-Elmer DSC8000, USA). The weight of the sample was about 5 mg. Firstly, heating the copolyester from room temperature to 130 ℃ at a heating rate of 60 ℃/min, then cooling to-30 ℃ at a cooling rate of 60 ℃/min, eliminating the thermal history, and then heating to 130 ℃ at a heating rate of 10 ℃/min to obtain a heating curve of a sample, as shown in figure 3; then, the temperature is reduced to minus 30 ℃ at the temperature rise rate of 10 ℃/min to obtain the temperature reduction curve of the sample, as shown in figure 4; repeating the procedure for three times, then reducing the temperature to 75 ℃ at a cooling rate of 10 ℃/min, and maintaining the temperature at 75 ℃ until the sample crystallization is finished to obtain isothermal crystallization curves of samples of examples 1-3 and comparative examples, as shown in fig. 5; the crystallization temperature and enthalpy change are shown in table 1.
As can be seen from FIG. 4, in the DSC curve of each sample, the comparative example hardly observed a crystallization peak, and examples 1 to 6 observed a distinct crystallization peak (T)c) This shows that examples 1-6, which contain terminal polyethylene oxalate blocks, crystallize more readily when the melt is cooled than the comparative examples.
As can be seen from FIG. 5, at 75 deg.C, the time required for the comparative example to complete crystallization from the start of crystallization is about 55min, that of example 1 is about 40min, that of example 2 is about 20min, that of example 3 is about 8min (the time required for crystallization is the shortest), and that of examples 1-3, the time required for completing crystallization is gradually shortened, indicating that the crystallization rate of the copolyester is gradually increased.
And (3) tensile property characterization: the injection molding temperature is 140 ℃, the film forming temperature is 25 ℃, and the copolyesters prepared in example 1, example 2 and comparative example 1 are made into standard dumbbell-shaped sample bars. The tensile property of the material is tested by a universal tester according to GB/T-1040-. The resulting tensile curve is shown in FIG. 6, and the tensile strength and tensile elongation are shown in Table 1.
Table 1: summary of product Properties
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