Furan ring-containing polyester elastomer, method for preparing the same, and use thereof

Abstract

This invention relates to the field of polymer technology, and more particularly to furan ring-containing polyester elastomers and methods for preparing the same. In this invention, by using a high molecular weight random copolymer aliphatic-aromatic copolymer ester elastomer containing furan rings, prepared by a method in which monomers are introduced into a reactor all at once and a continuous reaction is carried out, a high molecular weight product with a narrow distribution can be prepared, and the elastic recovery rate exceeds 70%. The preparation method provided in this invention is easy to operate, has strong process controllability, and therefore extends a novel method for preparing biodegradable thermoplastic copolymer polyester elastomers, and this method also enables easy industrialization of the product.

Description

Detailed description of the invention

[0001] [Technical Field] The present invention belongs to the field of polymer technology, and more particularly to furan ring-containing polyester elastomers, methods for preparing the same, and their use.

[0002] [Technical background] As a solution to the shortage of fossil resources such as petroleum, the use of renewable biomass resources to synthesize various monomers and polymers represents a new direction for the development of the chemical and energy industries. Bio-based polymer materials can effectively reduce environmental pollution and promote sustainable development. Typical bio-based polymers include polylactic acid (PLA), polybutylene succinate (PBS), and polyhydroxyalkanoate (PHA). Compared to petroleum-based polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), bio-based polymers have inferior heat resistance and mechanical properties. The fundamental reason for this is the lack of rigid aromatic rings in their molecular structure. 2,5-Franzicarboxylic acid (2,5-FDCA) is one of the 12 most promising bio-aromatic platform compounds selected by the U.S. Department of Energy. Compared to terephthalic acid (TPA)-based aliphatic-aromatic copolymer polyesters, biomass-derived FDCA-based aliphatic-aromatic copolymer polyesters possess comparable thermal / mechanical properties and are expected to replace petroleum-based aromatic platform compounds such as terephthalic acid, enabling the synthesis of high-performance bio-based polymer materials. Furthermore, they also possess potential biodegradability, making them superior and environmentally friendly materials.

[0003] PBST (poly(butylene succinate-co-terephthalate)) is a new type of aliphatic / aromatic copolymer polyester. PBST is a new type of biodegradable polymer obtained by chemical modification based on polybutylene succinate (PBS). PBST retains the biodegradability and good thermal properties of PBS while possessing the excellent mechanical properties, high melting point, and high crystallinity of polybutylene terephthalate (PBT). PBST is a biodegradable material with great potential. The properties of PBST copolymers are closely related to the ratio of aromatic copolymer units to aliphatic copolymer polyester units and the average sequence length.

[0004] [Summary of the Invention] This invention provides a furan ring-containing polyester elastomer. A bio-based furan ring monomer is introduced into the polyester material as a fourth monomer. An aliphatic-aromatic copolymer polyester material with excellent mechanical properties and degradation characteristics is obtained via an esterification melt polycondensation method. This copolymer polyester has excellent thermal / mechanical properties with respect to composition, exhibits elastomer properties within a certain composition range, has excellent resilience, and also has potential biodegradability.

[0005] A first object of the present invention is a furan ring-containing polyester elastomer comprising the reaction product of component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid and component (d) aliphatic dihydric alcohol; The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9~1.05), for example, 1:(0.95~1.02) or 1:(0.96~1.01); The molar ratio of component (a) to component (b) is 1:(0.4~1.8), preferably 1:(0.4-1.2); The objective is to provide a furan ring-containing polyester elastomer having a break elongation of over 1500% and an elastic recovery rate greater than 70%, preferably having an average elastic recovery rate of 80% or more, and more preferably having an average elastic recovery rate of 90% or more.

[0006] According to the present invention, the furan ring-containing polyester elastomer has a weight-average molecular weight greater than 60,000 and a molecular weight distribution of 1.6 to 2.3, and preferably, the furan ring-containing polyester elastomer has a weight-average molecular weight greater than 100,000 and a molecular weight distribution of 1.6 to 2.0.

[0007] According to the present invention, the furan ring-containing polyester elastomer has elastic self-enhancement ability, and preferably, when the elongation ratio of the furan ring-containing polyester elastomer is 500% or more, the elastic recovery rate is greater than 85%, and when the elongation ratio is 800% or more, the elastic recovery rate is greater than 90%.

[0008] According to the present invention, the elastomer has a tensile modulus of 10 to 75 MPa and a tensile strength at fracture of 4 to 20 MPa.

[0009] According to the present invention, in a furan ring-containing polyester elastomer: The aforementioned component (a) is at least one of 2,5-franzicarboxylic acid, dimethyl 2,5-franzicarboxylate, and diethyl 2,5-franzicarboxylate; The aforementioned component (b) is C8-C 18 Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid, and isophthalic acid esters, more preferably terephthalic acid; The aforementioned component (c) is C2-C 18It is at least one of the aliphatic dibasic acids, preferably at least one of sebacic acid, succinic acid, and adipic acid, and more preferably at least one of succinic acid and adipic acid; The component (d) is at least one C2-C8 dihydric alcohol, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol, and more preferably 1,4-butylene glycol.

[0010] According to the present invention, by using a specific ratio of furan ring-containing component (a) and aromatic ring-containing component (b), a certain amount of furan-based polyester segments is formed in the system, the degree of crystallinity of the polyester is adjusted, and the copolymerized polyester exhibits excellent resilience and elastomer properties.

[0011] A second object of the present invention is to provide a method for preparing the above-mentioned furan ring-containing polyester elastomer, the method comprising: sequentially subjecting component (a) franzi carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol to an esterification reaction, a preliminary polycondensation reaction, and a final polycondensation reaction to produce a furan ring-containing polyester elastomer. According to the present invention, the preparation method particularly includes the following steps: (1) A step of subjecting components (a), (b), (c), and (d) to an esterification reaction under the action of a first catalyst; (2) When the esterification rate reaches 92-98%, a preliminary polycondensation reaction is carried out under the action of a second catalyst; (3) A step of subjecting the reaction system obtained in step (2) to a final polycondensation reaction to produce the furan ring-containing polyester elastomer.

[0012] According to one embodiment of the present invention, in a method for preparing a furan ring-containing polyester elastomer: The component (a) is at least one of 2,5-franzicarboxylic acid, dimethyl 2,5-franzicarboxylate, and diethyl 2,5-franzicarboxylate; The aforementioned component (b) is C8-C 18 Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid, and isophthalic acid esters, more preferably terephthalic acid; The aforementioned component (c) is C2-C 18 It is at least one of the aliphatic dibasic acids, preferably at least one of sebacic acid, succinic acid, and adipic acid, and more preferably at least one of succinic acid and adipic acid; The component (d) is at least one of the C2-C8 dihydric alcohols, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol, and more preferably 1,4-butylene glycol; The first catalyst comprises an organotitanium compound and at least one compound comprising antimony, germanium, zirconium, tin, magnesium, cobalt, aluminum, or zinc, preferably comprising an organotitanium compound and at least one organotin compound; where the organotitanium compound is selected from tetrabutyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetraethyl titanate, and titanium glycolate, and the organotin compound is The first catalyst is comprised of at least one of stannous cutanoate, stannous oxalate, dibutyltin oxide, butyltin hydroxide oxide, dibutyltin diacetate, dioctyltin oxide, and butyltin tris(2-ethylhexanoate); the organotitanium compound is present in 45 to 85 parts by weight, for example, 55 to 75 parts by weight or 75 to 85 parts by weight, based on 100 parts by weight of the total amount of the first catalyst; the organotin compound is present in 15 to 55 parts by weight, for example, 25 to 45 parts by weight or 15 to 25 parts by weight; The second catalyst is at least one of lanthanide series metal compounds, and preferably at least one of lanthanum chloride, lanthanum acetylacetonate, neodymium isopropoxide, and lanthanum stearate.

[0013] According to one embodiment of the present invention, in the method for preparing a furan ring-containing polyester elastomer, in step (1): The ratio of the total molar amount of components (a), (b) and (c) to the molar amount of component (d) is 1:(1.05 - 4), preferably 1:(1.2 - 2); The ratio of the total molar amount of components (a) and (b) to the molar amount of component (c) is 1:(0.9 - 1.05), for example 1:(0.95 - 1.02), or 1:(0.96 - 1.01); The molar ratio of component (a) to component (b) is 1:(0.4 - 1.8), preferably 1:(0.4 - 1.2); The usage amount of the first catalyst is 0.01 - 1% by weight, for example 0.1 - 0.3% by weight or 0.05 - 0.2% by weight based on the total amount of components (a), (b) and (c); The conditions of the esterification reaction are as follows: the esterification temperature is 130 - 210°C, preferably 150 - 190°C; the reaction time can be 1 - 5 hours, preferably 2 - 3 hours; the reaction atmosphere is a protective gas, for example nitrogen gas.

[0014] According to one embodiment of the present invention, in the method for preparing a furan ring-containing polyester elastomer, in step (2): The usage amount of the second catalyst is 0.01 - 0.5% by weight, preferably 0.05 - 0.2% by weight based on the total amount of components (a), (b) and (c); The conditions of the preliminary polycondensation reaction are as follows: the reaction temperature is 150 - 220°C, preferably 190 - 210°C; the reaction time is 0.5 - 2.5 hours, preferably 1 - 1.5 hours; the degree of vacuum is 600 - 5000 Pa, preferably 1000 - 2000 Pa.

[0015] According to one embodiment of the present invention, in a method for preparing a furan ring-containing polyester elastomer, the conditions for the final polycondensation reaction in step (3) are as follows: The reaction temperature is 210-260°C, preferably 230-250°C; The reaction time is 1 to 5 hours, preferably 2 to 4 hours; The vacuum level is 300 Pa or less, for example, 150 Pa or less, or 50 Pa or less.

[0016] According to the present invention, a method for preparing a furan ring-containing polyester elastomer may be used with the following specific preparation procedure: Step 1: In the presence of a first catalyst and a protective gas atmosphere, components (a), (b), (c), and (d) are subjected to an esterification reaction in an esterification reactor until the esterification rate reaches 92-98%, at which point they are introduced into a polycondensation reactor for the next reaction; Step 2: In the presence of the second catalyst, the product from the esterification reactor is introduced into a pre-polycondensation reactor for polycondensation, and the vacuum reaction conditions are gradually established so that the vacuum is maintained at 600-5000 Pa. The reaction is carried out for a certain period of time, and the resulting pre-polycondensate is introduced into the next reaction; Step 3: The preliminary polycondensate is reacted in the final polycondensation reactor, and the vacuum level is controlled to 300 Pa or less to ultimately produce a furan ring-containing polyester elastomer.

[0017] A third object of the present invention is to provide the use of the above-described furan ring-containing polyester elastomer or the furan ring-containing polyester elastomer obtained by the above-described preparation method as a biodegradable material.

[0018] In this invention, the furan ring of component (a) and the benzene ring of component (b) have specific structural differences, which result in differences in the electronegativity, aromaticity, and heat resistance of the two acids. FDCA is a π-electron-rich heterocyclic system and has lower aromaticity than PTA. The electrophilicity of the carbon atoms of the carboxyl groups in FDCA is weakened due to the influence of the oxygen atoms of its own aliphatic ring. FDCA has two carboxyl groups with specific bond angles, and therefore FDCA is a polar molecule. Because the furan ring on the repeating unit of the aliphatic-aromatic copolymer polyester synthesized from these two acids is asymmetric, the chain segments are less likely to flip. At the same time, the furan ring has a permanent dipole moment because the positive and negative charge centers do not overlap, thereby generating an electrostatic force, increasing the interaction force between chains, increasing the rigidity of the chains, and decreasing the mobility of the chain segments. The prepared furan-based polyester exhibits the advantages of the asymmetric rigid ring structure in terms of mechanical properties, thermal properties, and barrier properties. Therefore, in this invention, by using a specific ratio of furan ring-containing component (a) and aromatic ring-containing component (b) and forming a certain amount of furan-based polyester segments in the system, the degree of crystallinity of the polyester is adjusted, so that the copolymerized polyester has excellent resilience, exhibits elastomer properties, and has excellent fatigue resistance and elastic self-reinforcing effects.

[0019] The bio-based furan ring-containing polyester elastomer of the present invention, which can be prepared using bio-based raw materials, reduces the consumption of petroleum materials and contributes to the sustainable development of resources by partially replacing the application of conventional petroleum-based elastomer materials. In addition, it not only has good thermal and mechanical properties but also potential biodegradability.

[0020] Compared to prior art, the present invention has the following beneficial effects: (1) The present invention employs an approach to prepare a high molecular weight, randomly copolymerized, furan ring-containing aliphatic-aromatic copolymer polyester elastomer by adding monomers in a single shot to a reactor and carrying out a continuous reaction, which is a high molecular weight polyester elastomer with a narrow distribution. Preferably, this polyester elastomer has a weight-average molecular weight greater than 100,000 and a molecular weight distribution of 1.6 to 2.0. (2) By optimizing the catalyst system and polymerization method and controlling the supply ratio, the present invention can produce polyester products having a copolymer unit ratio that matches the supply ratio. By adjusting the ratio of furan monomers to aromatic monomers, furan polyesters having different aromatic unit compositions can be obtained, thereby yielding aliphatic-aromatic copolymer polyesters with good toughness and resilience, and thereby yielding copolymer polyester elastomers that meet different usage requirements, further expanding their application fields. (3) In the present invention, it is not necessary to copolymerize the soft segment and the hard segment to obtain the elastomer material. Instead, the restorative properties of the resulting polyester material can be precisely controlled simply by combining furan monomers and aromatic monomers in a specific ratio. Furthermore, this polyester material can be an ideal bio-based elastic material used under repeated loading conditions, possessing excellent fatigue resistance and elastic self-reinforcing effects. (4) The preparation method provided by the present invention is easy to operate, has strong process controllability, and therefore provides a novel method for preparing biodegradable thermoplastic copolymer polyester elastomers, and the method facilitates the industrialization of the product.

[0021] [Description of the drawing] Figure 1 shows the hydrogen nuclear magnetic spectrum of the furan ring-containing polyester elastomer obtained in Comparative Example 1; Figure 2 shows the DSC spectrum of the furan ring-containing polyester elastomer obtained in Comparative Example 1; Figure 3 shows the hydrogen nuclear magnetic spectrum of the furan ring-containing polyester elastomer obtained in Example 1; Figure 4 shows the DSC spectrum of the furan ring-containing polyester elastomer obtained in Example 1; Figure 5 shows the cyclic tensile hysteresis loop of the furan ring-containing polyester elastomer obtained in Example 1 under strain conditions of 100-1400%; Figure 6 shows the elastic recovery rate corresponding force curve of the furan ring-containing polyester elastomer obtained in Example 1 under strain conditions of 100 to 1400%; Figure 7 shows (a) elastic recovery rate, (b) corresponding tensile modulus and dissipated energy during 10 consecutive stretching cycles under 300% strain conditions for the furan ring-containing polyester elastomer obtained in Example 1; Figure 8 shows the cyclic stretching curve of the furan ring-containing polyester elastomer obtained in Example 1: (a) the stretching curve for cycles 1 to 10 at 200% strain, and (b) the stretching curve for cycles 1 to 10 at 300% strain; the curves in the figure, from top to bottom, represent the stretching curves for cycles 1 to 10. Figure 9 shows the DSC spectrum of the PBST copolymer polyester obtained in Comparative Example 3; Figure 10 shows the DSC spectrum of the PBSF copolymer polyester obtained in Comparative Example 4; Figure 11 shows the stress-strain curve of the PBSF copolymer polyester obtained in Comparative Example 4; Figure 12 shows a before-and-after comparison of the tensile recovery performance of the sample strip of the furan ring-containing polyester elastomer obtained in Example 1: (a) is a photograph of the strip before rebound, and (b) is a photograph of the strip after rebound; Figure 13 shows the two-dimensional X-ray diffraction pattern (a) and the corresponding one-dimensional X-ray diffraction pattern (b) of Example 1 at different elongation factors; Figure 14 shows a comparison of the XRD patterns of the examples and comparative examples.

[0022] [Detailed explanation] The present invention will be described in detail below, along with specific embodiments. It is necessary to make it clear that the following embodiments are used solely for the purpose of further illustrating the present invention and should not be understood as limiting the scope of protection of the present invention. Some non-essential improvements and modifications of the present invention made by those skilled in the art based on the content of the present invention remain within the scope of protection of the present invention.

[0023] This application discloses the following technical solutions: 1. (F) Structural units derived from flangic carboxylic acid and / or its esters; (T) Structural units derived from aromatic dibasic acids and / or aromatic dibasic acid esters; (S) A structural unit derived from an aliphatic dibasic acid; (D) Structural units derived from aliphatic dihydric alcohols; A furan ring-containing polyester elastomer, The furan ring-containing polyester elastomer is a combination of the following structural units: SDS, where SDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends of it are structural units derived from aliphatic dibasic acids (e.g., succinic acid); TDT, where TDT represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are structural units derived from aromatic dibasic acids and / or aromatic dibasic acid esters (e.g., terephthalic acid); FDF, where FDF represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are structural units derived from frangic acid and / or its esters (e.g., frangic acid); SDT / TDS, where SDT / TDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are such that one end is a structural unit derived from an aliphatic dibasic acid (e.g., succinic acid) and the other end is a structural unit derived from an aromatic dibasic acid and / or an aromatic dibasic acid ester (e.g., terephthalic acid); SDF / FDS, where SDF / FDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are such that one end is a structural unit derived from an aliphatic dibasic acid (e.g., succinic acid) and the other end is a structural unit derived from a flangic acid and / or its ester (e.g., flangic acid); TDF / FDT, where TDF / FDT represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are such that one end is a structural unit derived from an aromatic dibasic acid and / or an aromatic dibasic acid ester (e.g., terephthalic acid), and the other end is a structural unit derived from a frangic acid and / or its ester (e.g., frangic acid); Includes, Here, based on the criterion that the total amount of the structural unit combinations SDS, TDT, FDF, SDT / TDS, SDF / FDS, and TDF / FDT is 100 mol%, The amount of the aforementioned combination of structural units (SDS) is 21-28 mol%; The amount of the TDT of the aforementioned structural unit combination is 2-9 mol%; The amount of FDF, a combination of the aforementioned structural units, is 6-15 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 13-28 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 22-38 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 9-14 mol%; Preferably, The amount of the aforementioned combination of structural units (SDS) is 23-26 mol%; The amount of the TDT of the aforementioned structural unit combination is 2-8 mol%; The amount of FDF, a combination of the aforementioned structural units, is 6-14 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 13-26 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 23-37 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 9-13 mol%; more, The amount of the aforementioned structural unit combination SDS is 23-26 mol%. The amount of the TDT of the aforementioned structural unit combination is 2-8 mol%; The amount of FDF, a combination of the aforementioned structural units, is 6-14 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 14-26 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 24-36 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 10-13 mol%. A polyester elastomer containing furan rings.

[0024] 2. A furan ring-containing polyester elastomer according to technical solution 1, comprising the reaction product of component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol; The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9~1.05), for example, 1:(0.95~1.02) or 1:(0.96~1.01); A furan ring-containing polyester elastomer having a molar ratio of component (a) to component (b) of 1:(0.4~1.8), preferably 1:(0.4~1.2).

[0025] 3. A furan ring-containing polyester elastomer comprising the reaction product of component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol; The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9~1.05), for example, 1:(0.95~1.02) or 1:(0.96~1.01); A furan ring-containing polyester elastomer having a molar ratio of component (a) to component (b) of 1:(0.4~1.8), preferably 1:(0.4~1.2).

[0026] 4. A furan ring-containing polyester elastomer according to any one of the technical solutions 1 to 3, characterized in that, in measurement of tensile properties according to GB / T 1040.1-2018, the elongation at break exceeds 1500%, preferably exceeds 1600%.

[0027] 5. A furan ring-containing polyester elastomer according to any one of the technical solutions 1 to 4, characterized in that its elastic recovery rate is greater than 70%.

[0028] 6. A furan ring-containing polyester elastomer according to any one of the technical solutions 1 to 5, characterized in that the weight-average molecular weight is greater than 60,000 and the molecular weight distribution is 1.6 to 2.3; preferably, the weight-average molecular weight is greater than 100,000 and the molecular weight distribution is 1.6 to 2.0.

[0029] 7. A furan ring-containing polyester elastomer according to any one of the technical solutions 1 to 6, characterized in that the average elastic recovery rate is 80% or more.

[0030] 8. The technical solution according to any one of claims 1 to 7, wherein the polyester elastomer containing a furan ring has self-enhancing elasticity, preferably, when the elongation ratio is 500% or more, the elastic recovery rate is greater than 85%, and when the elongation ratio is 800% or more, the elastic recovery rate is greater than 90%.

[0031] 9. The weight-average molecular weight is 9 to 15×10 4 whereas the number-average molecular weight is 5 to 10×10 4 whereas the molecular weight distribution is 1.6 to 2.3, and weight-average molecular weight × number-average molecular weight is 50 to 120×10 8 whereas preferably, the weight-average molecular weight is 10 to 14×10 4 whereas the number-average molecular weight is 5 to 9×10 4 whereas the molecular weight distribution is 1.6 to 2.0, and weight-average molecular weight × number-average molecular weight is 60 to 110×10 8 whereas it is characterized by being the polyester elastomer containing a furan ring according to any one of claims 1 to 8.

[0032] 10. In the measurement of tensile properties according to GB / T 1040.1-2018, the tensile modulus is 8 to 75 MPa, for example, 10 to 75 MPa, 8 to 25 MPa, or 10 to 16 MPa, whereas it is characterized by being the polyester elastomer containing a furan ring according to any one of claims 1 to 9.

[0033] 11. In the measurement of tensile properties according to GB / T 1040.1-2018, the tensile strength at break is 3 to 20 MPa, for example, 4 to 20 MPa, 3 to 8 MPa, or 4 to 6 MPa, whereas it is characterized by being the polyester elastomer containing a furan ring according to any one of claims 1 to 10.

[0034] 12. In the measurement of tensile properties according to GB / T 1040.1-2018, it is characterized by having no yield phenomenon, and being the polyester elastomer containing a furan ring according to any one of claims 1 to 11.

[0035] 13. A furan ring-containing polyester elastomer according to any one of the technical solutions 1 to 12, characterized in that: the francaric acid and / or its ester is at least one of 2,5-francaric acid, dimethyl 2,5-francarcarboxylate, and diethyl 2,5-francarcarboxylate; and / or The aforementioned aromatic dibasic acid and / or aromatic dibasic acid ester is C8-C 18 Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid, and isophthalic acid esters; and / or, The aforementioned aliphatic dibasic acid is C2-C 18 At least one aliphatic dibasic acid, preferably at least one of sebacic acid, succinic acid, and adipic acid; and / or, The aliphatic dihydric alcohol is at least one of the C2-C8 dihydric alcohols, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol.

[0036] 14. A method for preparing a furan ring-containing polyester elastomer according to any one of technical solutions 1 to 13, comprising the step of sequentially subjecting component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol to an esterification reaction, a preliminary polycondensation reaction, and a final polycondensation reaction to produce a furan ring-containing polyester elastomer.

[0037] 15. The preparation method according to technical solution 14, characterized in that it includes the following steps in particular: (1) A step of subjecting components (a), (b), (c), and (d) to an esterification reaction under the action of a first catalyst; (2) When the esterification rate reaches 92-98%, a preliminary polycondensation reaction is carried out under the action of a second catalyst; (3) A step of subjecting the reaction system obtained in step (2) to a final polycondensation reaction to produce the furan ring-containing polyester elastomer.

[0038] 16. A preparation method according to any one of the technical solutions 14 to 15, having the following characteristics: The component (a) is at least one of 2,5-franzicarboxylic acid, dimethyl 2,5-franzicarboxylate, and diethyl 2,5-franzicarboxylate; and / or, The aforementioned component (b) is C8-C 18 Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid, and isophthalic acid esters; and / or, The aforementioned component (c) is C2-C 18 At least one aliphatic dibasic acid, preferably at least one of sebacic acid, succinic acid, and adipic acid; and / or, The aforementioned component (d) is at least one of the C2-C8 dihydric alcohols, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol; and / or, The first catalyst comprises an organotitanium compound and at least one compound comprising antimony, germanium, zirconium, tin, magnesium, cobalt, aluminum, or zinc, preferably comprising an organotitanium compound and at least one organotin compound; and / or, The second catalyst is at least one of the lanthanide series metal compounds, preferably at least one of lanthanum chloride, lanthanum acetylacetonate, neodymium isopropoxide, and lanthanum stearate.

[0039] 17. A preparation method according to any one of the technical solutions 14 to 16, having the following characteristics: The organotitanium compound is selected from butyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetraethyl titanate, and titanium glycolate; and / or, The organotin compound is at least one of stannous octanoate, stannous oxalate, dibutyltin oxide, butyltin hydroxide oxide, dibutyltin diacetate, dioctyltin oxide, and butyltin tris(2-ethylhexanoate); and / or Based on a total amount of 100 parts by weight of the first catalyst, the organotitanium compound comprises 45 to 85 parts by weight, for example, 55 to 75 parts by weight or 75 to 85 parts by weight; and the organotin compound comprises 15 to 55 parts by weight, for example, 25 to 45 parts by weight or 15 to 25 parts by weight.

[0040] 18. The preparation method described in any one of the technical solutions 14 to 17, having the following characteristics in step (1): The ratio of the total number of moles of components (a), (b), and (c) to the number of moles of component (d) is 1:(1.05~4), preferably 1:(1.2~2); and / or, The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9~1.05), for example, 1:(0.95~1.02) or 1:(0.96~1.01); The molar ratio of component (a) to component (b) is 1:(0.4~1.8), preferably 1:(0.4~1.2); The amount of the first catalyst used is 0.01 to 1% by weight, for example, 0.1 to 0.3% by weight or 0.05 to 0.2% by weight, relative to the total amount of components (a), (b), and (c); and / or The conditions for the esterification reaction are as follows: the esterification temperature is 130-210°C, for example, 150-190°C; the reaction time is 1-5 hours, for example, 2-3 hours; and the reaction atmosphere is a protective gas.

[0041] 19. In step (2), the preparation method according to any one of the technical solutions 14 to 18 has the following characteristics: The amount of the second catalyst used is 0.01 to 0.5% by weight, preferably 0.05 to 0.2% by weight, relative to the total amount of components (a), (b), and (c); and / or, The conditions for the aforementioned preliminary polycondensation reaction are as follows: the reaction temperature is 150 to 220°C, for example 190 to 210°C; and / or the reaction time is 0.5 to 2.5 hours, for example 1 to 1.5 hours; and / or the vacuum level is 600 to 5000 Pa, for example 1000 to 2000 Pa.

[0042] 20. The preparation method according to any one of the technical solutions 14 to 19, characterized in that the conditions for the final polycondensation reaction in step (3) are as follows: The reaction temperature is 210-260°C, for example, 230-250°C; and / or, The reaction time is 1 to 5 hours, for example, 2 to 4 hours; and / or, The vacuum level is 300 Pa or less, for example, 150 Pa or less, or 50 Pa or less.

[0043] 21. Use of a furan ring-containing polyester elastomer described in any one of technical solutions 1 to 13, or a furan ring-containing polyester elastomer obtained by the preparation method described in any one of technical solutions 14 to 20, in a biodegradable material.

[0044] Definition: (1) Elastic recovery rate: The test specimen is shaped like a dumbbell with a neck 6 mm wide and 0.5 mm thick. At room temperature, the strain of the test specimen is fixed at 300%. The test specimen is stretched to 300% at a rate of 100 μm / s each time, and then the stress is returned to zero at the same rate. This stretching is repeated 10 times. The recovery rate is calculated according to the following formula, and the final result is the average value for each group of test specimens.

[0045]

number

[0046] (2) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are measured and calculated according to GB / T 36214.

[0047] (3) The tensile modulus (E), tensile strength at fracture (σb), elongation at fracture (εb), and yield stress (also known as yield strength σs) are calculated according to the methods specified in GB / T 1040.1-2018.

[0048] The test methods and test conditions used in this invention are as follows: GPC Testing: The molecular weight and molecular weight distribution of the two raw materials are characterized using a PL-GPC220 gel chromatography system from Polymer Laboratories, UK.

[0049] NMR test: 1 ¹H NMR is performed using a Bruker AMX300 Fourier transform NMR spectrometer at a resonance frequency of 300 MHz, with deuterated chloroform (CDCl3) as the solvent and tetramethylsilane (TMS) as the internal standard.

[0050] Mechanical properties: Samples for tensile and rebound testing are prepared by compression molding using a CARVER-4533 press from CARVER, Inc., USA. The compression molding temperature is 200°C, and the molten material is held at 5 MPa for 6 minutes, followed by quenching in an ice bath.

[0051] Tensile and rebound tests will be performed using an INSTRON-5965 tension meter from INSTRON, Inc., USA. The elongation rate will be 50 mm / min, and each component will be tested five times.

[0052] The yield stress and elongation at fracture are calculated according to the method specified in GB / T 1040.1-2018.

[0053] Elastic recovery test: The strain is fixed at 200% or 300%, and the test specimen is stretched to 200% or 300% at a rate of 100 μm / s each time, then the stress is returned to zero at the same rate, and the stretching is repeated 10 times.

[0054] Gradual elastic recovery test: The sample piece is first stretched to 100%, then returned to zero stress at the same rate; then stretched to 200%, then returned to zero stress at the same rate; then stretched to 300%, then returned to zero stress at the same rate; this process is continued until the 14th stretching cycle is completed.

[0055] Unless otherwise specified, the raw materials used in the examples and comparative examples are known in the prior art and can be purchased directly or prepared according to the preparation methods disclosed in the prior art.

[0056] [Example 1] 156 g of 2,5-franzicarboxylic acid, 166 g of terephthalic acid, 236 g of succinic acid, and 540 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 0.6 g of tetraisopropyl titanate, 0.2 g of stannous octanoate, and 0.5 g of lanthanum acetylacetonate were added. Esterification was carried out in the presence of a nitrogen atmosphere, and the temperature was gradually increased to 190°C. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 210°C. After 1.5 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 245°C for 3 hours to finally produce a copolymer polyester (denoted as PBSTF-3).

[0057] GPC testing showed that the PBSTF-3 copolymer polyester has a manganese content of 8.0 × 10⁶. 4Mw is 13.2 × 10 4 It was also shown that the molecular weight distribution was 1.66.

[0058] DSC test: The temperature corresponding to a 5% weight loss of PBSTF-3 copolymer polyester in an N2 atmosphere was 353°C, and the thermal decomposition temperature was 400°C.

[0059] Nuclear magnetic resonance (NEM) testing revealed that the molar ratio of succinic acid:terephthalic acid:franzicarboxylic acid in the PBSTF-3 copolymer polyester was 49.7:25.2:25.1, and this composition was consistent with the supply ratio.

[0060] Tensile properties testing revealed that the PBSTF-3 copolymer polyester exhibited a tensile modulus of 15.2 MPa, a tensile strength at break of 4.1 MPa, and an elongation at break exceeding 1700%. The elastic recovery rate after the initial stretch was greater than 70%, and no yielding phenomenon was observed, demonstrating the elastomer properties of the sample. The average elastic recovery rate was approximately 90%. As strain increased, stress continued to increase, the hysteresis loop area enclosed by the stress-strain curve gradually increased, and both the tensile modulus and dissipated energy gradually increased. The hysteresis loop for a single cycle recovery was relatively small, indicating relatively low stretch energy dissipation. As shown in Figure 6, when the strain increased to 1400%, the elastic recovery rate continued to gradually increase, indicating a self-reinforcing effect of elasticity. As shown in Figure 7, during successive stretching cycles, the dissipated energy gradually stabilized at a low value, demonstrating excellent fatigue resistance.

[0061] The hysteresis loop of the first repeating curve was significantly larger than the hysteresis loops of the subsequent repeating curves. This indicates that the sample underwent permanent deformation after the initial stretching, suggesting a significant change in the internal condensed state structure. In contrast, the area of ​​the hysteresis loops of the subsequent repeated stretching hardly changed, suggesting that the elastic recovery rate remained largely unchanged and the sample structure remained stable thereafter.

[0062] Two-dimensional X-ray diffraction patterns at different stretching factors showed that as the stretching factor increases, the orientation structure of the polymer chains becomes more ordered and crystallized. As the stretching factor increases, the intensity of the diffraction peaks increases, and crystalline microregions are formed, resulting in a denser overall crosslinking network, providing physical crosslinking points in the elastomer and resulting in self-reinforcing elastic restorative properties.

[0063] [Example 2] 218.4 g of 2,5-franzicarboxylic acid, 99.6 g of terephthalic acid, 236 g of succinic acid, and 540 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 1.0 g of tetra-n-butyl titanate, 0.5 g of lanthanum chloride, and 0.2 g of stannous octanoate were added. Esterification was carried out in the presence of a nitrogen atmosphere, and the temperature was gradually increased to 190°C. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 210°C. After 1.5 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 245°C for 3 hours to finally produce a copolymer polyester denoted as PBSTF-4.

[0064] GPC testing showed that the PBSTF-4 copolymer polyester has a manganese content of 6.0 × 10⁶. 4 Mw is 10.1 × 10 4 The molecular weight distribution was shown to be 1.71.

[0065] Nuclear magnetic resonance (NEM) testing revealed that the molar ratio of succinic acid:terephthalic acid:franzicarboxylic acid in the PBSTF-4 copolymer polyester was 49.7:15.1:35.2, and this composition was consistent with the supply ratio.

[0066] Tensile properties testing revealed that the PBSTF-4 copolymer polyester had a tensile modulus of 13.7 MPa, a tensile strength at break of 4.9 MPa, and an elongation at break exceeding 1600%. The elastic recovery rate after initial stretching was greater than 70%, the average elastic recovery rate was approximately 85%, and no yielding phenomenon was observed, thus proving that this sample possesses elastomer properties.

[0067] [Example 3] 184 g of dimethyl 2,5-franzicarboxylate, 166 g of terephthalic acid, 292.3 g of adipic acid, and 540 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 1.0 g of tetra-n-propyl titanate, 0.5 g of lanthanum chloride, and 0.2 g of stannous octanoate were added. Esterification was carried out in the presence of a nitrogen atmosphere, and the temperature was gradually increased to 190°C. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 210°C. After 1.5 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 245°C for 3 hours to finally produce a copolymer polyester denoted as PBATF.

[0068] GPC testing revealed that the PBATF copolymer polyester has a manganese content of 6.3 × 10⁶. 4 Mw is 11 x 10 4 It was also shown that the molecular weight distribution was 1.85.

[0069] Nuclear magnetic resonance (NEM) testing revealed that the molar ratio of adipic acid:terephthalic acid:franjicarboxylic acid in the PBATF copolymer polyester was 49.1:25.4:25.5, and this composition was consistent with the supply ratio.

[0070] Tensile properties tests revealed that the PBATF copolymer polyester had a tensile modulus of 12.1 MPa, a tensile strength at break of 5.3 MPa, and an elongation at break exceeding 1600%. The elastic recovery rate after initial stretching was greater than 70%, the average elastic recovery rate was approximately 80%, and no yielding phenomenon was observed, thus proving that this sample possesses elastomer properties.

[0071] [Comparative Example 1] 31.2 g of 2,5-franzicarboxylic acid, 299 g of terephthalic acid, 236 g of succinic acid, and 540 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 0.6 g of tetra-n-butyl titanate, 0.2 g of dibutyltin oxide, and 0.5 g of lanthanum acetylacetonate were added. Esterification was carried out in the presence of a nitrogen atmosphere, and the temperature was gradually increased to 190°C. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 210°C. After 1.5 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 245°C for 3 hours to finally produce a copolymer polyester denoted as PBSTF-1.

[0072] GPC testing showed that the PBSTF-1 copolymer polyester has a manganese content of 9.2 × 10⁶. 4 Mw is 16.4 × 10 4 The molecular weight distribution was shown to be 1.76. The temperature corresponding to a 5% weight loss under an N2 atmosphere was 360°C, and the thermal decomposition temperature was 406°C. Nuclear magnetic resonance testing showed that the molar ratio of succinic acid:terephthalic acid:franjiocarboxylic acid in the PBSTF-1 copolymer polyester was 49.7:45.3:5.0, and this composition was consistent with the supply ratio. Tensile properties testing showed that the PBSTF-1 copolymer polyester had a tensile modulus of 71.1 MPa, a tensile strength at break of 18.5 MPa, an elongation at break exceeding 1328%, and a yield strength of 8.5 MPa. The PBSTF-1 copolymer polyester did not exhibit good elasticity and recovery properties.

[0073] [Comparative Example 2] 110.4 g of dimethyl 2,5-franzicarboxylate, 232.4 g of terephthalic acid, 236 g of succinic acid, and 540 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 0.6 g of tetra-n-butyl titanate, 0.2 g of dibutyltin oxide, and 0.5 g of lanthanum acetylacetonate were added. Under a nitrogen atmosphere, the temperature was gradually increased to 190°C to carry out the esterification reaction. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 210°C. After 1.5 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 245°C for 3 hours to finally produce a copolymer polyester denoted as PBSTF-2.

[0074] GPC testing showed that the PBSTF-2 copolymer polyester has a manganese content of 5.1 × 10⁶. 4 Therefore, Mw is 12.6 × 10 4 The molecular weight distribution was shown to be 2.25. Nuclear magnetic resonance testing showed that the molar ratio of succinic acid:terephthalic acid:frangicarboxylic acid in the PBSTF-2 copolymer polyester was 48.7:36.1:15.2, and this composition was consistent with the supply ratio. Tensile properties testing showed that the PBSTF-2 copolymer polyester had a tensile modulus of 29.2 MPa, a tensile strength at break of 8.2 MPa, an elongation at break exceeding 1352%, and a yield strength of 4.6 MPa.

[0075] [Comparative Example 3] 424 g of terephthalic acid, 330 g of succinic acid, and 650 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 0.4 g of tetraisopropyl titanate, 0.2 g of dibutyltin oxide, and 0.9 g of lanthanum acetylacetonate were added. The esterification reaction was carried out in the presence of a nitrogen atmosphere, and the temperature was gradually increased to 220°C. When the esterification rate reached 98%, a preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 230°C. After 2 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 250°C for 5 hours to finally produce a copolymer polyester denoted as PBST.

[0076] GPC testing showed that the PBST copolymer polyester has a manganese content of 5.4 × 10⁶. 4 Therefore, Mw is 9.3 × 10 4 The molecular weight distribution was shown to be 1.72. Tensile properties tests showed that the PBST copolymer polyester had a tensile modulus of 94.6 MPa, an elongation at break exceeding 602%, and a yield strength of 10.0 MPa. The PBST copolymer polyester did not possess elasticity or recovery properties.

[0077] [Comparative Example 4] 436 g of 2,5-franzicarboxylic acid, 330 g of succinic acid, and 650 g of 1,4-butylene glycol were added to a reactor to form a slurry, and 0.4 g of tetraisopropyl titanate, 0.2 g of dioctyl tin oxide, and 0.9 g of lanthanum acetylacetonate were added. Under a nitrogen atmosphere, the temperature was gradually increased to 191°C to carry out the esterification reaction. When the esterification rate reached 98%, the preliminary polycondensation reaction was started, and the vacuum reaction conditions were gradually set. The pressure was reduced to 1 kPa, and the temperature was gradually increased to 200°C. After 2 hours of reaction, the polycondensation reaction was started. The vacuum was controlled to be lower than 150 Pa, and the reaction was carried out at 235°C for 5 hours to finally produce a copolymer polyester denoted as PBSF. GPC testing showed that the PBSF copolymer polyester had a manganese content of 6.9 × 10⁶. 4 Therefore, Mw is 11.9 × 104 The molecular weight distribution was shown to be 1.71. Tensile properties tests showed that the PBSF copolymer polyester had a tensile modulus of 31.1 MPa and an elongation at break exceeding 1138%. Mechanical tests showed slight yielding, with a yield strength of 2.2 MPa, similar to that of elastomer materials, and an elastic recovery rate of less than 50%.

[0078] [Example Test] Characteristics of the arrangement structure in furan ring-containing polyester elastomers

[0079] 1 The 1H NMR experiment was performed using an Agilent 600MHz DD2 nuclear magnetic resonance spectrometer. The solvent was CDCl3, the sample concentration was approximately 35% (w / v), and the test temperature was room temperature. The latency period for the hydrogen spectrum was 10 seconds, the pulse was 45°, and the number of samples was 16.

[0080] The 1.60–2.10 ppm peak in the hydrogen spectrum corresponds to the proton peaks of the two intermediate methylene groups of the butylene glycol unit, and the 4.00–4.50 ppm peak corresponds to the proton peaks of the two methylene groups adjacent to the oxygen atom of the butylene glycol unit. This splitting is due to different dicarboxylic acids adjacent to the butylene glycol. The sequence distribution is calculated based on the areas of the split peaks at 1.60–2.10 ppm and 4.00–4.50 ppm. The peak area at 1.71 ppm corresponds to the SS sequence, the peak area at 1.98 ppm corresponds to the TT sequence, the peak area at 1.92 ppm corresponds to the FF sequence, the peak areas at 1.93–1.97 ppm correspond to the TF / FT sequence, and the peak areas at 4.07–4.20 ppm correspond to the ST, SF, and SS sequences. Peak fitting was performed in this region using Dmfit software to determine the peak areas of ST, SF, and SS. The peak area of ​​SS corresponds to the SS sequence. The peak areas of ST and SF were doubled, respectively, to correspond to the ST / TS and SF / FS sequences. By dividing the corresponding peak area of ​​each sequence by the sum of the peak areas of all sequences, the proportion of different two-component segment sequence structures can be determined, where SS represents that both dibasic acids adjacent to both ends of butylene glycol are succinic acid, TT represents that both dibasic acids adjacent to both ends of butylene glycol are terephthalic acid, FF represents that both dibasic acids adjacent to both ends of butylene glycol are frangic acid; ST / TS represents that one of the dibasic acids adjacent to both ends of butylene glycol is succinic acid and the other is terephthalic acid; SF / FS represents that one of the dibasic acids adjacent to both ends of butylene glycol is succinic acid and the other is frangic acid; TF / FT represents that one of the dibasic acids adjacent to both ends of butylene glycol is terephthalic acid and the other is frangic acid.

[0081] Table 1 shows the results of the proportion of two-component segment arrangement structures in the furan ring-containing polyester elastomers prepared in the examples and comparative examples.

[0082] [Table 1] Table 2 shows the mechanical properties of the copolymerized polyesters prepared in Examples 1-2 and Comparative Examples 1-4.

[0083] [Table 2]

[0084] As shown in the XRD comparative data for the examples and comparative examples in Figure 14, the introduction of the fourth monomer, a frangic acid compound, in the present invention alters the crystallinity of PBST. As the amount of the frangic acid compound increases, the crystallinity peak of PBST first gradually weakens and then strengthens, accompanied by a significant change in thermodynamic properties. This indicates that the rigid furan polyester chain segments formed in the system disrupt the structure and crystalline arrangement of the PBST polymer chain. The copolymer arrangement data in Table 1 shows that after the addition of the frangic acid compound, a certain proportion of furan and aromatic units link to form the two-component unit FT / TF, which affects the molecular chain arrangement and regularity of polymer PBST, and thereby affects its crystallinity. The arrangement of the polymer arrangement structure directly affects various performance properties of the polymer material in use. In the present invention, the product exhibits amorphous (or weakly crystalline) behavior in its unextended state only when the four component units are present in specific ratios, and crystallinity is induced upon extension. As a result, the material acquires excellent chain entanglement and crystalline micro-regions that act as physical crosslinking points, thereby conferring elastomer properties, outstanding resilience, excellent fatigue resistance, and elastic self-reinforcing effects to the material. [Brief explanation of the drawing]

[0085] [Figure 1] Figure 1 shows the hydrogen nuclear magnetic spectrum of the furan ring-containing polyester elastomer obtained in Comparative Example 1. [Figure 2]Figure 2 shows the DSC spectrum of the furan ring-containing polyester elastomer obtained in Comparative Example 1. [Figure 3] Figure 3 shows the hydrogen nuclear magnetic spectrum of the furan ring-containing polyester elastomer obtained in Example 1. [Figure 4] Figure 4 shows the DSC spectrum of the furan ring-containing polyester elastomer obtained in Example 1. [Figure 5] Figure 5 shows the cyclic tensile hysteresis loop of the furan ring-containing polyester elastomer obtained in Example 1 under strain conditions of 100 to 1400%. [Figure 6] Figure 6 shows the elastic recovery rate corresponding force curve of the furan ring-containing polyester elastomer obtained in Example 1 under strain conditions of 100 to 1400%. [Figure 7a] Figure 7 shows (a) the elastic recovery rate, (b) the corresponding tensile modulus and dissipated energy during 10 consecutive stretching cycles under 300% strain conditions for the furan ring-containing polyester elastomer obtained in Example 1. [Figure 7b] Figure 7 shows (a) the elastic recovery rate, (b) the corresponding tensile modulus and dissipated energy during 10 consecutive stretching cycles under 300% strain conditions for the furan ring-containing polyester elastomer obtained in Example 1. [Figure 8a] Figure 8 shows the cyclic stretching curve of the furan ring-containing polyester elastomer obtained in Example 1: (a) the stretching curve for cycles 1 to 10 under 200% strain conditions, and (b) the stretching curve for cycles 1 to 10 under 300% strain conditions; the curves in the figure, from top to bottom, represent the stretching curves for cycles 1 to 10. [Figure 8b]Figure 8 shows the cyclic stretching curve of the furan ring-containing polyester elastomer obtained in Example 1: (a) the stretching curve for cycles 1 to 10 under 200% strain conditions, and (b) the stretching curve for cycles 1 to 10 under 300% strain conditions; the curves in the figure, from top to bottom, represent the stretching curves for cycles 1 to 10. [Figure 9] Figure 9 shows the DSC spectrum of the PBST copolymer polyester obtained in Comparative Example 3. [Figure 10] Figure 10 shows the DSC spectrum of the PBSF copolymer polyester obtained in Comparative Example 4. [Figure 11] Figure 11 shows the stress-strain curve of the PBSF copolymer polyester obtained in Comparative Example 4. [Figure 12a] Figure 12 shows a before-and-after comparison of the tensile rebound performance of the sample strip of the furan ring-containing polyester elastomer obtained in Example 1: (a) is a photograph of the strip before rebound, and (b) is a photograph of the strip after rebound. [Figure 12b] Figure 12 shows a before-and-after comparison of the tensile rebound performance of the sample strip of the furan ring-containing polyester elastomer obtained in Example 1: (a) is a photograph of the strip before rebound, and (b) is a photograph of the strip after rebound. [Figure 13a] Figure 13 shows the two-dimensional X-ray diffraction pattern (a) and the corresponding one-dimensional X-ray diffraction pattern (b) of Example 1 at different elongation factors. [Figure 13b] Figure 13 shows the two-dimensional X-ray diffraction pattern (a) and the corresponding one-dimensional X-ray diffraction pattern (b) of Example 1 at different elongation factors. [Figure 14] Figure 14 shows a comparison of the XRD patterns of the examples and comparative examples.

Claims

1. (F) Structural units derived from flangic acid and / or its esters; (T) Structural units derived from aromatic dibasic acids and / or aromatic dibasic acid esters; (S) Structural unit derived from an aliphatic dibasic acid; (D) Structural units derived from aliphatic dihydric alcohols; A furan ring-containing polyester elastomer, The furan ring-containing polyester elastomer is a combination of the following structural units: SDS, where SDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends of it are structural units derived from aliphatic dibasic acids (e.g., succinic acid); TDT, where TDT represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are structural units derived from aromatic dibasic acids and / or aromatic dibasic acid esters (e.g., terephthalic acid); FDF, where FDF represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are structural units derived from frangic acid and / or its esters (e.g., frangic acid); SDT / TDS, where SDT / TDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are structural units where one end is derived from an aliphatic dibasic acid (e.g., succinic acid) and the other end is derived from an aromatic dibasic acid and / or an aromatic dibasic acid ester (e.g., terephthalic acid); SDF / FDS, where SDF / FDS represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are such that one end is a structural unit derived from an aliphatic dibasic acid (e.g., succinic acid) and the other end is a structural unit derived from frangic acid and / or its ester (e.g., frangic acid); TDF / FDT, where TDF / FDT represents a structural unit derived from an aliphatic dihydric alcohol (e.g., butylene glycol), and the dibasic acids adjacent to both ends are such that one end is a structural unit derived from an aromatic dibasic acid and / or an aromatic dibasic acid ester (e.g., terephthalic acid), and the other end is a structural unit derived from a frangic acid and / or its ester (e.g., frangic acid); Includes, Here, based on the criterion that the total amount of the structural unit combinations SDS, TDT, FDF, SDT / TDS, SDF / FDS, and TDF / FDT is 100 mol%, The amount of the aforementioned structural unit combination SDS is 21 to 28 mol%; The amount of TDT for the combination of the aforementioned structural units is 2 to 9 mol%; The amount of FDF in the combination of the aforementioned structural units is 6 to 15 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 13 to 28 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 22 to 38 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 9 to 14 mol%; Preferably, The amount of the aforementioned structural unit combination SDS is 23 to 26 mol%; The amount of TDT for the combination of the aforementioned structural units is 2 to 8 mol%; The amount of FDF in the combination of the aforementioned structural units is 6 to 14 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 13 to 26 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 23 to 37 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 9 to 13 mol%; more, The amount of the aforementioned structural unit combination SDS is 23 to 26 mol%; The amount of TDT for the combination of the aforementioned structural units is 2 to 8 mol%; The amount of FDF in the combination of the aforementioned structural units is 6 to 14 mol%; The amount of the aforementioned structural unit combination SDT / TDS is 14 to 26 mol%; The amount of the aforementioned structural unit combination SDF / FDS is 24 to 36 mol%; and The amount of the aforementioned structural unit combination TDF / FDT is 10 to 13 mol%. A polyester elastomer containing furan rings.

2. A furan ring-containing polyester elastomer comprising the reaction product of component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol, The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9–1.05), for example, 1:(0.95–1.02), or 1:(0.96–1.01); A furan ring-containing polyester elastomer having a molar ratio of component (a) to component (b) of 1:(0.4 to 1.8), preferably 1:(0.4 to 1.2).

3. The furan ring-containing polyester elastomer according to claim 1 or 2 is characterized in that it has one, two, three, four, five, six, seven, eight or nine of the following features: (1) In the measurement of tensile properties according to GB / T 1040.1-2018, the elongation at break is greater than 1500%, preferably greater than 1600%; (2) Elastic recovery rate is greater than 70%; (3) The weight-average molecular weight is greater than 60,000 and the molecular weight distribution is 1.6 to 2.3; preferably, the weight-average molecular weight is greater than 100,000 and the molecular weight distribution is 1.6 to 2.0; (4) The average elastic recovery rate is 80% or higher; (5) Having elastic self-reinforcing ability, preferably, when the elongation ratio is 500% or more, the elastic recovery rate is greater than 85%, and when the elongation ratio is 800% or more, the elastic recovery rate is greater than 90%; (6) Weight-average molecular weight is 9 to 15 × 10 ４ The number-average molecular weight is 5 to 10 × 10 ４ The molecular weight distribution is 1.6 to 2.3, and the weight-average molecular weight × number-average molecular weight is 50 to 120 × 10⁻¹⁰. ８ Preferably, the weight-average molecular weight is 10 to 14 × 10 ４ The number-average molecular weight is 5 to 9 × 10⁻⁶. ４ The molecular weight distribution is 1.6 to 2.0, and the weight-average molecular weight × number-average molecular weight is 60 to 110 × 10 ８ It is; (7) In the measurement of tensile properties according to GB / T 1040.1-2018, the tensile modulus is 8 to 75 MPa, for example 10 to 75 MPa, 8 to 25 MPa, and 10 to 16 MPa; (8) In the measurement of tensile properties according to GB / T 1040.1-2018, the tensile strength at fracture is 3 to 20 MPa, for example 4 to 20 MPa, 3 to 8 MPa, or 4 to 6 MPa; and (9) No yield phenomenon was observed in the measurement of tensile properties according to GB / T 1040.1-2018.

4. The furan ring-containing polyester elastomer according to claim 1, having the following characteristics: The frangic acid and / or ester thereof is at least one of 2,5-frangic acid, dimethyl 2,5-frangic carboxylate, and diethyl 2,5-frangic carboxylate; and / or The aforementioned aromatic dibasic acid and / or aromatic dibasic acid ester is C ８ -C １８ Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid and isophthalic acid esters; and / or where the aliphatic dibasic acid is C ２ -C １８ at least one of the aliphatic dibasic acids, preferably at least one of sebacic acid, succinic acid, and adipic acid; and / or The aliphatic dihydric alcohol is C ２ -C ８ The alcohol is at least one of the dihydric alcohols, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol.

5. A method for preparing a furan ring-containing polyester elastomer according to any one of claims 1 to 4, comprising the step of sequentially subjecting component (a) franc carboxylic acid and / or its ester, component (b) aromatic dibasic acid and / or aromatic dibasic acid ester, component (c) aliphatic dibasic acid, and component (d) aliphatic dihydric alcohol to an esterification reaction, a preliminary polycondensation reaction, and a final polycondensation reaction to produce a furan ring-containing polyester elastomer.

6. The preparation method according to claim 5, characterized in that it includes the following steps in particular: (1) A step of subjecting components (a), (b), (c), and (d) to an esterification reaction under the action of the first catalyst; (2) When the esterification rate reaches 92-98%, a preliminary polycondensation reaction is carried out under the action of a second catalyst; (3) A step of subjecting the reaction system obtained in step (2) to a final polycondensation reaction to produce the furan ring-containing polyester elastomer.

7. The preparation method according to claim 6, having the following characteristics: The component (a) is at least one of 2,5-franzicarboxylic acid, dimethyl 2,5-franzicarboxylate, and diethyl 2,5-franzicarboxylate; and / or The aforementioned component (b) is C ８ -C １８ Selected from aromatic dibasic acids or aromatic dibasic acid ester compounds, preferably at least one of terephthalic acid, terephthalic acid esters, isophthalic acid, and isophthalic acid esters; and / or The aforementioned component (c) is C ２ -C １８ At least one aliphatic dibasic acid, preferably at least one of sebacic acid, succinic acid, and adipic acid; and / or The aforementioned component (d) is C ２ -C ８ At least one dihydric alcohol, preferably at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, and neopentyl glycol; and / or The first catalyst comprises an organotitanium compound and at least one compound comprising antimony, germanium, zirconium, tin, magnesium, cobalt, aluminum, or zinc, preferably comprising an organotitanium compound and at least one organotin compound; and / or The second catalyst is at least one of the lanthanide series metal compounds, preferably at least one of lanthanum chloride, lanthanum acetylacetonate, neodymium isopropoxide, and lanthanum stearate.

8. The preparation method according to claim 7, having the following characteristics: The organotitanium compound is selected from butyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetraethyl titanate, and titanium glycolate; and / or, The organotin compound is at least one of stannous octanoate, stannous oxalate, dibutyltin oxide, butyltin hydroxide oxide, dibutyltin diacetate, dioctyltin oxide, and butyltin tris(2-ethylhexanoate); and / or Based on a total amount of 100 parts by weight of the first catalyst, the organotitanium compound contains 45 to 85 parts by weight, for example, 55 to 75 parts by weight or 75 to 85 parts by weight; and the organotin compound contains 15 to 55 parts by weight, for example, 25 to 45 parts by weight or 15 to 25 parts by weight.

9. The preparation method according to claim 6, wherein step (1) has the following characteristics: The ratio of the total number of moles of component (a), component (b), and component (c) to the number of moles of component (d) is 1:(1.05 to 4), preferably 1:(1.2 to 2); and / or The ratio of the total number of moles of component (a) and component (b) to the number of moles of component (c) is 1:(0.9–1.05), for example, 1:(0.95–1.02), or 1:(0.96–1.01); The molar ratio of component (a) to component (b) is 1:(0.4 to 1.8), preferably 1:(0.4 to 1.2); The amount of the first catalyst used is 0.01 to 1% by weight, for example, 0.1 to 0.3% by weight or 0.05 to 0.2% by weight, relative to the total amount of component (a), component (b), and component (c); and / or The conditions for the esterification reaction are as follows: the esterification temperature is 130 to 210°C, for example, 150 to 190°C; the reaction time is 1 to 5 hours, for example, 2 to 3 hours; and the reaction atmosphere is a protective gas.

10. The preparation method according to claim 6, wherein step (2) has the following characteristics: The amount of the second catalyst used is 0.01 to 0.5% by weight, preferably 0.05 to 0.2% by weight, relative to the total amount of component (a), component (b), and component (c); and / or The conditions for the aforementioned pre-polycondensation reaction are as follows: the reaction temperature is 150 to 220°C, for example 190 to 210°C; and / or the reaction time is 0.5 to 2.5 hours, for example 1 to 1.5 hours; and / or the vacuum level is 600 to 5000 Pa, for example 1000 to 2000 Pa.

11. The preparation method according to claim 6, characterized in that, in step (3), the conditions for the final polycondensation reaction are as follows: The reaction temperature is 210 to 260°C, for example, 230 to 250°C; and / or The reaction time is 1 to 5 hours, for example, 2 to 4 hours; and / or The vacuum level is 300 Pa or less, for example, 150 Pa or less, or 50 Pa or less.

12. Use of a furan ring-containing polyester elastomer according to any one of claims 1 to 4, or a furan ring-containing polyester elastomer obtained by the preparation method according to any one of claims 5 to 11, in a biodegradable material.

Images