High-wear-resistance anti-aging thermoplastic elastomer foamed synthetic leather for automotive trim and preparation method thereof

Abstract

The invention discloses high-wear-resistance anti-aging thermoplastic elastomer foamed synthetic leather for automotive interiors and a preparation method thereof. The high-wear-resistance anti-aging thermoplastic elastomer foamed synthetic leather comprises bio-based diamine, bio-based binary acid, a functional comonomer, nano silicon dioxide fibers, superfine aluminum oxide fibers and other materials. The size effect and the high specific surface area of the nano silicon dioxide fibers and the superfine aluminum oxide fibers promote dispersity in a polyamide matrix, the hardness and rigidity of the material are improved, combination between the wear-resistant reinforcing agent and the anti-aging agent can be promoted, the nano silicon dioxide fibers and the superfine aluminum oxide fibers can form a grid structure, and the wear resistance of the material is improved. According to the synthetic leather material, the compactness of the synthetic leather material is enhanced, a barrier effect is provided, the wear resistance and the oxidation resistance of the synthetic leather are enhanced, the wear resistance and the aging resistance of the synthetic leather are enhanced, and the defect that the wear resistance and the aging resistance of the synthetic leather are insufficient in the prior art is overcome.

Description

Technical Field

[0001] The invention relates to the technical field of synthetic leather preparation, in particular to a polymer material synthetic leather, and in particular to a highly wear-resistant and anti-aging automobile interior thermoplastic elastomer foamed synthetic leather and a preparation method thereof. Background Art

[0002] With the continuous advancement and innovation of science and technology, the design and manufacturing of automotive interiors have also ushered in new opportunities. The continuous emergence of new materials, new processes and new technologies has provided strong support for the upgrading of automotive interiors. For example, the application of environmentally friendly materials such as spray-free plastics, low-odor plastics, and low-VOC plastics is becoming more and more widespread; the application of textile materials in many aspects of the car also meets people's higher expectations for comfort, safety and environmental protection.

[0003] Thermoplastic elastomer foamed synthetic leather is a lightweight, highly elastic synthetic leather made from thermoplastic elastomers by forming a large number of tiny bubbles inside the material through physical or chemical foaming methods. During production and use, thermoplastic elastomer foamed synthetic leather does not contain harmful substances, meets environmental protection requirements, is harmless to the human body, and is suitable for automotive interiors and other places with high environmental requirements. It has excellent touch, is soft and comfortable, and can enhance the comfort experience of drivers and passengers.

[0004] However, during use, when the thermoplastic elastomer foamed synthetic leather car seat interior is used, the car seat interior will be worn and aged due to friction and sunlight during use, which will reduce the service life and affect the use effect.

[0005] Therefore, it is necessary to improve the synthetic leather in the prior art to solve the above problems. Summary of the invention

[0006] The invention overcomes the shortcomings of the prior art and provides a highly wear-resistant and anti-aging automobile interior thermoplastic elastomer foamed synthetic leather and a preparation method thereof.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, consisting of component A, component B and component C, wherein:

[0008] The A component comprises: a bio-based diamine, a bio-based dibasic acid and a functional comonomer, wherein the mass ratio of the bio-based diamine, the bio-based dibasic acid and the functional comonomer is 40-50:35-45:10-20;

[0009] The B component includes: nano-silicon dioxide fibers and ultra-fine alumina fibers, and the mass ratio of the nano-silicon dioxide fibers to the ultra-fine alumina fibers is 1:2-4;

[0010] The C component includes: a cross-linking agent, a wear-resistant enhancer, an anti-aging agent and a catalyst, and the mass ratio of the cross-linking agent, the wear-resistant enhancer, the anti-aging agent and the catalyst is: 1-2:3-5:3-5:2-3;

[0011] The mass ratio of the A component, the B component and the C component is 60-70:25-35:10-15.

[0012] In a preferred embodiment of the present invention, the bio-based diamine, the bio-based dibasic acid and the functional comonomer are hexamethylenediamine, dodecanedioic acid and methyl methacrylate, respectively.

[0013] In a preferred embodiment of the present invention, the diameters of the nano-silica fibers and the ultrafine alumina fibers are 100-300 nm and 200-400 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers are 2-3 mm and 1-2 mm, respectively.

[0014] In a preferred embodiment of the present invention, the cross-linking agent, the wear-resistant enhancer, the anti-aging agent, and the catalyst are trimethylolpropane triacrylate, polysiloxane, 2,6-di-tert-butyl-4-methylphenol, and TiO2, respectively.

[0015] To achieve the above object, the technical solution adopted by the present invention is: a method for preparing a highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather, based on a highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather, comprising the following steps:

[0016] S1: adding hexamethylenediamine, dodecanedioic acid, methyl methacrylate and TiO2 into a reaction kettle in a mass ratio of 45:35:15, heating to carry out polymerization reaction at a heating temperature of 230-240° C. for 2-4 hours to obtain a polyamide melt;

[0017] S2: adding the nano-silica fiber and the ultrafine alumina fiber to the polyamide melt in S1 and stirring for 10-30 minutes to obtain a polyamide mixed melt;

[0018] S3: adding a crosslinking agent, a wear-resistant reinforcing agent and an anti-aging agent to the polyamide mixed melt in S3 and stirring the mixture at a stirring speed of 200-400 rpm, a stirring time of 30-60 min, and a stirring temperature of 220-230° C. to obtain a polyamide modified melt, and calendering the polyamide modified melt and a base fabric to obtain a base fabric composite material;

[0019] S4: transferring the base fabric composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to a CO2 supercritical state, performing a foaming reaction for 1-2 hours, and slowly reducing the pressure to normal pressure at a pressure reduction rate of 0.1-0.2 MPa / min after the foaming reaction to obtain a polyamide foam;

[0020] S5: drying the polyamide foam in S4 at room temperature for 2-4 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0021] In a preferred embodiment of the present invention, when the polymerization reaction in S1 is carried out, the gas pressure in the reactor is gradually increased from normal pressure to 110 kPa.

[0022] In a preferred embodiment of the present invention, the nano-silica fibers and the ultrafine alumina fibers in S2 are respectively subjected to surface activation treatment before being added to the polyamide melt. The specific treatment process is to immerse the nano-silica fibers and the ultrafine alumina fibers in a sodium dodecyl sulfate solution with a mass fraction of 0.5-1% for 1-2 hours, take them out and dry them.

[0023] In a preferred embodiment of the present invention, the stirring process in S2 is firstly carried out at a speed of 200-250 rpm for 5-10 min, and then increased to a speed of 350-400 rpm for stirring.

[0024] In a preferred embodiment of the present invention, the supercritical state conditions of the CO2 in the S4 are 30.8-31.4°C and 7.38-7.39MPa.

[0025] In a preferred embodiment of the present invention, the cooling rate when adjusting to the supercritical state of CO2 in S4 is 1-1.5°C / min.

[0026] The present invention solves the defects existing in the background technology and has the following beneficial effects:

[0027] (1) The present invention provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, comprising materials such as bio-based diamines, bio-based dibasic acids, functional copolymers, nano-silica fibers and ultrafine alumina fibers. The size effect and high specific surface area of ​​the nano-silica fibers and ultrafine alumina fibers promote their dispersibility in a polyamide matrix, improve the hardness and stiffness of the material, and promote the combination of wear-resistant enhancers and anti-aging agents. Compared with the synthetic leather in the prior art, the nano-silica fibers and ultrafine alumina fibers can form a grid structure, enhance the density of the synthetic leather material, provide a barrier effect, enhance the wear resistance and antioxidant capacity of the synthetic leather, thereby enhancing the wear resistance and aging resistance of the synthetic leather, and solving the problem of insufficient wear resistance and aging resistance of the synthetic leather in the prior art.

[0028] (2) In the present invention, supercritical CO2 foaming is used when foaming the polyamide modified melt. Supercritical CO2 foaming can form uniformly distributed tiny bubbles in the synthetic leather. Compared with the prior art, the bubbles can disperse the stress on the surface of the material and reduce the wear during the friction process. The uniform pore structure helps to reduce the heat accumulation inside the material, reduce the aging rate caused by the increase in temperature, and improve the friction resistance and anti-aging performance of the synthetic leather.

[0029] (3) In the present invention, the nano-silica fibers and ultrafine alumina fibers are first stirred at a speed of 200-250 rpm for 5-10 min and then increased to a speed of 350-400 rpm. The low-speed stirring can reduce the agglomeration of the fibers during the initial mixing, and the high-speed stirring can provide sufficient shear force. Compared with the prior art, it can break up the fiber aggregates and achieve a finer and more uniform dispersion state, optimize the dispersion of the fibers in the polyamide melt, provide a more stable grid structure, and better maintain the wear resistance and aging resistance of the synthetic leather.

[0030] (4) In the present invention, the nano-silica fibers and ultrafine alumina fibers are respectively subjected to surface-active treatment with sodium dodecyl sulfate before being added to the polyamide melt, thereby reducing the surface tension between the fibers and the polyamide melt and promoting the chemical reaction between the fiber surface and the polyamide melt. Compared with the prior art, more stable chemical bonds can be formed while improving the fiber dispersion, thereby improving the overall structural stability of the material, improving the antioxidant performance, and increasing the anti-aging ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.

[0032] Figure 1 It is a method step diagram of a preferred embodiment of the present invention. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein. Therefore, the protection scope of the present invention is not limited to the specific embodiments disclosed below.

[0035] A highly wear-resistant and anti-aging automobile interior thermoplastic elastomer foamed synthetic leather, comprising component A, component B and component C, wherein:

[0036] Component A includes: bio-based diamine, bio-based dibasic acid and functional comonomer, and the mass ratio of bio-based diamine, bio-based dibasic acid and functional comonomer is 40-50:35-45:10-20;

[0037] Component B includes: nano-silica fiber and ultra-fine alumina fiber, and the mass ratio between the nano-silica fiber and the ultra-fine alumina fiber is 1:2-4;

[0038] Component C includes: a cross-linking agent, a wear-resistant enhancer, an anti-aging agent and a catalyst, and the mass ratio of the cross-linking agent, the wear-resistant enhancer, the anti-aging agent and the catalyst is: 1-2:3-5:3-5:2-3;

[0039] The mass ratio of component A, component B and component C is: 60-70:25-35:10-15.

[0040] The invention comprises materials such as bio-based diamines, bio-based dibasic acids, functional copolymers, nano-silica fibers and ultrafine alumina fibers. The size effect and high specific surface area of ​​the nano-silica fibers and ultrafine alumina fibers promote their dispersion in the polyamide matrix, improve the hardness and stiffness of the material, and promote the combination of wear-resistant enhancers and anti-aging agents. The nano-silica fibers and ultrafine alumina fibers can form a grid structure, enhance the density of the synthetic leather material, provide a barrier effect, enhance the wear resistance and antioxidant capacity of the synthetic leather, thereby enhancing the wear resistance and aging resistance of the synthetic leather, and solving the defect of insufficient wear resistance and aging resistance of the synthetic leather in the prior art.

[0041] The bio-based diamine, bio-based dibasic acid and functional comonomer are hexamethylenediamine, dodecanedioic acid and methyl methacrylate respectively. Hexamethylenediamine, dodecanedioic acid and methyl methacrylate all have good chemical stability, and using hexamethylenediamine, dodecanedioic acid and methyl methacrylate as the base material of synthetic leather can increase the oxidation resistance of synthetic leather.

[0042] The diameters of nano-silica fibers and ultra-fine alumina fibers are 100-300nm and 200-400nm respectively, and the lengths of nano-silica fibers and ultra-fine alumina fibers are 2-3mm and 1-2mm respectively. The smaller diameter helps the fibers to be better dispersed in the polyamide matrix, reducing agglomeration and thus reinforcing the material more evenly. The nano-silica fibers and ultra-fine fibers form a reinforced network structure in the polyamide matrix. This network structure not only improves the strength and stiffness of the material, but also increases the toughness of the material. When subjected to external forces, the network structure can disperse and absorb energy to prevent the material from breaking or wearing.

[0043] Although nano-silica fibers themselves do not directly provide anti-aging properties, they indirectly improve the anti-aging ability of the material by enhancing the overall performance of the material. Due to their excellent chemical stability, ultrafine fibers can maintain good performance during long-term use and are not prone to aging. The strong bond between ultrafine fibers and the polyamide matrix also helps prevent external factors from eroding the synthetic leather, improving the anti-aging and friction resistance of synthetic leather.

[0044] Nano-silica fiber has a certain UV shielding effect, which can reduce the direct exposure of UV rays to materials, thereby reducing the photoaging effect caused by UV rays. This shielding effect complements the UV absorption function of the antioxidant, and together improves the anti-aging performance of the material.

[0045] The cross-linking agent, wear-resistant enhancer, anti-aging agent, and catalyst are trimethylolpropane triacrylate, polysiloxane, 2,6-di-tert-butyl-4-methylphenol, and TiO2, respectively. As a cross-linking agent, trimethylolpropane triacrylate can react with the amino or carboxyl groups on the polyamide chain to form a three-dimensional network structure, thereby improving the cross-linking density and mechanical properties of the material. As a wear-resistant enhancer, polysiloxane can improve the surface hardness and wear resistance of synthetic leather. The low friction coefficient and high chemical stability of siloxane help to reduce wear. 2,6-di-tert-butyl-4-methylphenol is a highly effective anti-aging agent that can capture free radicals and prevent the oxidative breakage of polymer chains, thereby improving the anti-aging performance and service life of synthetic leather. As a catalyst, TiO2 can accelerate the rate of polymerization and cross-linking reactions and improve production efficiency. At the same time, TiO2 can also improve the light stability of the material and prevent photodegradation. The combination of trimethylolpropane triacrylate, polysiloxane, 2,6-di-tert-butyl-4-methylphenol and TiO2 can improve the friction resistance and aging resistance of synthetic leather.

[0046] like Figure 1 As shown, in order to achieve the above purpose, the technical solution adopted by the present invention is: a method for preparing a highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather, based on a highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather, comprising the following steps:

[0047] S1: adding bio-based diamine, bio-based dibasic acid, functional comonomer and catalyst into a reactor, heating to carry out polymerization reaction, the heating temperature is 230-240° C., the heating time is 2-4 hours, and a polyamide melt is obtained;

[0048] S2: adding nano-silica fibers and ultrafine alumina fibers to the polyamide melt in S1 and stirring for 10-30 minutes to obtain a polyamide mixed melt;

[0049] S3: adding a crosslinking agent, a wear-resistant reinforcing agent and an anti-aging agent to the polyamide mixed melt in S3 and stirring the mixture at a stirring speed of 200-400 rpm, a stirring time of 30-60 min, and a stirring temperature of 220-230° C. to obtain a polyamide modified melt, and calendering the polyamide modified melt and a base fabric to obtain a base fabric composite material;

[0050] S4: transferring the base fabric composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to a CO2 supercritical state, performing a foaming reaction for 1-2 hours, and slowly reducing the pressure to normal pressure at a pressure reduction rate of 0.1-0.2 MPa / min after the foaming reaction to obtain a polyamide foam;

[0051] S5: drying the polyamide foam in S4 at room temperature for 2-4 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0052] During the polymerization reaction in S1, the pressure in the reactor is gradually increased from normal pressure to 110 kPa. Increasing the pressure can increase the collision frequency between the reactant molecules, thereby increasing the rate of the polymerization reaction. In the polymerization reaction, increasing the pressure can sometimes promote chain growth, thereby increasing the molecular weight of the polymer. The increase in the molecular weight of the polymer increases the material density of the synthetic leather, thereby having stronger anti-aging and friction resistance.

[0053] The nano-silica fiber and ultrafine alumina fiber in S2 are treated with surface activity before being added to the polyamide melt. The specific treatment process is to soak the nano-silica fiber and ultrafine alumina fiber in a sodium dodecyl sulfate solution with a mass fraction of 0.5-1% for 1-2 hours, take them out and dry them. Sodium dodecyl sulfate can reduce the surface tension between the fiber and the polyamide melt, making the fiber easier to disperse in the melt and reducing agglomeration. Sodium dodecyl sulfate promotes the chemical reaction between the fiber surface and the polyamide melt, helps to form a more stable chemical bond, improves the overall structural stability of the material, improves the antioxidant performance, and increases the anti-aging ability.

[0054] The stirring process in S2 is first stirred at a speed of 200-250rpm for 5-10min, and then increased to 350-400rpm for stirring. Low-speed stirring can reduce the agglomeration of fibers during initial mixing, and high-speed stirring can provide sufficient shear force to help break up fiber aggregates, achieve a finer and more uniform dispersion state, optimize the dispersion of fibers in polyamide melt, and improve the mechanical properties of the composite material.

[0055] The base fabric in S3 is a polyester fabric, which can be tightly combined with the polyamide modified melt, so that in the subsequent foaming step, the polyamide modified melt on the polyester fabric can still be tightly combined with the polyester fabric during foaming.

[0056] The supercritical state conditions of CO2 in S4 are 30.8-31.4℃ and 7.38-7.39MPa. In the supercritical state, CO2 has a high solubility and can be dissolved in a large amount in the polyamide melt, providing a sufficient gas source for the subsequent foaming reaction. The uniform dissolution of supercritical CO2 helps to form uniformly distributed tiny bubbles in the polyamide melt, thereby obtaining a uniform foaming structure. Supercritical CO2 foaming can reduce defects on the material surface, such as unevenness and bubble rupture, thereby obtaining a smoother surface quality.

[0057] Supercritical CO2 foaming can form evenly distributed tiny bubbles in synthetic leather, which can disperse the stress on the surface of the material and reduce wear during friction, thereby improving the friction resistance. The uniform pore structure helps to reduce the heat accumulation inside the material and reduce the aging rate caused by increased temperature, thereby improving the anti-aging performance of synthetic leather. Supercritical CO2 foaming can improve the durability of synthetic leather, allowing it to maintain its performance during long-term use and reduce performance degradation caused by friction and aging. Alumina fibers act as nucleation points to promote the nucleation and uniform distribution of carbon dioxide bubbles, thereby obtaining a more uniform foam structure. The high hardness of alumina fibers helps to improve the wear resistance of the material. The microporous structure formed by carbon dioxide bubbles can disperse surface stress and reduce frictional heat and wear.

[0058] The high shear force provided by supercritical CO2 foaming helps to further disperse the nano-silica fibers and ultrafine alumina fibers and reduce agglomeration, thereby forming a more uniform reinforcement phase in the synthetic leather and improving the overall performance of the material. Supercritical CO2 foaming increases the interfacial bonding between the fiber and the matrix, and the supercritical fluid can penetrate into the microscopic gaps between the fiber and the matrix to promote the interaction between the two. CO2 treatment can increase the smoothness and uniformity of the surface of synthetic leather, which helps to reflect ultraviolet rays and reduce the damage of ultraviolet rays to the material, thereby improving the anti-aging property. The chemical inertness of CO2 means that it will not react adversely with other chemicals in synthetic leather, which helps to maintain the chemical stability of the material and reduce aging caused by chemical reactions. CO2 treatment can enhance the tolerance of synthetic leather to chemicals and reduce material aging caused by chemical corrosion.

[0059] The cooling rate when adjusting to the CO2 supercritical state in S4 is 1-1.5℃ / min. Slow cooling can reduce the thermal stress caused by the temperature gradient inside the material, avoid the cracking or deformation of the material caused by rapid cooling, make the foamed synthetic leather have better dimensional stability and lower shrinkage, and ensure the stability of the bubble structure.

[0060] Embodiment 1

[0061] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0062] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0063] S2: 10 parts of nano-silica fibers and 10 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0064] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0065] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.1MPa / min to obtain a polyamide foam;

[0066] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0067] Embodiment 2

[0068] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0069] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0070] S2: 10 parts of nano-silica fibers and 20 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0071] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0072] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.1MPa / min to obtain a polyamide foam;

[0073] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0074] Embodiment 3

[0075] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0076] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0077] S2: 10 parts of nano-silica fibers and 30 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0078] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0079] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.1MPa / min to obtain a polyamide foam;

[0080] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0081] Embodiment 4

[0082] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0083] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0084] S2: 10 parts of nano-silica fibers and 40 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0085] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0086] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.1MPa / min to obtain a polyamide foam;

[0087] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0088] Embodiment 5

[0089] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0090] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0091] S2: 10 parts of nano-silica fibers and 50 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0092] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0093] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.1MPa / min to obtain a polyamide foam;

[0094] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0095] Embodiment 6

[0096] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0097] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0098] S2: 10 parts of nano-silica fibers and 30 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0099] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0100] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, the temperature during the adjustment process is cooled at a rate of 1.5°C / min, and the foaming reaction is carried out for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.05MPa / min to obtain a polyamide foam;

[0101] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0102] Embodiment 7

[0103] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0104] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0105] S2: 10 parts of nano-silica fibers and 30 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0106] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0107] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.15MPa / min to obtain a polyamide foam;

[0108] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0109] Embodiment 8

[0110] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0111] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0112] S2: 10 parts of nano-silica fibers and 30 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0113] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0114] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, cooling the temperature during the adjustment process at a rate of 1.5°C / min, and performing a foaming reaction for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.2MPa / min to obtain a polyamide foam;

[0115] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0116] Embodiment 9

[0117] This embodiment provides a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, and the preparation method is as follows:

[0118] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid, 10 parts of methyl methacrylate and 3 parts of TiO2 are added into a reactor and heated for polymerization reaction at a temperature of 235°C for 4 hours. During heating, the pressure in the reactor is gradually increased from normal pressure to 110 kPa to obtain a polyamide melt;

[0119] S2: 10 parts of nano-silica fibers and 30 parts of ultrafine alumina fibers, which were respectively soaked in a 1% sodium dodecyl sulfate solution for 1 hour and then taken out and dried, were added to the polyamide melt in S1 and stirred, wherein the diameters of the nano-silica fibers and the ultrafine alumina fibers were 200 nm and 300 nm, respectively, and the lengths of the nano-silica fibers and the ultrafine alumina fibers were 3 mm and 2 mm, respectively. The stirring process was first carried out at a speed of 250 rpm for 10 minutes, and then increased to a speed of 400 rpm for 20 minutes to obtain a polyamide mixed melt;

[0120] S3: adding 1 part of trimethylolpropane triacrylate, 3 parts of polysiloxane and 5 parts of 2,6-di-tert-butyl-4-methylphenol to the polyamide mixed melt in S3 and stirring at a stirring speed of 300 rpm for 60 min at a stirring temperature of 225° C., calendering the polyamide modified melt and the polyester fabric to obtain a polyester composite material;

[0121] S4: transferring the polyester composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to 31.1°C and 7.385MPa, the temperature during the adjustment process is cooled at a rate of 1.5°C / min, and the foaming reaction is carried out for 2h after the adjustment is completed. After the foaming reaction, the pressure is slowly reduced to normal pressure at a pressure reduction rate of 0.25MPa / min to obtain a polyamide foam;

[0122] S5: Dry the polyamide foam in S4 at a temperature of 31.1° C. for 3 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

[0123] Comparative Example 1

[0124] This comparative example provides a synthetic leather, and the preparation method is as follows:

[0125] S1: 30 parts of hexamethylenediamine, 25 parts of dodecanedioic acid and 3 parts of TiO2 are added into a reactor, and the polymerization reaction is carried out by heating at a temperature of 235°C for 4 hours to obtain a polyamide melt, and the polyamide melt is calendered with a polyester fabric to obtain a polyester composite material;

[0126] S2: The polyester composite material in S1 was cooled to room temperature at a rate of 1.5°C / min, and then dried at a temperature of 31.1°C for 3 hours to obtain a synthetic leather.

[0127] Samples of the same mass as those in Examples 1 to 9 and Comparative Example 1 were taken and their anti-aging ability was tested using an aging tester, that is, after being irradiated with a high-intensity fluorescent lamp for an amount of light equivalent to 500 hours of sunlight, the tensile strength before and after the irradiation was measured, and the tensile strength retention rate was calculated. Based on the GB / T 21196.3-2007 standard, the samples were subjected to a friction resistance test, the sample mass before and after friction was measured, and the mass wear rate was calculated. The test results are shown in Table 1.

[0128] Table 1 Anti-aging and friction resistance test data of Examples 1 to 9 and Comparative Example 1

[0129]

[0130]

[0131] It can be seen from Table 1 that the tensile strength retention rates of Examples 1 to 9 are all greater than that of Comparative Example 1, and the mass wear rates of Examples 1 to 9 are all less than that of Comparative Example 1. The highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather of the present application has superiority.

[0132] In Examples 1 to 5, as the mass proportion of ultrafine alumina fibers gradually increases, the tensile strength retention of the samples first increases and then decreases, and the mass wear of the samples first decreases and then increases. This is because the ultrafine alumina fibers can be evenly dispersed in the matrix to form a good microstructure, reduce local stress concentration, and thus improve the tensile strength. Ultrafine alumina fibers with a high specific surface area also have high hardness, and their distribution on the surface of synthetic leather can improve the wear resistance of synthetic leather. However, when the mass proportion of ultrafine alumina fibers is excessive, fiber aggregation may occur, resulting in an uneven microstructure of the material, causing the tensile strength retention rate to begin to decrease. At high fiber content, the protruding parts of the fibers become the dominant factor in wear, resulting in an increase in the wear rate. The preferred embodiment is Example 3.

[0133] In Example 3 and Examples 6 to 9, as the depressurization rate after foaming gradually increases, the tensile strength retention of the sample first increases and then decreases, and the mass wear of the sample first decreases and then increases. This is because at an appropriate depressurization rate, the bubbles inside the material can grow and stabilize evenly to form a uniform and moderately sized bubble structure, which helps to improve the tensile strength and tensile strength retention rate of the material. The uniform and dense material structure can reduce the friction coefficient of the material surface and reduce the mass wear rate. When the depressurization rate is too high, it will cause the bubbles to expand and rupture rapidly, thereby forming larger holes and cracks in the material. These defects will reduce the tensile strength of the material and increase the surface roughness of the synthetic leather, thereby increasing the mass wear rate. The preferred embodiment is Example 7.

[0134] The above is based on the ideal embodiment of the present invention. Through the above description, relevant personnel can make various changes and modifications without departing from the technical concept of the present invention. The technical scope of the present invention is not limited to the content in the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather, characterized in that: It consists of component A, component B and component C, wherein: The A component comprises: a bio-based diamine, a bio-based dibasic acid and a functional comonomer, wherein the mass ratio of the bio-based diamine, the bio-based dibasic acid and the functional comonomer is 40-50:35-45:10-20; The B component includes: nano-silicon dioxide fibers and ultra-fine alumina fibers, and the mass ratio of the nano-silicon dioxide fibers to the ultra-fine alumina fibers is 1:2-4; The C component includes: a cross-linking agent, a wear-resistant enhancer, an anti-aging agent and a catalyst, and the mass ratio of the cross-linking agent, the wear-resistant enhancer, the anti-aging agent and the catalyst is: 1-2:3-5:3-5:2-3； The mass ratio of the A component, the B component and the C component is 60-70:25-35:10-15.

2. The highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 1, characterized in that: The bio-based diamine, the bio-based dibasic acid and the functional comonomer are hexamethylenediamine, dodecanedioic acid and methyl methacrylate respectively.

3. The highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 1, characterized in that: The diameters of the nano-silica fiber and the ultra-fine alumina fiber are 100-300 nm and 200-400 nm, respectively, and the lengths of the nano-silica fiber and the ultra-fine alumina fiber are 2-3 mm and 1-2 mm, respectively.

4. The highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 1, characterized in that: The crosslinking agent, the wear resistance enhancer, the anti-aging agent and the catalyst are trimethylolpropane triacrylate, polysiloxane, 2,6-di-tert-butyl-4-methylphenol and TiO2 respectively.

5. A method for preparing a highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather, based on the highly wear-resistant and aging-resistant automotive interior thermoplastic elastomer foamed synthetic leather according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: adding bio-based diamine, bio-based dibasic acid, functional comonomer and catalyst into a reactor, heating to carry out polymerization reaction, the heating temperature is 230-240° C., the heating time is 2-4 hours, and a polyamide melt is obtained; S2: adding nano-silica fibers and ultrafine alumina fibers to the polyamide melt in S1 and stirring for 10-30 minutes to obtain a polyamide mixed melt; S3: adding a crosslinking agent, a wear-resistant reinforcing agent and an anti-aging agent to the polyamide mixed melt in S3 and stirring the mixture at a stirring speed of 200-400 rpm, a stirring time of 30-60 min, and a stirring temperature of 220-230° C. to obtain a polyamide modified melt, and calendering the polyamide modified melt and a base fabric to obtain a base fabric composite material; S4: transferring the base fabric composite material in S3 to a foaming device, injecting CO2 and adjusting the reaction conditions in the foaming device to a CO2 supercritical state, performing a foaming reaction for 1-2 hours, and slowly reducing the pressure to normal pressure at a pressure reduction rate of 0.1-0.2 MPa / min after the foaming reaction to obtain a polyamide foam; S5: drying the polyamide foam in S4 at room temperature for 2-4 hours to obtain a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather.

6. The method for preparing a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 5, characterized in that: When the polymerization reaction in S1 is carried out, the gas pressure in the reactor is gradually increased from normal pressure to 110 kPa.

7. The method for preparing a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 5, characterized in that: The nano-silica fiber and the ultrafine alumina fiber in S2 are subjected to surface activation treatment before being added into the polyamide melt. The specific treatment process is to immerse the nano-silica fiber and the ultrafine alumina fiber in a sodium dodecyl sulfate solution with a mass fraction of 0.5-1% for 1-2 hours, take them out and dry them.

8. The method for preparing a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 5, characterized in that: The stirring process in S2 is firstly carried out at a speed of 200-250 rpm for 5-10 min, and then increased to a speed of 350-400 rpm for stirring.

9. The method for preparing a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 5, characterized in that: The supercritical state conditions of the CO2 in the S4 are 30.8-31.4°C and 7.38-7.39MPa.

10. The method for preparing a highly wear-resistant and anti-aging automotive interior thermoplastic elastomer foamed synthetic leather according to claim 9, characterized in that: The cooling rate when adjusting the CO2 to the supercritical state in S4 is 1-1.5°C / min.

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