Polyamide elastomer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of material preparation, and discloses a polyamide elastomer and a preparation method and application thereof, and the preparation method of the polyamide elastomer comprises the following steps: mixing raw materials, and carrying out amidation reaction to obtain an amide compound; then adding a catalyst B, and carrying out polyesterification reaction to obtain a polyamide elastomer; the raw materials comprise binary acid, diamine, polyether glycol, a catalyst A and water, the reaction temperature of the amidation reaction is 150-180 DEG C, and the addition amount of the water is 20-40% of the total mass of the binary acid, the diamine and the polyether glycol. The polyamide elastomer which is relatively regular in structure and excellent in comprehensive performance can be prepared, the reaction efficiency can be effectively improved, and the preparation method is suitable for industrial large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of material preparation, in particular to a polyamide elastomer and a preparation method and application thereof. Background Art

[0002] Polyamide elastomers are thermoplastic elastomer materials whose molecular chains are formed by block copolymerization of rigid polyamide hard segments and flexible polyether soft segments. Commonly used polyamide hard segments include PA6, PA66, PA12, and PA1012, while typical polyether soft segments include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Thanks to the performance advantages of the soft and hard segments and their unique microphase separation structure, polyamide elastomers typically exhibit excellent mechanical strength, high elasticity, and flexibility. Furthermore, through precise control of the ratio of soft and hard segments and their chemical structure, polyamide elastomers can achieve multifunctional integration such as chemical resistance, fatigue resistance, and shape memory. Therefore, they are widely used in the automotive industry (lightweight structural parts, oil-resistant seals), high-end sports equipment (shoe midsoles), structural foams, electronic packaging materials, and biomedicine (medical catheters and medical cannulas). In particular, they have shown breakthrough application potential in emerging scenarios such as high-performance membrane separation (seawater desalination, gas separation) and new flexible electronic devices, becoming an important development direction for high-end engineering elastomer materials.

[0003] The current synthesis process of polyamide elastomers can be mainly divided into two technical routes: the "one-pot" continuous polymerization method and the "two-step" staged polycondensation method. Among them, the "one-pot" continuous polymerization method refers to the process of adding all raw materials such as dibasic acid, diamine, polyether diol, reaction aid, etc. into the reaction system at one time, and completing the multi-step polymerization reaction in a single reactor. It has the outstanding advantages of low equipment requirements, short process flow, and high production efficiency. The "two-step" staged polycondensation method requires the pre-preparation of a polyamide prepolymer with active end groups, and then undergoes a polycondensation reaction with a soft segment such as polyether diol. Its advantages are that the chemical structure of the hard segment (active end groups and molecular chain length) can be precisely controlled and the product properties can be easily controlled. However, it should be pointed out that although the "two-step" staged polycondensation method can obtain elastomer materials with regular chemical structure and excellent comprehensive properties due to its controllable polymerization reaction characteristics, its time-consuming, low-efficiency, and long production cycle process seriously restrict its large-scale production. In contrast, while the "one-pot" continuous polymerization method has technical drawbacks such as difficulty controlling product structure and the resulting degradation of polyamide mechanical properties, its inherently continuous polymerization reaction characteristics and process-intensive nature give it significant potential for industrial scale-up. Therefore, overcoming the challenges of "one-pot" continuous polymerization, including product structure control and poor mechanical properties, through innovative reaction engineering and process optimization will be a key breakthrough in promoting the large-scale industrial development of polyamide elastomers. Summary of the Invention

[0004] In view of this, the present invention provides a polyamide elastomer and a preparation method and application thereof, so as to solve the problem that the product structure is difficult to control when preparing polyamide elastomer by the existing "one-pot" continuous polymerization method, which leads to poor mechanical properties of the polyamide elastomer.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] On the one hand, the present invention provides a method for preparing a polyamide elastomer, comprising the following steps: mixing raw materials, performing an amidation reaction, and obtaining an amide compound; then adding a catalyst B, performing a polyesterification reaction, and obtaining a polyamide elastomer; the raw materials include a dibasic acid, a diamine, a polyether diol, a catalyst A, and water; the reaction temperature of the amidation reaction is 150-180°C; and the amount of water added is 20-40% of the total mass of the dibasic acid, diamine, and polyether diol.

[0007] Preferably, the amidation reaction is carried out under an inert atmosphere, and the reaction time is 2-3 hours.

[0008] Preferably, the polyesterification reaction is carried out under vacuum conditions, the reaction temperature is 240-260° C., and the reaction time is 3-5 h.

[0009] Preferably, the total molar ratio of the diamine and polyether diol to the molar ratio of the dibasic acid is 1:1-1.05.

[0010] Preferably, the molar ratio of the diamine to the polyether diol is 1:0.25-4.

[0011] Preferably, the dicarboxylic acid is at least one of glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and tetradecanedioic acid.

[0012] Preferably, the diamine is at least one of pentamethylenediamine, hexamethylenediamine, decamethylenediamine, undecanediamine, dodecanediamine, tridecanediamine and tetradecanediamine.

[0013] Preferably, the polyether diol is at least one of polyethylene glycol and polytetramethylene ether glycol, and the molecular weight of the polyether diol is 650-10000 g / mol.

[0014] Preferably, the method further comprises the following step: after the amidation reaction is completed, the reaction system is depressurized.

[0015] Preferably, the added amount of the catalyst A is 1-2‰ of the total mass of the dibasic acid, diamine and polyether diol.

[0016] Preferably, the catalyst A comprises one or more of sodium hypophosphite, antimony trioxide, antimony glycolate and germanium oxide.

[0017] Preferably, the added amount of the catalyst B is 2-4‰ of the total mass of the dibasic acid, diamine and polyether diol.

[0018] Preferably, the catalyst B includes one or more of tetrabutyl titanate, tetrabutyl zirconate and isopropyl titanate.

[0019] Preferably, the raw materials further include an antioxidant, and the added amount of the antioxidant is 2-4‰ of the total mass of the dibasic acid, diamine and polyether diol.

[0020] Preferably, the antioxidant includes one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], and 2,6-di-tert-butyl-4-methyl-phenol.

[0021] On the other hand, the present invention also provides a polyamide elastomer prepared by the above method.

[0022] Preferably, the content of polyether soft segment in the polyamide elastomer is 60-95%.

[0023] Furthermore, the present invention further provides a polyamide elastomer prepared by any of the methods described above, or use of any of the polyamide elastomers described above in a phase change material.

[0024] The present invention provides a polyamide elastomer and a preparation method thereof. Compared with the prior art, the present invention has the following advantages:

[0025] The present invention adopts a "one-pot" polymerization process to prepare a polyamide elastomer. In the initial amidation reaction process, a relatively low reaction temperature is adopted to suppress the polyesterification reaction. At the same time, a relatively large amount of water is added in the initial stage, which is used to promote the amidation reaction on the one hand and suppress the polyesterification reaction on the other hand. After the amidation reaction is basically completed, the polyesterification reaction is rapidly carried out under the catalytic conditions of catalyst B, thereby achieving the purpose of regulating the reaction process through the reaction process. Ultimately, not only can a polyamide elastomer with a relatively regular structure and excellent comprehensive performance be prepared, but the reaction efficiency can also be effectively improved, and the elastomer is suitable for industrial large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] 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 or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0027] Figure 1 This is an infrared spectrum of the polyamide elastomer of Example 1-4;

[0028] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the polyamide elastomer of Example 1-4;

[0029] Figure 3 This is a curve showing the change in thermal enthalpy of the polyamide elastomer under cyclic heating / cooling conditions in Example 1;

[0030] Figure 4 The differential scanning calorimetry curves of the polyamide elastomer under different processing conditions of Example 1 are shown;

[0031] Figure 5 This is a diagram showing the physical state changes of the polyamide elastomer and polytetramethylene ether glycol (PTMG) of Example 3-4 at different temperatures. DETAILED DESCRIPTION

[0032] The present invention will be described below by specific embodiment, and it will be appreciated by those skilled in the art that the specific embodiment below is only for illustrative purposes, and does not limit the scope of the present invention in any way. In addition, in the following examples, unless otherwise stated, the reagent and equipment used are all commercially available. If in the following examples, concrete treatment conditions and treatment process are not clearly described, then conditions and methods well known in the art can be adopted to process.

[0033] In one aspect of the present invention, a method for preparing a polyamide elastomer is provided, comprising the following steps: mixing raw materials, performing an amidation reaction, and obtaining an amide compound; then adding a catalyst B, performing a polyesterification reaction, and obtaining a polyamide elastomer; the raw materials include a dibasic acid, a diamine, a polyether diol, a catalyst A, and water; the reaction temperature of the amidation reaction is 150-180°C, and the amount of water added is 20-40% of the total mass of the dibasic acid, diamine, and polyether diol.

[0034] In the present invention, the amount of water added can be 20%, 30%, or 40%, etc. The water can be conventional experimental water such as deionized water or purified water. In the preparation process of traditional polyamide elastomers, the amount of water added is generally about 10% of the material mass. The present invention significantly increases the amount of water added. By increasing the amount of water added, on the one hand, it can promote the amidation reaction, and on the other hand, it can inhibit the polyesterification reaction to accelerate the reaction rate of the amidation reaction. The reaction temperature of the amidation reaction can be specifically 150°C, 160°C, 170°C, or 180°C. In the preparation process of traditional polyamide elastomers, the reaction temperature of the amidation reaction is generally above 190°C. The present invention can effectively inhibit the occurrence of the polyesterification reaction in this stage by lowering the temperature of the amidation reaction stage, thereby further accelerating the reaction rate of the amidation reaction and improving production efficiency. By adjusting the water and reaction temperature, the present invention can make the amidation reaction and polyesterification reaction proceed separately, thereby obtaining a polyamide elastomer with a relatively regular structure and excellent comprehensive properties.

[0035] In some embodiments of the present invention, the amidation reaction is carried out under an inert atmosphere for a reaction time of 2-3 hours. The reaction temperature for the amidation reaction can be, for example, 2 hours, 2.5 hours, or 3 hours. The inert atmosphere can be nitrogen, argon, or the like, and is not particularly limited thereto.

[0036] In some embodiments of the present invention, the polyesterification reaction is carried out under vacuum conditions at a reaction temperature of 240-260°C and a reaction time of 3-5 hours. Specifically, the polyesterification reaction temperature can be 240°C, 250°C, or 260°C, and the reaction time can be 3 hours, 4 hours, or 5 hours. The vacuum pressure is less than 100 Pa. Specifically, vacuum conditions can be achieved by reducing the system pressure to below 100 Pa within 0.5-1 hour. Slowly evacuating the system to a vacuum environment effectively removes moisture from the reaction system, accelerating the polyesterification reaction and improving reaction efficiency.

[0037] In some embodiments of the present invention, the molar ratio of the total molar amount of the diamine and the polyether diol to the molar amount of the dibasic acid is 1:1-1.05, specifically 1:1, 1:1.02, 1:1.05, etc.; the molar ratio of the diamine and the polyether diol is 1:0.25-4, specifically 1:0.25, 1:1, 1:2, 1:3 and 1:4, etc. By adjusting the molar ratio of the diamine and the polyether diol, a polyamide elastomer with different hard segments and soft segments can be obtained. The dibasic acid is at least one of glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid; the diamine is at least one of pentamethylenediamine, hexamethylenediamine, decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid; the polyether diol is at least one of polyethylene glycol and polytetramethylene glycol, and the molecular weight of the polyether diol is 650-10,000 g / mol, preferably 1,000-6,000 g / mol, specifically 650 g / mol, 1,000 g / mol, 3,000 g / mol, 5,000 g / mol, 8,000 g / mol, and 10,000 g / mol. By limiting the molecular weight of the polyether diol to this range, not only can good reactivity be ensured, but also the resulting elastomer can have excellent physical and mechanical properties and phase change properties.

[0038] In some embodiments of the present invention, the amount of catalyst A added is 1-2‰ of the total mass of the dibasic acid, diamine, and polyether diol, specifically 1‰, 1.5‰, and 2‰, etc. The catalyst A comprises one or more of sodium hypophosphite, antimony trioxide, antimony glycol, and germanium oxide. Catalyst A can accelerate the amidation reaction and increase the reaction rate.

[0039] In some embodiments of the present invention, the amount of catalyst B added is 2-4‰ of the total mass of the dibasic acid, diamine, and polyether diol, specifically 2‰, 3‰, and 4‰, etc. The catalyst B comprises one or more of tetrabutyl titanate, tetrabutyl zirconate, and isopropyl titanate. Catalyst B can accelerate the polyesterification reaction and increase the reaction rate.

[0040] In some embodiments of the present invention, the raw materials further include an antioxidant, and the added amount of the antioxidant is 2-4‰ of the total mass of the dibasic acid, diamine and polyether diol, specifically 2‰, 3‰ and 4‰, etc. The antioxidant includes one or more of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester (antioxidant 1010), N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (antioxidant 1098) and 2,6-di-tert-butyl-4-methyl-phenol.

[0041] Some embodiments of the present invention further include the step of depressurizing the reaction system after the amidation reaction is completed. The amidation reaction is preferably conducted in a sealed reactor. After completion, the pressure is released to remove excess water from the system. The reaction temperature is then raised, and the polyesterification reaction is conducted under vacuum conditions. The pressure release removes water from the reaction system, while the vacuum draws out water generated during the polyesterification reaction, ensuring that the polyesterification reaction is conducted under anhydrous conditions and accelerating the polyesterification reaction.

[0042] In some embodiments of the present invention, after the polyesterification reaction is completed, the system is filled with an inert gas to return to normal pressure, and the material is discharged to obtain a polyamide elastomer. The inert gas may be nitrogen, argon, or the like, and is not particularly limited thereto. Normal pressure refers to atmospheric pressure.

[0043] In another aspect of the present invention, the present invention also provides a polyamide elastomer prepared by the above method.

[0044] In some embodiments of the present invention, the content of the polyether soft segment in the polyamide elastomer is 60-95%, specifically 60%, 70%, 80%, 90%, 95%, etc.

[0045] In another aspect of the present invention, the present invention also provides a use of the above-mentioned polyamide elastomer in a phase change material.

[0046] Based on the unique two-phase structure and microphase separation characteristics of polyamide elastomers, solid-solid phase transitions are achieved through the melt-crystallization transition of the polyether soft segment, while the polyamide hard segment provides the phase change material with excellent mechanical strength, thermal stability, and long-term temperature resistance. This overcomes the bottlenecks of traditional paraffin / inorganic phase change materials, such as poor mechanical properties, leakage, and low interfacial compatibility, and opens up new application directions for polyamide elastomers in new high-value-added scenarios such as intelligent temperature control and flexible electronics, demonstrating extremely excellent development prospects and application potential.

[0047] The following will be combined with specific embodiments to clearly and completely describe the technical solutions of the present invention. The embodiments of this application are only for example, and all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0048] Example 1

[0049] This embodiment provides a method for preparing a polyamide elastomer, and the specific steps are as follows:

[0050] (1) Adding a dibasic acid, a diamine, a polyether diol, deionized water, a catalyst A, and an antioxidant into a reaction kettle, replacing the air in the reaction kettle with an inert gas, and then sealing the reaction kettle, heating it to 170° C. and reacting at this temperature for 2 hours to obtain an amide compound;

[0051] The molar ratio of the dibasic acid, the diamine and the polyether diol is 2:1:1, the dibasic acid is sebacic acid, the diamine is decanediamine, and the polyether diol is polytetramethylene glycol (molecular weight 1000 g / mol); the amount of catalyst A is 2‰ of the total mass of the dibasic acid, the diamine and the polyether diol, and the catalyst A is sodium hypophosphite; the amount of antioxidant is 2‰ of the total mass of the dibasic acid, the diamine and the polyether diol, and the antioxidant is antioxidant 1010; and the amount of deionized water is 30% of the total mass of the dibasic acid, the diamine and the polyether diol.

[0052] (2) The reactor is depressurized, then heated to 250°C and catalyst B is added. The reactor is then evacuated to below 100 Pa within 0.75 h, and the reaction is continued at 250°C for 4 h before being stopped. The reactor is then filled with inert gas to restore the environment in the reactor to normal pressure, thereby obtaining a polyamide elastomer.

[0053] The amount of catalyst B used is 2‰ of the total mass of the dibasic acid, diamine and polyether diol, and catalyst B is tetrabutyl titanate.

[0054] Example 2

[0055] This embodiment is substantially the same as Example 1, except that the molecular weight of the polytetramethylene ether glycol is 2000 g / mol.

[0056] Example 3

[0057] This embodiment is substantially the same as Example 1, except that the molecular weight of the polytetramethylene ether glycol is 3000 g / mol.

[0058] Example 4

[0059] This embodiment is substantially the same as Example 1, except that the molecular weight of the polytetramethylene ether glycol is 4000 g / mol.

[0060] like Figure 1 As shown in the figure, it is the infrared spectrum of the polyamide elastomer of Example 1-4. From the figure, it can be observed that the characteristic absorption peaks are respectively attributed to the polyamide hard segment and the polyether soft segment, and are located at 1735cm -1 The characteristic absorption peak corresponds to the stretching vibration of C=O on the ester bond, which shows that the polyamide hard segment and the polyether soft segment are connected by an ester bond, which proves the successful preparation of the target polyamide elastomer.

[0061] like Figure 2As shown, it is the nuclear magnetic resonance hydrogen spectrum of the polyamide elastomer of Example 1-4. It can be observed from the figure that the characteristic chemical shift peak at a corresponds to the proton hydrogen of the carbon directly connected to the oxygen atom on the ester bond, which can also prove the successful synthesis of the target polyamide elastomer.

[0062] like Figure 3 As shown in the figure, the enthalpy change curve of the polyamide elastomer under the cyclic heating / cooling conditions of Example 1 is shown. It can be seen from the figure that after the polyamide elastomer undergoes multiple heating / cooling cycles, its melting temperature (T m ), crystallization temperature (T c ), melting enthalpy change (ΔHm) and crystallization enthalpy change (ΔHc) remain stable, that is, the phase change properties can be maintained basically unchanged, indicating that the phase change properties of polyamide elastomers are extremely stable.

[0063] like Figure 4 As shown in the figure, the differential scanning calorimetry curves of the polyamide elastomer of Example 1 under different processing conditions are shown. It can be seen from the figure that the unprocessed polyamide elastomer, the polyamide elastomer after hot pressing and the polyamide elastomer after washing at 60°C for 2 hours can maintain the phase change properties basically unchanged regardless of the crystallization condition or the melting condition, indicating that the phase change properties of the polyamide elastomer are extremely stable.

[0064] like Figure 5 As shown, the physical state change diagram of the polyamide elastomers and polytetramethylene glycol (PTMG) of Examples 3-4 at different temperatures. It can be seen from the figure that as the temperature gradually increases, polytetramethylene glycol with a molecular weight of 1000 g / mol and 4000 g / mol melts, and is prone to leakage when used as an encapsulated phase change material; while the polyamide elastomers of Examples 3 and 4 do not melt as the temperature gradually increases, that is, when the polyamide elastomers of the present application are used as encapsulated phase change materials, leakage is not likely to occur, and their stability in use is good.

[0065] Example 5

[0066] This embodiment is substantially the same as embodiment 1, except that the polyether diol is polyethylene glycol, and the molecular weight of the polyethylene glycol is 1000 g / mol;

[0067] The reaction temperature of the amidation reaction in step (1) is 180°C, and the reaction temperature of the polyesterification reaction in step (2) is 240°C.

[0068] Comparative Example 1

[0069] This comparative example provides a method for preparing a polyamide elastomer by a traditional "two-step method", the specific steps are as follows:

[0070] 1) Add the dibasic acid, diamine, deionized water and antioxidant into a reactor together, replace the air in the reactor with an inert gas, then seal the reactor, heat it to 200°C and react at this temperature for 2 hours, then depressurize the reactor, evacuate it to an absolute pressure below 3000 Pa after reaching normal pressure, and react at this temperature for 15 minutes, then fill it with inert gas to restore the environment in the reactor to normal pressure, release the materials while hot, cool, crush and dry the materials, and obtain polyamide 1010 hard segment;

[0071] The molar ratio of the dibasic acid to the diamine is 2:1, the dibasic acid is sebacic acid, the diamine is decanediamine, the amount of the antioxidant is 2‰ of the total mass of the dibasic acid and the diamine, and the antioxidant is antioxidant 1010; the amount of deionized water is 10% of the total mass of the dibasic acid and the diamine.

[0072] (2) Adding polyamide 1010 hard segment, polyether diol, antioxidant and catalyst into a reactor, heating under an inert atmosphere, and when the temperature reaches 250°C, evacuating the reactor to below 100 Pa within 0.75 hours, and reacting at 250°C for 8 hours, stopping, filling the reactor with inert gas to restore the environment in the reactor to normal pressure, taking out the material, cooling, pelletizing and drying, and obtaining a polyamide elastomer;

[0073] Among them, the molar ratio of polyether diol and polyamide 1010 hard segment is 1:1, and the polyether diol is polytetramethylene ether diol (molecular weight 1000g / mol); the amount of catalyst used is 2‰ of the total mass of the polyether diol and the polyamide 1010 hard segment, and the catalyst is tetrabutyl titanate; the amount of antioxidant used is 2‰ of the total mass of the polyether diol and the polyamide 1010 hard segment, and the antioxidant is antioxidant 1010.

[0074] Comparative Example 2

[0075] This comparative example is basically the same as comparative example 1, with the only difference being that in step (2), the reaction was stopped after being kept at a constant temperature of 250° C. for 4 hours.

[0076] The soft segment content, tensile properties and phase change properties of the polyamide elastomers of Examples 1-5 and Comparative Examples 1-2 were tested. The test results are shown in Table 1.

[0077] Table 1

[0078]

[0079] A comparison of Example 1 and Comparative Example 1 reveals that the mechanical properties of the polyamide elastomer prepared by the "one-pot" polymerization process of the present invention and the conventional "two-step" process of Comparative Example 1 are similar. However, the time required to prepare the polyamide elastomer in Example 1 is significantly shortened, i.e., production efficiency is significantly improved. A comparison of Example 1 and Comparative Example 2 reveals that when the time required to prepare the polyamide elastomer by the "one-pot" polymerization process of the present invention is similar to that of the conventional "two-step" process of Comparative Example 1, the mechanical properties of the polyamide elastomer prepared by the present invention are significantly better. In other words, compared to the conventional "two-step" process, the "one-pot" polymerization process of the present invention not only effectively shortens preparation time and improves production efficiency, but also produces a polyamide elastomer with mechanical properties comparable to those of the conventional "two-step" process in a shorter time. This is highly beneficial for the industrial development of polyamide elastomer phase change materials.

[0080] In addition, by comparing Examples 1-4, it can be found that with the increase of the molecular weight of the soft segment polyether (ie, the increase of the soft segment content), the soft segment crystallization temperature (T c-SS ), soft segment melting temperature (T m-SS ), soft segment crystallization enthalpy change (ΔH c-SS ) and the soft segment melting enthalpy change (ΔH m-SS ) gradually increase; more importantly, the polyamide elastomer phase change materials obtained in Example 3 and Example 4 not only have a higher phase change enthalpy value, but also their melting phase transition temperature is between the human body's thermal comfort temperature (20-27°C), which means that they can be further used to manufacture flexible materials for human body thermal management, such as electronic skin, smart fibers, etc., and have excellent development potential.

[0081] In summary, the "one-pot method" for preparing polyamide elastomers of the present invention has the outstanding advantages of short reaction time and high efficiency, and is very suitable for further industrial scale-up production; moreover, based on the unique two-phase structure and microphase separation characteristics of polyamide elastomers, their application in the field of phase change materials can open up the application development direction of polyamide elastomers in new high-value-added scenarios such as intelligent temperature control and flexible electronics, showing extremely excellent development prospects and application potential.

[0082] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a polyamide elastomer, characterized in that: The following steps are involved: The raw materials are mixed and subjected to an amidation reaction to obtain an amide compound; then a catalyst B is added to carry out a polyesterification reaction to obtain a polyamide elastomer; The raw materials include dibasic acid, diamine, polyether diol, catalyst A and water. The reaction temperature of the amidation reaction is 150-180° C. The amount of water added is 20-40% of the total mass of the dibasic acid, diamine and polyether diol.

2. The method for preparing a polyamide elastomer according to claim 1, wherein: The amidation reaction is carried out under an inert atmosphere for 2-3 hours; The polyesterification reaction is carried out under vacuum conditions, the reaction temperature is 240-260° C., and the reaction time is 3-5 hours.

3. The method for preparing a polyamide elastomer according to claim 1, wherein: The molar ratio of the total molar amount of the diamine and the polyether diol to the molar amount of the dibasic acid is 1:1-1.05; The molar ratio of the diamine to the polyether diol is 1:0.25-4.

4. The method for preparing a polyamide elastomer according to claim 1, wherein The dicarboxylic acid is at least one of glutaric acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and tetradecanedioic acid; The diamine is at least one of pentamethylenediamine, hexamethylenediamine, decamethylenediamine, undecanediamine, dodecanediamine, tridecanediamine and tetradecanediamine; The polyether diol is at least one of polyethylene glycol and polytetramethylene ether glycol, and the molecular weight of the polyether diol is 650-10000 g / mol.

5. The method for preparing a polyamide elastomer according to claim 1, wherein: The following steps are also included: After the amidation reaction is completed, the reaction system is depressurized.

6. The method for preparing a polyamide elastomer according to claim 1, wherein: The addition amount of the catalyst A is 1-2‰ of the total mass of the dibasic acid, diamine and polyether diol, and the catalyst A comprises one or more of sodium hypophosphite, antimony trioxide, ethylene glycol antimony and germanium oxide; The addition amount of the catalyst B is 2-4‰ of the total mass of the dibasic acid, diamine and polyether diol, and the catalyst B includes one or more of tetrabutyl titanate, tetrabutyl zirconate and isopropyl titanate.

7. The method for preparing a polyamide elastomer according to any one of claims 1 to 6, characterized in that: The raw materials also include an antioxidant, and the added amount of the antioxidant is 2-4‰ of the total mass of the dibasic acid, diamine and polyether diol; The antioxidant includes one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] and 2,6-di-tert-butyl-4-methyl-phenol.

8. A polyamide elastomer prepared by the method according to any one of claims 1 to 7.

9. The polyamide elastomer according to claim 8, characterized in that The content of the polyether soft segment in the polyamide elastomer is 60-95%.

10. Use of the polyamide elastomer prepared by the method according to any one of claims 1 to 7 or the polyamide elastomer according to any one of claims 8 to 9 in a phase change material.

Images