Butenediol-based polyester elastomer and production method

Abstract

The present invention provides a butenediol-based polyester elastomer and a method for producing the same, the structure of which is as follows: [Formula 1] TIFF2023510414000012.tif127170In this invention, 1,4-butenediol, which contains a highly stable double bond, is used instead of itaconic acid to synthesize a series of butenediol-based polyester elastomers with high molecular weights and narrow molecular weight distributions.The high relative molecular weights and narrow relative molecular weight distributions make it easier to control crosslinking in subsequent processing, and the amount of vulcanizing agent used is equivalent to that of conventional rubber.

Description

[Technical field]

[0001] The present invention relates to the technical field of polymeric materials, and more particularly to butenediol-based polyester elastomers and methods for producing same. [Background technology]

[0002] Polyester is a kind of degradable polymer, and related research has been actively conducted in the field of polymer materials, attracting great attention. At present, the annual production volume of the polyester industry has already reached 10 million tons, but its use is limited to plastics, fibers, etc., and its use in the rubber field has been very little. In response to the concept of "bio-based engineering elastomer" proposed in 2008, Beijing University of Chemical Technology has proposed and synthesized many bio-based polyester elastomer materials in advance, expanding the application fields of polyester.

[0003] The polyester elastomer is designed as follows: A monomer containing a carbon-carbon double bond is introduced to destroy the crystallization behavior of the polyester molecular chain by multi-component copolymerization and provide reactive sites for the subsequent polyester elastomer crosslinking. However, in the polyester elastomer products developed so far, the monomer providing the double bond is limited to dibasic acid, especially itaconic acid. For example, patent CN101450985B discloses a polyester-type bioengineering rubber and its manufacturing method, and itaconic acid is still used as the double bond donor in the subsequent chemical crosslinking. On the other hand, the reactivity of the double bond in itaconic acid is very high, there is a risk of gelation in the polycondensation stage, and the relative molecular weight distribution of the sample is relatively wide. In addition, when using peroxide for crosslinking, the crosslinking reaction speed is very fast and the amount of crosslinking agent used is very small, so the degree of crosslinking cannot be well controlled.

[0004] Therefore, a new polyester elastomer should be developed. Summary of the Invention

[0005] In order to solve the problems in the prior art, the present invention provides a butenediol-based polyester elastomer and a manufacturing method thereof. In the present invention, 1,4-butenediol containing a highly stable double bond is used instead of itaconic acid to synthesize a series of butenediol-based polyester elastomers with high molecular weight and narrow distribution. The reason for the high relative molecular weight and narrow relative molecular weight distribution is that 1,4-butenediol has very high stability in the high-temperature polycondensation process and does not cause side reactions like itaconic acid (broadening the molecular weight distribution of the product). In addition, crosslinking is easier to control in the subsequent processing process, and the amount of vulcanizing agent used is the same as that of conventional rubber.

[0006] A first object of the present invention is to provide a butenediol-based polyester elastomer.

[0007] The structure of the butenediol-based polyester elastomer is as follows: [ka] R m1 , R m2 is a branched or unbranched chain alkyl group, R m1 , R m2 may be the same or different. Here, m1 and m2 represent the numbers of carbon atoms, and are 2≦m1≦14. Preferably, 2≦m1≦10 and 2≦m2≦14. Preferably, 2≦m2≦10. m1 and m2 may be equal or unequal. R n1 , R n2 is a branched or unbranched chain alkyl group, R n1 , R n2 may be the same or different. Here, n1 and n2 represent the numbers of carbon atoms, and are 2≦n1≦12, preferably 2≦n1≦8 and 2≦n2≦12. Preferably, 2≦n2≦8. n1 and n2 may be equal or unequal. x and y are integers of 1 to 3, and x and y may or may not be equal.

[0008] a, b, c, d, e, f, g, h, i, j, k, l, m, n, and o indicate the degree of polymerization. Among them, a, c, m, and o cannot be 0 at the same time. e and k cannot be 0 at the same time. The rest can be 0 at the same time.

[0009] A second object of the present invention is to provide a method for producing a butenediol-based polyester elastomer according to the first object of the present invention, which comprises an esterification reaction and a polymerization reaction of a diol, a dibasic acid and / or a lactic acid, an antioxidant, and a polymerization inhibitor under the action of a catalyst to obtain a butenediol-based polyester elastomer. The diol may be 1,4-butenediol or another diol. The other diol may be HO-R m -OH, diethylene glycol, triethylene glycol, tetraethylene glycol or a combination thereof. Here, R m is a branched or unbranched chain alkyl group, where m represents the number of carbon atoms and 2≦m≦14. Preferably, 2≦m≦10. The dibasic acid is HOOC-R n -COOH or a combination thereof. Here, R n is a branched or unbranched chain alkyl group, where n represents the number of carbon atoms and 2≦n≦12, preferably 2≦n≦8.

[0010] Here, the molar percentage of the diol occupying 1,4-butenediol is preferably 2 to 60%, and more preferably 5 to 30%.

[0011] The catalyst may be a conventional catalyst in the prior art, and in the present invention, selenium dioxide, antimony trioxide, ethylene glycol antimony, p-toluenesulfonic acid, acetate, alkylaluminum having 1 to 12 carbon atoms, organotin compounds, titanate esters, or a combination thereof are preferred. Since polyester products have the problem of heavy metals remaining, titanate ester catalysts that do not contain heavy metal elements are preferred, such as tetrabutyl titanate and tetraisopropyl titanate. The catalyst may be added in the esterification section or the pre-polycondensation section, and the amount of catalyst used is 0.02 to 0.5% of the total mass of the diol, dibasic acid, and / or lactic acid.

[0012] The antioxidant may be a conventional antioxidant used in the prior art, and in the present invention, a phosphoric acid or phosphorous acid compound is preferred, and preferably one or two of phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester, phenyl phosphate, and phenyl phosphite. The amount of the antioxidant used is 0.01 to 0.2% of the total mass of the diol, dibasic acid, and / or lactic acid, and preferably 0.04 to 0.08%. As the polymerization inhibitor, a conventional polymerization inhibitor in the prior art can be used, and in the present invention, a phenol polymerization inhibitor, an ether polymerization inhibitor, a quinone polymerization inhibitor, or an aromatic amine polymerization inhibitor is preferred, and preferably, one or two of hydroquinone, 4-tert-butylpyrocatechol, 4-methoxyphenol, benzoquinone, diphenylamine, and p-phenylenediamine are used. The amount of the polymerization inhibitor used is 0.01 to 0.5% of the total mass of the diol, dibasic acid, and / or lactic acid. It is preferably 0.05 to 0.2%.

[0013] The alcohol / acid molar ratio of diol, dibasic acid and / or lactic acid is 1.05:1 to 1.8:1, preferably 1.1 to 1.5:1. Here, the alcohol / acid molar ratio refers to the molar ratio of the number of -OH and -COOH functional groups.

[0014] The esterification reaction is preferably carried out in a protective gas atmosphere at a temperature of 130 to 240° C. for 1 to 5 hours. The protective gas is a gas that does not affect the progress of the reaction and does not react with the raw materials, and is preferably an inert gas or nitrogen gas.

[0015] The polymerization reaction is preferably carried out by carrying out prepolycondensation at 190 to 250° C. and 3 to 10 kPa for 1 to 4 hours, followed by evacuation at 200 to 250° C. until the pressure reaches 500 Pa or less, and carrying out final polycondensation for 0.5 to 10 hours.

[0016] Specifically, the present invention can adopt the following technical solutions: A method for producing a butenediol-based polyester elastomer includes the steps of: In a protective gas atmosphere, a diol (containing at least 1,4-butenediol), a dibasic acid and / or lactic acid are added to a reaction vessel in an alcohol / acid ratio of 1.05:1 to 1.8:1, and at the same time, an antioxidant in an amount of 0.01 to 0.2% of the total mass of the monomers and a polymerization inhibitor in an amount of 0.01 to 0.5% of the total mass of the monomers are added. Then, in a protective gas atmosphere, the temperature is raised to 130 to 240°C to effect esterification for 1 to 5 hours, and then, under the action of a catalyst, pre-polycondensation is carried out at 190 to 250°C and 3 to 10 kPa for 1 to 4 hours. Finally, the mixture is evacuated to a vacuum of 500 Pa or less at 200 to 250°C, and final polycondensation is carried out for 0.5 to 10 hours to obtain a butenediol-based polyester elastomer.

[0017] In the present invention, a direct esterification method is adopted, and the process is simple, so that it is easy to carry out and has high operability.

[0018] In the present invention, the butenediol-based polyester elastomer is vulcanized with a peroxide crosslinking agent commonly used in the rubber industry, preferably dicumyl peroxide, which is the most commonly used.

[0019] In the present invention, since the double bonds in the butenediol-based polyester elastomer have extremely high stability, when vulcanization is performed using a peroxide crosslinking agent, the amount of the crosslinking agent used is 0.2 to 3%, preferably 0.5 to 2%, of the total mass of the polyester elastomer.

[0020] In the present invention, the molecular weight of the butenediol-based polyester elastomer is high, and the mechanism of crosslinking reaction is similar to that of conventional rubber, so that it can be reinforced with carbon black and / or white carbon and vulcanized with a peroxide crosslinking agent to produce a high-performance polyester elastomer / white carbon (and / or carbon black) rubber composite material, which is expected to be used in fields such as low-temperature and oil-resistant rubber and degradable tires. Effect of the Invention

[0021] Compared with the prior art, the present invention has the following advantages: 1. In the present invention, 1,4-butenediol is introduced into polyester elastomer for the first time, and a novel polyester elastomer product is developed. 2. In the present invention, the double bond in butenediol has very high stability during the polymerization process and is less likely to undergo side reactions, so that a polyester elastomer product with a high molecular weight and narrow molecular weight distribution can be obtained. 3. The method for producing butenediol-based polyester elastomer products according to the present invention is simple and easy to implement, and since many of the available monomers have been produced on a large scale, it is possible to realize large-scale production and has the prospect of widespread use. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 is an FTIR spectrum of the butenediol-based polyester elastomer produced in Example 1. [Diagram 2] FIG. 2 is a H-NMR spectrum of the butenediol-based polyester elastomer produced in Example 1. [Diagram 3]FIG. 3 is a DSC double heating curve of the butenediol-based polyester elastomer produced in Example 1.

[0023] The structure of the butenediol-based polyester produced was verified by FTIR and H-NMR. The presence of -C=O and -COC=O peaks in the FTIR spectrum proves that it contains a large amount of ester groups, the -CH2- peak corresponds to a large amount of aliphatic chains, and the presence of -C=C- and -CH=CH- peaks proves that the introduction of butenediol is successful, that is, the obtained material is a butenediol-based polyester. In the H-NMR spectrum, the k and j peaks correspond to two types of hydrogen atoms in the butenediol structure, which proves that the introduction of butenediol is successful, and similar peaks are seen in all examples. In Example 1, the a and b peaks correspond to two types of hydrogen in 1,3-propanediol, the c and d peaks correspond to two types of hydrogen in 1,4-butanediol, e corresponds to one type of hydrogen in succinic acid, and f, g, h, and i correspond to four types of hydrogen in sebacic acid. This proves that the structure of the butenediol-based polyester obtained is as expected.

[0024] The DSC curve proves that the obtained butenediol-based polyester is an elastomer. As can be seen from Figure 3, there is only one glass transition in the curve, and there is no crystallization and melting behavior, which proves that the butenediol-based polyester obtained in Example 1 is amorphous and is a novel polyester elastomer with a glass transition temperature (Tg) of -51°C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The present invention will now be described in detail with reference to the drawings and specific embodiments, and the following embodiments are merely provided for further explanation of the present invention and cannot be understood as limiting the scope of protection of the present invention. Any non-essential improvements or adjustments made by those skilled in the art based on the content of the present invention will fall within the scope of protection of the present invention.

[0026] All raw materials used in the examples are commercially available products.

[0027] GPC measurement (commonly used in the prior art): polystyrene is used as the standard and tetrahydrofuran is used as the mobile phase to measure the relative molecular weight and distribution of the obtained polyester elastomer. See Table 1 for the experimental results.

[0028] DSC measurement (commonly used in the prior art): Under a nitrogen atmosphere, the sample is heated from 25°C to 200°C at a rate of 10°C / min and held for 5 minutes. The sample is then cooled from 200°C to -100°C at a rate of 10°C / min and held for 10 minutes. The temperature is then increased from -100°C to 200°C at a rate of 10°C / min. The Tg and Tm values ​​of the obtained polyester elastomer are read from the second heating curve. See Table 1 for the experimental results.

[0029] Example 1: In a reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system, 565 g (7.43 mol) of 1,3-propanediol, 669 g (7.43 mol) of 1,4-butanediol, 145 g (1.65 mol) of 1,4-butenediol, 1050 g (8.89 mol) of succinic acid, 770 g (3.81 mol) of sebacic acid, 0.32 g of phosphorous acid, and 1.28 g of hydroquinone were added. Then, under a nitrogen atmosphere, the temperature was raised to 180°C, and esterification was carried out under normal pressure for 2 hours. Then, tetrabutyl titanate was added as a catalyst in an amount of 0.1% of the total monomer mass, and the temperature was raised to 220°C, and pre-polycondensation was carried out under 3 kPa for 1 hour. Finally, the mixture was evacuated to 500 Pa or less at 220°C, and final polycondensation was carried out for 9 hours to obtain a butenediol-based polyester elastomer.

[0030] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] Here, m1=3, m2=4, n1=2, n2=8, Also, (a+c+e):(k+m+o) ≒ 9.52:4.08.

[0031] Example 2: A reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system was charged with 598 g (6.63 mol) of 1,4-butanediol, 212 g (2.41 mol) of 1,4-butenediol, 931 g (10.33 mol) of lactic acid, 153 g (1.29 mol) of succinic acid, 1306 g (6.46 mol) of sebacic acid, 3.2 g of tris(2,4-di-tert-butylphenyl) phosphite, and 12.8 g of 4-methoxyphenol. Then, under a nitrogen atmosphere, the temperature was raised to 130°C and esterification was carried out under normal pressure for 2 hours, and the temperature was further raised to 190°C and esterification was continued under normal pressure for 2 hours. Then, tetraisopropyl titanate was added as a catalyst in an amount of 0.05% of the total mass of monomers, and the temperature was raised to 190°C and prepolycondensation was carried out under 10 kPa for 4 hours. Finally, the pressure was evacuated to 500 Pa or less at 210° C., and final polycondensation was carried out for 6 hours to obtain a butenediol-based polyester elastomer.

[0032] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] Here, m1=4, m2=0 (equivalent to m1=m2=4), n1=2, n2=8, Also, (b+d+f):(a+e):(k+m) ≒ 10.33:1.29:6.46.

[0033] Example 3: In a reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system, 709 g (7.86 mol) of 1,4-butanediol, 277 g (3.15 mol) of 1,4-butenediol, 501 g (4.72 mol) of diethylene glycol, 851 g (7.21 mol) of succinic acid, 862 g (5.90 mol) of adipic acid, 1.6 g of triphenyl phosphite, and 8 g of p-phenylenediamine were added. Then, under a nitrogen atmosphere, the temperature was raised to 185°C and esterification was carried out for 3 hours under normal pressure. Then, p-toluenesulfonic acid was added as a catalyst in an amount of 0.40% of the total monomer mass, and the temperature was raised to 210°C and pre-polycondensation was carried out for 2 hours under 5 kPa. Finally, the mixture was evacuated to 500 Pa or less at 230°C and final polycondensation was carried out for 7 hours to obtain a butenediol-based polyester elastomer.

[0034] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] Here, m1=4, m2=0 (equivalent to m1=m2=4), n1=2, n2=4, x=y=1, Also, (a+e+g):(i+k+o) ≒ 7.21:5.90.

[0035] Example 4: In a reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system, 687 g (11.07 g) of ethylene glycol, 321 g (1.84 mol) of decanediol, 488 g (5.53 mol) of 1,4-butenediol, 934 g (7.91 mol) of succinic acid, 770 g (5.27 mol) of adipic acid, 2.56 g of trimethyl phosphate, and 6.4 g of benzoquinone were added. Then, under a nitrogen atmosphere, the temperature was raised to 180°C, and esterification was carried out under normal pressure for 3 hours. Then, tetrabutyl titanate was added as a catalyst in an amount of 0.20% of the total monomer mass, and the temperature was raised to 200°C, and pre-polycondensation was carried out under 5 kPa for 2 hours. Finally, the mixture was evacuated to 500 Pa or less at 225°C, and final polycondensation was carried out for 4 hours to obtain a butenediol-based polyester elastomer.

[0036] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] Here, m1=2, m2=10, n1=2, n2=4, Also, (a+c+e):(k+m+o) ≒ 7.91:5.27.

[0037] Example 5: A reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system was charged with 550 g (7.22 mol) of 1,3-propanediol, 163 g (1.81 mol) of 2,3-butanediol, 796 g (9.03 mol) of 1,4-butenediol, 1137 g (9.63 g) of succinic acid, 555 g (2.41 mol) of dodecanedioic acid, 4.8 g of phosphorous acid, and 16 g of 4-methoxyphenol. Then, under a nitrogen atmosphere, the temperature was raised to 160°C and esterification was carried out under normal pressure for 1 hour, and then the temperature was raised to 180°C and esterification was continued for 3 hours. Then, ethylene glycol antimony was added as a catalyst in an amount of 0.50% of the total mass of the monomers, and the temperature was raised to 200°C and pre-polycondensation was carried out under 10 kPa for 2 hours. Finally, the pressure was evacuated to 500 Pa or less at 230° C., and final polycondensation was carried out for 3 hours to obtain a butenediol-based polyester elastomer.

[0038] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] where m1=3, m2=4 (branched alkyl group having 4 carbon atoms), n1=2, n2=10, Also, (a+c+e):(k+m+o) ≒ 9.63:2.41.

[0039] Example 6: A reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system was charged with 543 g (6.02 mol) of 1,4-butanediol, 1086 g (12.05 mol) of 2,3-butanediol, 177 g (2.01 mol) of 1,4-butenediol, 1395 g (11.81 mol) of succinic acid, 3.2 g of trimethyl phosphate, and 12.8 g of 4-methoxyphenol. Then, under a nitrogen atmosphere, the temperature was raised to 170°C and esterification was carried out under normal pressure for 2 hours, followed by raising the temperature to 210°C and esterification for 1 hour, followed by raising the temperature to 240°C and continuing esterification for 30 minutes. Then, ethylene glycol antimony was added as a catalyst in an amount of 0.25% of the total mass of the monomers, and the temperature was raised to 250°C and pre-polycondensation was carried out under 10 kPa for 1 hour. Finally, the pressure was evacuated to 500 Pa or less at 250° C., and final polycondensation was carried out for 30 minutes to obtain a butenediol-based polyester elastomer.

[0040] The structure of the butenediol-based polyester elastomer produced is as follows: [ka] where m1=4, m2=4 (branched alkyl group having 4 carbon atoms), n1=2, n2=0 (equivalent to n1=n2=2), Also, a:c:e ≒ 6.02:12.05:2.01.

[0041] Comparative Example 1: In a reactor equipped with mechanical stirring, a heating device, a temperature measuring device, a nitrogen gas supply system, and a vacuum system, 633 g (8.32 mol) of 1,3-propanediol, 750 g (8.32 mol) of 1,4-butanediol, 952 g (8.06 mol) of succinic acid, 699 g (3.46 mol) of sebacic acid, 166 g (1.28 mol) of itaconic acid, 0.32 g of phosphorous acid, and 1.28 g of hydroquinone were added. Then, under a nitrogen atmosphere, the temperature was raised to 180°C, and esterification was carried out for 2 hours under normal pressure. Then, tetrabutyl titanate was added as a catalyst in an amount of 0.1% of the total monomer mass, and the temperature was raised to 220°C, and pre-polycondensation was carried out for 1 hour under 3 kPa. Finally, the mixture was evacuated to 500 Pa or less at 220°C, and final polycondensation was carried out for 6 hours to obtain an itaconic acid-based polyester elastomer.

[0042] The structure of the itaconic acid-based polyester elastomer produced is as follows: [ka] Here, m1=3, m2=4, n1=2, n2=8, Also, (a+c):(m+o):(e'+k') ≒ 8.06:3.46:1.28.

[0043] [Table 1] a The alcohol / acid ratio in this invention is the molar ratio of -OH and -COOH in the monomer when the raw materials are added. In the case of a reaction system containing lactic acid, the -OH and -COOH contained in lactic acid are also included in the calculation of the molar ratio. b :BeDO%mol is the mole percent of diol in 1,4-butenediol, where diol is defined generally and includes saturated diols, ethylene glycol, and 1,4-butenediol. cThe absence of Tc and Tm in the two heating curves proves that the polyester material obtained has only one glass transition temperature below room temperature, and crystallization and melting do not occur, making it an elastomeric material. d : "10% mol IA" refers to the molar percentage of the total amount of dibasic acid in itaconic acid being 10%, and since 1 mol of itaconic acid and 1 mol of butenediol both contain 1 mol of double bonds, the number of double bonds contained in the "10% mol IA" reaction system is theoretically equivalent to "10% mol BeDO".

[0044] As can be seen from the data in Table 1, the butenediol-based polyester elastomer prepared in the present invention generally has a higher relative molecular weight and a narrower relative molecular weight distribution than the itaconic acid-based polyester elastomer. When the amount of butenediol used is low, the relative molecular weight distribution is about 2.0, which is close to saturated polyester plastics such as PBS and PBA, so it has been proven that butenediol has very high stability. When the amount of butenediol used increases, the relative molecular weight distribution becomes wider, but it still has the advantage of "high molecular weight and narrow distribution" compared to the itaconic acid reaction system. The main reason is that compared with itaconic acid, the double bond in butenediol is more stable, so side reactions are less likely to occur in the high-temperature melting and polycondensation process, and the narrow relative molecular weight distribution is guaranteed.

Claims

1. A butenediol-based polyester elastomer having the following structure: 【Chemistry 1】 (Here, R ｍ１ , R ｍ２ is a branched or unbranched chain alkyl group, R ｍ１ , R ｍ２ may be the same or different, where m1 and m2 represent the numbers of carbon atoms, 2≦m1≦14, 2≦m2≦14, and m1 and m2 may be equal or unequal; R ｎ１ , R ｎ２ is a branched or unbranched chain alkyl group, R ｎ１ , R ｎ２ are different, where n1 and n2 represent the number of carbon atoms, 2≦n1≦12, 2≦n2≦12, and n1 and n2 may or may not be equal; However, a, c, m, and o cannot be 0 at the same time, and e and k cannot be 0 at the same time. x and y are integers from 1 to 3, and x and y may or may not be equal. The butenediol-based polyester elastomer is selected from any one of the following compounds: 【Chemistry 2】 Here, (a+c+e):(k+m+o) = 9.52:4.

08. 【Chemistry 3】 Here, (b+d+f):(a+e):(k+m) = 10.33:1.29:6.

46. 【Chemistry 4】 Here, (a+e+g):(i+k+o) = 7.21:5.

90. 【Chemistry 5】 Here, (a+c+e):(k+m+o) = 7.91:5.

27. 【Chemistry 6】 Here, (a+c+e):(k+m+o)=9.63:2.

41. 【Chemistry 7】 Here, a:c:e = 6.02:12.05:2.

01.

2. The butenediol-based polyester elastomer is produced by subjecting a diol, a dibasic acid, an antioxidant, and a polymerization inhibitor to an esterification reaction and a polymerization reaction under the action of a catalyst, or by subjecting a glycol, a dibasic acid, a lactic acid, an antioxidant, and a polymerization inhibitor to an esterification reaction and a polymerization reaction under the action of a catalyst, the diol is one or a combination of 1,4-butenediol and other diols selected from 1,3-propanediol, 1,4-butanediol, ethylene glycol, decanediol, 2,3-butanediol, and diethylene glycol; 2. The method for producing a butenediol-based polyester elastomer according to claim 1, wherein the dibasic acid is selected from at least one of succinic acid, sebacic acid, adipic acid, and dodecanedioic acid.

3. the catalyst is one or a combination of selenium dioxide, antimony trioxide, ethylene glycol antimony, p-toluenesulfonic acid, acetate, alkylaluminum having 1 to 12 carbon atoms, organotin compound, titanate; The antioxidant is one or a combination of phosphoric acid or phosphorous compounds; 3. The method for producing a butenediol-based polyester elastomer according to claim 2, wherein the polymerization inhibitor is one or a combination of a phenol polymerization inhibitor, an ether polymerization inhibitor, a quinone polymerization inhibitor, or an aromatic amine polymerization inhibitor.

4. the molar ratio of the number of —OH and —COOH functional groups due to the diol, diacid and lactic acid is from 1.05:1 to 1.8:1; The amount of the antioxidant used is 0.01 to 0.2% of the total mass of the diol, the dibasic acid, and the lactic acid.

3. The method for producing a butenediol-based polyester elastomer according to claim 2, wherein the amount of the polymerization inhibitor used is 0.01 to 0.5% of the total mass of the diol, the dibasic acid and the lactic acid.

5. the molar ratio of the number of —OH to —COOH functional groups due to the diol, diacid and lactic acid is 1.1-1.5:1; The amount of antioxidant used is 0.04 to 0.08% of the total mass of the diol, dibasic acid, and lactic acid; 5. The method for producing a butenediol-based polyester elastomer according to claim 4, wherein the amount of the polymerization inhibitor used is 0.05 to 0.2% of the total mass of the diol, dibasic acid and lactic acid.

6. 3. The method for producing a butenediol-based polyester elastomer according to claim 2, wherein the amount of the catalyst used is 0.02 to 0.5% of the total mass of the diol, dibasic acid and lactic acid.

7. The method for producing a butenediol-based polyester elastomer according to claim 2, characterized in that the esterification reaction is carried out at a temperature of 130 to 240°C in a protective gas atmosphere, and the esterification reaction time is 1 to 5 hours.

8. The method for producing a butenediol-based polyester elastomer according to claim 2, characterized in that the polymerization reaction is carried out by carrying out pre-polycondensation at 190 to 250°C and 3 to 10 kPa for 1 to 4 hours, followed by evacuation to 500 Pa or less at 200 to 250°C and final polycondensation for 0.5 to 10 hours.

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