A polyamide elastomer and its preparation method and application

Abstract

The present invention belongs to the technical field of bio-based polymer materials, and specifically relates to a polyamide elastomer, a preparation method thereof, and an application thereof. The polyamide elastomer provided by the present invention comprises alternating hard segment polymers and soft segment polymers; the polyamide elastomer has a structure shown in Formula I; the hard segment is a bio-based polyamide prepolymer having a structure shown in Formula II; the number average molecular weight of the hard segment polymer is 1000 to 5000 g / mol; and the amount of the hard segment polymer in the elastomer accounts for 10% to 50%. The polyamide elastomer provided by the present invention has good heat resistance and mechanical properties. Formula I.

Description

Technical Field

[0001] The present invention belongs to the technical field of bio-based polymer materials, and in particular relates to a polyamide elastomer and a preparation method and application thereof. Background Art

[0002] In the development of high-performance elastomeric materials, how to achieve synergistic optimization between toughness, heat resistance and strength has always been the core challenge of material structure design. Polyamide elastomers are usually composed of rigid hard segments and flexible soft segments. The hard segments are responsible for providing the strength and thermal stability of the material, while the soft segments give it stretchability and elastic recovery. However, the significant differences between the hard and soft segments in polarity, crystallinity, rigidity and flexibility often lead to poor interfacial compatibility and uncontrollable microphase separation structure in the system, which in turn causes a contradiction between mechanical properties and heat resistance that is difficult to balance. In the context of constructing elastomers with bio-based raw materials, this problem is particularly prominent. How to construct polyamide elastomers with high temperature stability, excellent toughness and strength without relying on petroleum-based monomers is still a key technical problem that needs to be solved in the current field of bio-based polymers. Summary of the Invention

[0003] The purpose of the present invention is to provide a polyamide elastomer and a preparation method and application thereof. The polyamide elastomer provided by the present invention has good heat resistance and mechanical properties.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a polyamide elastomer, which comprises hard segment polymers and soft segment polymers arranged alternately; the hard segment polymer is a bio-based polyamide prepolymer;

[0006] The polyamide elastomer has a structure shown in formula I;

[0007] Formula I;

[0008] A1 and A2 are independently or , and A1 and A2 are not simultaneously or ;

[0009] M1 and M2 are independently or , and M1 and M2 are not simultaneously or ;

[0010] The hard segment polymer has the structure described in Formula II:

[0011] Formula II;

[0012] The number average molecular weight of the hard segment polymer is 1000-5000 g / mol;

[0013] The amount of the hard segment polymer in the polyamide elastomer is 10% to 50%.

[0014] Preferably, the soft segment polymer accounts for 50% to 90% of the polyamide elastomer.

[0015] Preferably, the number average molecular weight of the polyamide elastomer is 15,000-25,000 g / mol.

[0016] The present invention also provides a method for preparing the polyamide elastomer described in the above technical solution, comprising the following steps:

[0017] (1) 2,5-thiophenedicarboxylic acid, decanediamine, sebacic acid, water and a polycondensation catalyst are mixed to carry out a polycondensation reaction to obtain a bio-based polyamide prepolymer; the 2,5-thiophenedicarboxylic acid is derived from glucaric acid and muconic acid; the decanediamine and sebacic acid are derived from castor oil;

[0018] The structural formula of the bio-based polyamide prepolymer is:

[0019] ;

[0020] (2) mixing a bio-based polyamide prepolymer, a bio-based polytrimethylene ether glycol, an isosorbide-based poly(arylene ether sulfone) and tetrabutyl titanate, and performing block polymerization to obtain a block copolymer with alternating soft and hard segments;

[0021] The structural formula of the isosorbide-based poly(arylene ether sulfone) is:

[0022] ;

[0023] (3) The block structure copolymer with alternating soft and hard segments is sequentially extruded, pelletized and dried to obtain the polyamide elastomer.

[0024] Preferably, the polycondensation reaction is carried out in the presence of a polycondensation catalyst, and the polycondensation catalyst comprises sodium hypophosphite and / or sodium hypophosphite.

[0025] Preferably, the molar ratio of decanediamine to the total moles of 2,5-thiophenedicarboxylic acid and sebacic acid is 0.7-0.98:1.0.

[0026] Preferably, the block polymerization is carried out sequentially as a preliminary block polymerization and a final block polymerization;

[0027] The temperature of the preliminary block polymerization is 210-230° C., the pressure is 0.1-0.3 MPa, and the time is 1.0-3.0 h;

[0028] The final block polymerization is carried out under vacuum conditions, with a temperature of 240-250° C. and a time of 1.0-3.0 h.

[0029] Preferably, the polycondensation reaction is a process of mixing 2,5-thiophenedicarboxylic acid, decanediamine, sebacic acid, water and a polycondensation catalyst, followed by salt formation and polymerization.

[0030] Preferably, the temperature of the salt formation is 100°C and the pressure is 0.5 MPa;

[0031] The polymerization includes a first polymerization, a second polymerization, a third polymerization and a fourth polymerization carried out sequentially;

[0032] The first polymerization temperature is 200°C, the pressure is 1.3-1.5 MPa, and the time is 1.0 h;

[0033] The temperature of the second polymerization is 220-240°C, the pressure is 1.6-1.8 MPa, and the time is 1.0-1.2 h; the temperature of the third polymerization is 220-240°C, the pressure is atmospheric pressure, and the time is 1.0-1.2 h;

[0034] The fourth polymerization is carried out under vacuum, the vacuum pressure is -80 kPa, the temperature of the fourth polymerization is 220-240° C., and the time is 0.5-0.6 h.

[0035] The present invention also provides applications of the polyamide elastomer described in the above technical solution or the polyamide elastomer prepared by the above preparation method in civil aviation, automobile manufacturing and intelligent sensing.

[0036] The polyamide elastomer of this invention consists of an alternating arrangement of bio-based polyamide prepolymers, bio-based polytrimethylene ether glycol (PO3G), and isosorbide-based poly(arylene ether sulfone) (IPAES), chemically linked to form a molecular chain structure that combines rigidity and flexibility. The introduction of 2,5-thiophenedicarboxylic acid significantly enhances the rigidity and heat resistance of the polyamide hard segment. The acid-terminated polyamide prepolymer design controls the molecular weight of the hard segment and adjusts the ratio of the hard and soft segments, resulting in a controllable microphase separation between the ordered crystalline regions of the hard segment and the amorphous regions of the soft segment. The IPAES, through the introduction of isosorbide groups and ether bonds, enhances the rigidity and flexibility of the soft segment. It also copolymerizes with the hard segment through a hydrogen bonding network, improving the material's elastic recovery and energy dissipation capabilities. This structural design breaks away from the single crosslinking or simple blending model of traditional elastomers. Through the synergistic innovation of bio-based block sequences and dynamic crosslinking networks, it provides a new approach for the structural design of high-performance elastomers.

[0037] The data of the examples show that the tensile strength of the polyamide elastomer provided by the present invention is 50-70 MPa; and the elongation at break is 500-600%. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 This is the infrared spectrum of the bio-based polyamide prepolymer prepared in Example 1;

[0040] Figure 2 This is the infrared spectrum of the bio-based polyamide elastomer prepared in Example 1. DETAILED DESCRIPTION

[0041] The present invention provides a polyamide elastomer, which comprises hard segment polymers and soft segment polymers arranged alternately; the hard segment polymer is a bio-based polyamide prepolymer;

[0042] The polyamide elastomer has a structure shown in formula I;

[0043] Formula I;

[0044] A1 and A2 are independently or , and A1 and A2 are not simultaneously or ;

[0045] M1 and M2 are independently or , and M1 and M2 are not simultaneously or ;

[0046] The hard segment polymer has the structure described in Formula II:

[0047] Formula II;

[0048] The number average molecular weight of the hard segment polymer is 1000-5000 g / mol;

[0049] The amount of the hard segment polymer in the elastomer is 10% to 50%.

[0050] As an embodiment of the present invention, the amount of hard segment polymer in the polyamide elastomer is 10% to 50%, specifically 10%, 20%, 30%, 40% or 50%, and the amount of soft segment polymer is 50% to 90%, specifically 90%, 80%, 70%, 60% or 50%. As an embodiment of the present invention, the number average molecular weight of the polyamide elastomer is 15,000 to 25,000 g / mol. As an embodiment of the present invention, the melt index of the polyamide elastomer is 12 to 15 g / 10 min at 190°C.

[0051] The polyamide elastomer of the present invention enhances the rigidity and thermal stability of the hard segment by introducing the aromatic ring structure 2,5-thiophenedicarboxylic acid, and combines with the soft segment through hydrogen bonds to improve the interface compatibility between the hard segment and the soft segment. By introducing the isosorbide group and ether bond in IPAES, the heat resistance and mechanical properties of the soft segment are synergistically improved. The elastic recovery ability and energy dissipation capacity of the material are improved by copolymerization of the hard segment and formation of a hydrogen bond network between molecular chains.

[0052] As an embodiment of the present invention, the tensile strength of the polyamide elastomer may be 50-70 MPa; the elongation at break may be 500-600%.

[0053] As an embodiment of the present invention, the intrinsic viscosity of the polyamide elastomer may be 1.3-1.5 dL / g (concentrated sulfuric acid, 25° C.), and the elasticity retention rate may be 85-90%.

[0054] The present invention also provides a method for preparing the polyamide elastomer described in the above technical solution, comprising the following steps:

[0055] (1) 2,5-thiophenedicarboxylic acid (TDCA), decanediamine, sebacic acid, water and a polycondensation catalyst are mixed to carry out a polycondensation reaction to obtain a bio-based polyamide prepolymer; the 2,5-thiophenedicarboxylic acid is derived from glucaric acid and muconic acid; the decanediamine and sebacic acid are derived from castor oil;

[0056] The structural formula of the bio-based polyamide prepolymer is:

[0057] ;

[0058] (2) Bio-based polyamide prepolymer, bio-based polytrimethylene ether glycol (PO3G), isosorbide-based poly(arylene ether sulfone) (IPAES) and tetrabutyl titanate were mixed and block polymerized to obtain a block copolymer with alternating soft and hard segments.

[0059] (3) Extruding and pelletizing the copolymer to obtain the polyamide elastomer.

[0060] The present invention mixes 2,5-thiophenedicarboxylic acid (TDCA), decanediamine, sebacic acid, water and a polycondensation catalyst, and performs polycondensation to obtain a bio-based polyamide prepolymer.

[0061] Decanediamine structure ;

[0062] Sebacic acid structural formula: ;

[0063] 2,5-Thiophenedicarboxylic acid structural formula: ;

[0064] As an embodiment of the present invention, the polycondensation catalyst includes sodium hypophosphite and / or sodium hypophosphite. Specifically, the polycondensation reaction is preferably carried out by mixing 2,5-thiophenedicarboxylic acid (TDCA), decanediamine, sebacic acid, water and the polycondensation catalyst, followed by salt formation and polymerization.

[0065] In one embodiment of the present invention, the decanediamine and sebacic acid are derived from castor oil; the 2,5-thiophenedicarboxylic acid is derived from glucaric acid and muconic acid; and the amount of 2,5-thiophenedicarboxylic acid accounts for 10-50% of the total amount of acid in the raw materials. In another embodiment of the present invention, the molar ratio of decanediamine to the total moles of TDCA and sebacic acid is 0.7-0.98:1.0, specifically 0.89:1. The mass of the water can be 10-12% of the combined mass of decanediamine, sebacic acid, and TDCA; and the mass of the polycondensation catalyst can be 0.15% of the combined mass of decanediamine, sebacic acid, TDCA, and water.

[0066] As an embodiment of the present invention, the temperature of the salt formation can be 100°C and the pressure can be 0.2 MPa; pre-activation is also included before the salt formation, and the pre-activation is preferably carried out under nitrogen and stirring conditions; the heating rate for heating to the pre-activation temperature can be 5°C / min; and the stirring speed can be 50 rpm.

[0067] As an embodiment of the present invention, the polymerization includes a first polymerization, a second polymerization, a third polymerization and a fourth polymerization performed sequentially.

[0068] As an embodiment of the present invention, the temperature of the first polymerization can be 200°C, the pressure can be 1.3~1.5 MPa, specifically 1.5 MPa, and the time can be 1.0 h. As an embodiment of the present invention, the temperature of the second polymerization can be 220~240°C, specifically 240°C, the pressure can be 1.6~1.8 MPa, specifically 1.8 MPa, and the time can be 1.0~1.2 h, specifically 1.0 h. As an embodiment of the present invention, the temperature of the third polymerization can be 220~240°C, specifically 240°C, the pressure can be atmospheric pressure, and the time can be 1.0~1.2 h, specifically 1 h. As an embodiment of the present invention, the fourth polymerization is carried out under vacuum, the vacuum pressure is -80 kPa, the temperature of the fourth polymerization can be 220~240°C, specifically 240°C, and the time can be 0.5~0.6 h, specifically 0.5 h.

[0069] After obtaining the bio-based polyamide prepolymer, the present invention mixes the bio-based polyamide prepolymer, PO3G, IPAES and tetrabutyl titanate, and performs block polymerization to obtain a copolymer with a block structure in which soft and hard segments are alternately arranged.

[0070] As an embodiment of the present invention, the structural formula of the PO3G is:

[0071]

[0072] As one embodiment of the present invention, the molecular weight of the bio-based polytrimethylene glycol ether can be 1900~2000 g / mol, and the PO3G can be ECOTRION H2000 provided by SK Group of South Korea; as another embodiment of the present invention, the bio-based polytrimethylene glycol ether is preferably obtained by polymerizing 1,3-propylene glycol fermented from corn sugar.

[0073] As an embodiment of the present invention, the structural formula of the isosorbide-based poly(arylene ether sulfone) is:

[0074]

[0075] As an embodiment of the present invention, the isosorbide-based poly(arylene ether sulfone) can be prepared according to “Belgacem, C.; Medimagh, R.; Fildier, A.et. al. Synthesis and Characterization of Isosorbide-Based α,ω-Dihydroxyethersulfone Oligomers. Des. Monomers Polym. 2015, 18 (1), 64-72”.

[0076] As an embodiment of the present invention, the ratio of the amount of the bio-based polyamide prepolymer to the total amount of PO3G and IPAES can be 0.1-1.0:1.0, specifically 0.43:1. As an embodiment of the present invention, the amount of tetrabutyl titanate can be 2‰ of the total mass of the bio-based polyamide prepolymer, bio-based polytrimethylene ether glycol, and water.

[0077] As an embodiment of the present invention, the block polymerization is preferably performed by mixing a bio-based polyamide prepolymer, PO3G, IPAES and tetrabutyl titanate, and sequentially performing preliminary block polymerization and final block polymerization.

[0078] As an embodiment of the present invention, the preliminary block polymerization is 210~220℃, specifically 210℃ or 220℃; the pressure can be 0.1~0.3 MPa, specifically 0.25 MPa, and the time can be 1.5~3.0 h; the temperature of the final block polymerization can be 230~240℃, specifically 230℃ or 240℃; the time of the final block polymerization can be 2h; and the final block polymerization is carried out under vacuum conditions.

[0079] After obtaining the copolymer, the present invention sequentially extrude, pelletize and dry the copolymer to obtain the polyamide elastomer.

[0080] This invention introduces the aromatic rigid dicarboxylic acid 2,5-thiophenedicarboxylic acid (TDCA) into the hard segment to enhance the chain rigidity and heat resistance of the polyamide backbone. At the same time, isosorbide-based poly(arylene ether sulfone) (IPAES) is used as a flexible soft segment to synergize with traditional polytrimethylene ether glycol (PO3G) to construct a structure, significantly improving the thermal stability and hydrogen bonding ability of the material at the soft segment level. During the polymerization process, the two randomly connect with the acid-terminated polyamide prepolymer through an esterification reaction, forming a disordered block structure. This effectively avoids the conventional block structure's reliance on sequence regularity while enhancing the synergistic effect between the soft and hard segments. This structural approach balances the flexible responsiveness of the microphase region with the thermomechanical stability of the overall network, providing a new path for achieving high-performance polyamide elastomers.

[0081] The present invention also provides the polyamide elastomer described in the above technical solution or the application of the polyamide elastomer described in the above technical solution in civil aviation, automobile manufacturing and intelligent sensing.

[0082] As an embodiment of the present invention, the operating temperature range of the polyamide elastomer is -50~240°C. When used at the above temperature, the polyamide elastomer provided by the present invention has good stability.

[0083] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0084] Example 1

[0085] (1) Weigh 2.35 mol of sebacic acid, 1.00 mol of 2,5-thiophenedicarboxylic acid, and 3.00 mol of decanediamine, add 130 g of deionized water, and 0.15% of the total mass of the reaction system of sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat at a rate of 5 °C / min under nitrogen pressure of 0.2 MPa. Stirring is started at 100 °C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0086] In the second stage, the temperature was further increased to 200°C at a heating rate of 5°C / min, and the pressure was increased to 1.5 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.8 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour. The vacuum reaction was then carried out for 0.5 hour (the vacuum pressure was -80 kPa). When the water output reached 95 wt% of the theoretical mass of water (water added + reaction generation), the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain a bio-based polyamide prepolymer (denoted as Pre-PA1010).

[0087] (2) Weigh 0.015 mol of Pre-PA1010, 0.0175 mol of IPAES, and 0.0175 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Pour the mixture into a glass reactor, evacuate the reactor, and purge the air in the reactor with nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging and drying to obtain a bio-based polyamide elastomer.

[0088] Figure 1 This is the infrared spectrum of the bio-based polyamide prepolymer prepared in Example 1;

[0089] Figure 2 This is the infrared spectrum of the bio-based polyamide elastomer prepared in Example 1.

[0090] Example 2

[0091] (1) Weigh 1.675 mol of sebacic acid, 1.675 mol of 2,5-thiophenedicarboxylic acid, and 3.00 mol of decanediamine, add 130 g of deionized water, and 0.15% of the total mass of the reaction system of sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat the mixture at a heating rate of 5 °C / min under a nitrogen pressure of 0.2 MPa. Stirring is started at 100 °C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0092] In the second stage, the temperature was further increased to 200°C at a heating rate of 5°C / min, and the pressure was increased to 1.5 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.8 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour, followed by vacuum reaction for 0.5 hour. When the water output reached 95 wt% of the theoretical mass of water (water added + reaction generation), the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain a bio-based polyamide prepolymer (denoted as Pre-PA1010).

[0093] (2) Weigh 0.015 mol of Pre-PA1010, 0.0175 mol of IPAES, and 0.0175 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Pour the mixture into a glass reactor, evacuate the reactor, and purge the air in the reactor with nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging and drying to obtain a bio-based polyamide elastomer.

[0094] Example 3

[0095] (1) Weigh 1.675 mol of sebacic acid, 1.675 mol of 2,5-thiophenedicarboxylic acid, and 3.00 mol of decanediamine, add 130 g of deionized water, and 0.15% of the total mass of the reaction system of sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat the mixture at a heating rate of 5 °C / min under a nitrogen pressure of 0.2 MPa. Stirring is started at 100 °C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0096] In the second stage, the temperature was further increased to 200°C at a heating rate of 5°C / min, and the pressure was increased to 1.5 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.8 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour, followed by vacuum reaction for 0.5 hour. When the water output reached 95 wt% of the theoretical mass of water (water added + reaction generation), the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain a bio-based polyamide prepolymer (denoted as Pre-PA1010).

[0097] (2) Weigh 0.015 mol of Pre-PA1010, 0.0105 mol of IPAES, and 0.0245 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Pour the mixture into a glass reactor, evacuate the reactor, and purge the air in the reactor with nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging and drying to obtain a bio-based polyamide elastomer.

[0098] Example 4

[0099] (1) Weigh 2.35 mol of sebacic acid, 1.00 mol of 2,5-thiophenedicarboxylic acid, and 3.00 mol of decanediamine, add 130 g of deionized water, and 0.15% of the total mass of the reaction system of sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat at a rate of 5 °C / min under nitrogen pressure of 0.2 MPa. Stirring is started at 100 °C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0100] In the second stage, the temperature was further increased to 200°C at a heating rate of 5°C / min, and the pressure was increased to 1.5 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.8 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour, followed by vacuum reaction for 0.5 hour. When the water output reached 95 wt% of the theoretical mass of water (water added + reaction generation), the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain a bio-based polyamide prepolymer (denoted as Pre-PA1010).

[0101] (2) Weigh 0.015 mol of Pre-PA1010, 0.0105 mol of IPAES, and 0.0245 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Pour the mixture into a glass reactor, evacuate the reactor, and purge the air in the reactor with nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging and drying to obtain a bio-based polyamide elastomer.

[0102] Comparative Example 1

[0103] (1) Weigh 3.36 mol of sebacic acid and 3.01 mol of decanediamine, add 10% of the mass of deionized water and 0.15% of the mass of sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat the mixture at a rate of 5°C / min under a nitrogen pressure of 0.2 MPa. Stirring is started at 100°C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0104] In the second stage, the temperature was further increased to 200°C at a heating rate of 5°C / min, and the pressure was increased to 1.5 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.8 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour, followed by vacuum reaction for 0.5 hour. When the water output reached 95 wt% of the theoretical mass of water (water added + reaction generation), the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain a bio-based polyamide prepolymer (denoted as Pre-PA1010).

[0105] (2) Weigh 0.015 mol of Pre-PA1010 and 0.035 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Add the mixture to a glass reactor, then purge the air from the reactor and fill it with 0.25 MPa of nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging, pelletizing, and drying to obtain a bio-based polyamide elastomer.

[0106] Comparative Example 2

[0107] (1) Weigh 3.36 mol of dodecanedioic acid and 3.01 mol of 1,12-dodecanediamine, add 10% of the mass of dodecanedioic acid and 1,12-dodecanediamine in deionized water, and 0.15% of the mass of dodecanedioic acid, 1,12-dodecanediamine, and deionized water in sodium hypophosphite. Add all the above raw materials into a polymerization kettle, and heat the mixture at a heating rate of 5°C / min under a nitrogen pressure of 0.2 MPa. Stirring is started at 100°C, the stirring rate is controlled at 50 rpm, and the stirring time is 0.5 h to promote the salt formation of the diacid and diamine monomers in the solution.

[0108] In the second stage, the temperature was further increased to 180°C at a heating rate of 5°C / min, and the pressure was increased to 1.0 MPa. Appropriate exhaust was performed to maintain the pressure stable. After maintaining the temperature and pressure at this state for 1 hour, the temperature was again increased to 240°C, and the pressure was adjusted to 1.7 MPa. After maintaining this state for 1 hour, the pressure was released to atmospheric pressure, and the reaction was continued for 1 hour, followed by vacuum reaction for 0.5 hour. When the water output reached 95 wt% of the total water added, the discharge valve was opened to flash evaporate the material, which was then crushed and dried to obtain the bio-based PA1010 prepolymer.

[0109] (2) Weigh 0.015 mol of Pre-PA1010 and 0.035 mol of PO3G, and add 2‰ of tetrabutyl titanate to the total mass of the system. Add the mixture to a glass reactor, then purge the air from the reactor and fill it with 0.25 MPa of nitrogen. Raise the temperature to 220°C and continue polymerization for 2 h. Evacuate the reactor and heat the high-pressure reactor to 240°C. Allow the mixture to react under vacuum for a further 2 h before discharging, pelletizing, and drying to obtain a bio-based polyamide elastomer.

[0110] Table 1 Comparison of performance indicators of Examples 1 to 4 and Comparative Examples 1 to 2

[0111]

[0112] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A polyamide elastomer, characterized in that The polyamide elastomer comprises hard segment polymers and soft segment polymers arranged alternately; the hard segment polymer is a bio-based polyamide prepolymer; The polyamide elastomer has a structure shown in formula I; Formula I; A1 and A2 are independently or , and A1 and A2 are not simultaneously or ; M1 and M2 are independently or , and M1 and M2 are not simultaneously or ; The hard segment polymer has the structure described in Formula II: Formula II; The number average molecular weight of the hard segment polymer is 1000-5000 g / mol; The amount of the hard segment polymer in the polyamide elastomer is 10% to 50%.

2. The polyamide elastomer according to claim 1, wherein The amount of the soft segment polymer in the polyamide elastomer accounts for 50% to 90%.

3. The polyamide elastomer according to claim 1, wherein The number average molecular weight of the polyamide elastomer is 15000-25000 g / mol.

4. The method for preparing the polyamide elastomer according to any one of claims 1 to 3, comprising the following steps: (1) 2,5-thiophenedicarboxylic acid, decanediamine, sebacic acid, water and a polycondensation catalyst are mixed to carry out a polycondensation reaction to obtain a bio-based polyamide prepolymer; the 2,5-thiophenedicarboxylic acid is derived from glucaric acid and muconic acid; the decanediamine and sebacic acid are derived from castor oil; The structural formula of the bio-based polyamide prepolymer is: ； (2) mixing a bio-based polyamide prepolymer, a bio-based polytrimethylene ether glycol, an isosorbide-based poly(arylene ether sulfone) and tetrabutyl titanate, and performing block polymerization to obtain a block copolymer with alternating soft and hard segments; The structural formula of the isosorbide-based poly(arylene ether sulfone) is: ； (3) The block structure copolymer with alternating soft and hard segments is sequentially extruded, pelletized and dried to obtain the polyamide elastomer.

5. The preparation method according to claim 4, wherein The polycondensation reaction is carried out in the presence of a polycondensation catalyst, wherein the polycondensation catalyst comprises sodium hypophosphite and / or sodium hypophosphite.

6. The preparation method according to claim 4, wherein The molar ratio of the decanediamine to the total moles of 2,5-thiophenedicarboxylic acid and sebacic acid is 0.7-0.98:1.

0.

7. The preparation method according to claim 4, wherein The block polymerization is carried out sequentially as preliminary block polymerization and final block polymerization; The temperature of the preliminary block polymerization is 210-230° C., the pressure is 0.1-0.3 MPa, and the time is 1.0-3.0 h; The final block polymerization is carried out under vacuum conditions, with a temperature of 240-250° C. and a time of 1.0-3.0 h.

8. The preparation method according to claim 4, wherein The polycondensation reaction is a process of mixing 2,5-thiophenedicarboxylic acid, decanediamine, sebacic acid, water and a polycondensation catalyst, followed by salt formation and polymerization.

9. The preparation method according to claim 8, wherein The salt formation temperature is 100°C and the pressure is 0.5 MPa; The polymerization includes a first polymerization, a second polymerization, a third polymerization and a fourth polymerization carried out sequentially; The first polymerization temperature is 200°C, the pressure is 1.3-1.5 MPa, and the time is 1.0 h; The temperature of the second polymerization is 220-240°C, the pressure is 1.6-1.8 MPa, and the time is 1.0-1.2 h; the temperature of the third polymerization is 220-240°C, the pressure is atmospheric pressure, and the time is 1.0-1.2 h; The fourth polymerization is carried out under vacuum, the vacuum pressure is -80 kPa, the temperature of the fourth polymerization is 220-240° C., and the time is 0.5-0.6 h.

10. Use of the polyamide elastomer according to any one of claims 1 to 3 or the polyamide elastomer prepared by the preparation method according to any one of claims 4 to 9 in civil aviation, automobile manufacturing and intelligent sensing.

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