Low-temperature-resistant wear-resistant bio-based composite fabric and preparation method thereof

Abstract

The application relates to the technical field of layered composite fabrics, and discloses an anti-low-temperature wear-resistant bio-based composite fabric and a preparation method thereof. The preparation method comprises the following steps: spinning bio-based polytrimethylene terephthalate fibers and modified wool fibers to obtain a single-layer blended fabric, impregnating the single-layer blended fabric with a finishing liquid, obtaining an outer layer / inner layer composite fabric after compounding, and coating a polyurethane-based coating material to obtain the anti-low-temperature wear-resistant bio-based composite fabric. The composite fabric has good low-temperature-resistant and warm-keeping performance and good wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of layered composite fabric, in particular to an anti-low-temperature wear-resistant bio-based composite fabric and a preparation method thereof. BACKGROUND

[0002] In a low-temperature environment, the human body surface will lose heat, and the anti-low-temperature thermal fabric worn to maintain the body heat is an effective equipment to protect the human body from low temperature. The existing anti-low-temperature thermal fabric has two main thermal principles, namely, passive and active. The passive thermal principle is mainly achieved by preventing the rapid loss of body heat, so as to form a microclimate layer between the body and the fabric, and a large amount of air with extremely low thermal conductivity is stored between the fabric layers, which can effectively isolate heat transfer. The active thermal principle is to convert other forms of energy into heat energy, so as to maintain the body heat and achieve the effect of thermal protection.

[0003] The performance of fabric against abrasion caused by friction with another object is called wear resistance. Textile fabrics are subjected to various forces during daily use and wearing, and thus are abraded. Therefore, improving the wear resistance of fabric has a positive effect on improving the durability of textile fabrics.

[0004] The prior art such as Chinese patent CN103381689A discloses a moisture-absorbing, wear-resistant, alkali-resistant, anti-pilling and flame-retardant fabric. Acrylic yarn, artificial fiber, spandex, and wool blended yarn are used as warp yarn, and acrylic yarn, artificial fiber, spandex, wool blended yarn, and regenerated cellulose fiber blended yarn are used as weft yarn to form a fabric surface layer. Then, a flame-retardant layer is pasted to form a layered fabric with good thermal properties, anti-pilling, moisture absorption, wear resistance, and flame retardance. Although the fabric has good thermal properties, it belongs to passive thermal, and the low-temperature resistance of the material is limited. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provide an anti-low-temperature wear-resistant bio-based composite fabric and a preparation method thereof. The composite fabric has good low-temperature thermal properties and wear resistance.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A preparation method of an anti-low-temperature wear-resistant bio-based composite fabric, comprising the following steps:

[0008] Step one, preparing an outer / inner layer composite fabric;

[0009] Step (1), blending bio-based polytrimethylene terephthalate fibers and wool fibers to obtain blended yarn; weaving the blended yarn as warp and weft to obtain a single-layer blended fabric;

[0010] The single-layer blended fabric is immersed in a reducing agent, reacted, taken out after the reaction, washed with water, dried, and a modified single-layer blended fabric is obtained;

[0011] Step (2), the modified single-layer blended fabric is immersed in a finishing liquid, taken out after the immersion, and dried to obtain an outer layer fabric and an inner layer fabric, respectively;

[0012] The finishing liquid is prepared by the following steps:

[0013] S11, amino nano far infrared ceramic powder, glutaraldehyde, and water are mixed, reacted, filtered, washed, and an intermediate product is obtained;

[0014] The intermediate product, chitosan quaternary ammonium salt, and water are mixed and continuously reacted, filtered, washed, and dried to obtain a chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material;

[0015] S12, the chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material, water, N-acetyl-L-cysteine, and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide are mixed, a pH regulator is added to adjust the pH value, reacted, and purified after the reaction to obtain a thiolated chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material;

[0016] The thiolated chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material is mixed with water to obtain a finishing liquid;

[0017] Step (3), the outer layer fabric and the inner layer fabric are attached and aligned, and the outer layer fabric and the inner layer fabric are sewn together by a multi-layer fabric quilting machine using a bio-based polypropylene terephthalate sewing thread to obtain an outer layer / inner layer composite fabric;

[0018] Step two, a polyurethane-based coating material is coated on one side of the outer layer / inner layer composite fabric having the outer layer fabric, a coating is formed after the coating is completed, and baking is performed to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric;

[0019] The polyurethane-based coating material is prepared by the following steps:

[0020] S21, trifluoropropylmethylcyclotrisiloxane and 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane are mixed, a catalyst is added, and the reaction is carried out at an elevated temperature, and an addition-type fluorosilicone rubber is obtained after the reaction is completed;

[0021] S22, the addition-type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator, and tetrahydrofuran are mixed uniformly, reacted, and after the reaction is completed, mercapto silicon carbide is added and the reaction is continued, and after the reaction is completed, rotary evaporation and drying are performed to obtain a wear-resistant additive;

[0022] S23, mixing isophorone diisocyanate, polytetramethylene ether glycol, catalyst dibutyl tin dilaurate, reacting, after the reaction is completed, adding 1,4-butanediol and wear-resistant additive, continuing to react, after the reaction is completed, diluting to obtain polyurethane-based coating material.

[0023] Preferably, in the step of preparing the outer / inner composite fabric, in step (1): the mass ratio of bio-based polytrimethylene terephthalate fibers to wool fibers is 40-50:50-60; the yarn count of the blended yarn is 60-80S in English count; the grammage of the single-layer blended fabric is 220-240g / m 2 .

[0024] Preferably, in the step of preparing the outer / inner composite fabric, in step (1): the bath ratio of the single-layer blended fabric to the reducing agent is 1:40-50; the reaction conditions are: reacting at room temperature for 4-5h.

[0025] Preferably, in the step of preparing the outer / inner composite fabric, the reducing agent in step (1) is prepared by the following steps:

[0026] Mixing tri(2-carboxyethyl)phosphine, water and ethanol uniformly in a mass ratio of 1:40-50:50-60, adding sodium carbonate / sodium bicarbonate buffer solution to adjust the pH value to neutral to obtain the reducing agent.

[0027] Preferably, in the step of preparing the outer / inner composite fabric, in step (2): the bath ratio of the modified single-layer blended fabric to the finishing liquid is 1:20-30; the pad-dry conditions are: dipping for 20-30min at room temperature, two dipping and two padding, and the pick-up rate is 88-92%; the drying conditions are: drying in air atmosphere at room temperature for 24-30h.

[0028] Preferably, in the step of preparing the outer / inner composite fabric, in S11 of step (2): the mass ratio of amino nano far-infrared ceramic powder, glutaraldehyde and water is 1:0.8-1:80-120; the reaction conditions are: stirring and reacting at room temperature for 3-4h; the mass ratio of the intermediate product, chitosan quaternary ammonium salt and water is 1:4.5-5:100; the continuous reaction conditions are: continuing to react at room temperature for 2-3h.

[0029] Preferably, in the step of preparing the outer / inner composite fabric, in S12 of step (2), the mass ratio of the quaternary ammonium salt of chitosan / nano-far infrared ceramic powder composite material, water, N-acetyl-L-cysteine and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide is 7:500-550:9.5-10:5.8-6; the reaction condition is stirring reaction at room temperature in dark environment at pH 5-5.5 for 3-4 h; and the mass ratio of the thiolated quaternary ammonium salt of chitosan / nano-far infrared ceramic powder composite material to water is 5-8:100.

[0030] Preferably, the adjusting agent comprises 5 mol / L sodium hydroxide aqueous solution.

[0031] Preferably, the purification operation comprises: taking the reaction product obtained after the reaction, adding 5-8 times the mass of the reaction product of ethanol, filtering, and taking the filter cake to dry at a temperature of 50-60℃ for 12-18 h.

[0032] Preferably, in step (2), the coating thickness is 0.8-1 mm; and the baking operation comprises: pre-baking at a temperature of 80-90℃ for 15-20 min and baking at a temperature of 100-110℃ for 3-4 min.

[0033] Preferably, in the step of preparing the polyurethane-based coating material in step (2), in S21, the mass ratio of trifluoropropylmethylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and catalyst is 70-72:5.1-5.5:0.4-0.5; and the reaction condition is reaction at a temperature of 120-130℃ for 1-3 h.

[0034] Further, the catalyst is potassium hydroxide, and the addition temperature is 50-60℃.

[0035] Preferably, in the step of preparing the polyurethane-based coating material in step (2), in S22, the mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, initiator and tetrahydrofuran is 10-12:0.15:5-6:0.05-0.06:40-50; the reaction condition is reaction at room temperature in the environment of ultraviolet light with a wavelength of 365 nm for 5-10 min; and the continuous reaction condition is continuous reaction at room temperature in the environment of ultraviolet light with a wavelength of 365 nm for 0.5-1 h.

[0036] Further, the initiator is benzoin dimethyl ether.

[0037] Preferably, in the preparation of the polyurethane-based coating material in the second step, in S23: the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol and 1,4-butanediol is 3:1-1.2:1.3-1.5, the amount of catalyst dibutyltin dilaurate added is 0.5wt% of polytetrahydrofuran ether diol, and the amount of wear-resistant additive added is 15-20wt% of the polyurethane-based coating material.

[0038] Preferably, in the preparation of the polyurethane-based coating material in the second step, in S23: the reaction conditions are: reaction under a nitrogen atmosphere at a temperature of 70-80℃ for 3-4h; the continued reaction conditions are: continued reaction at a temperature of 75-85℃ for 2-3h; and the solid content of the polyurethane-based coating material is 30-35wt%.

[0039] Preferably, the diluent used in the dilution operation comprises acetone.

[0040] Preferably, an anti-low-temperature wear-resistant bio-based composite fabric prepared by the preparation method of the anti-low-temperature wear-resistant bio-based composite fabric as described above.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] The nano far infrared ceramic powder is a nano powder material that can radiate far infrared rays, wherein the far infrared rays have strong penetration and radiation, and exhibit a significant temperature control effect; when applied to fabric finishing, the nano far infrared ceramic powder can endow the fabric with the performance of light absorption and heat generation, and improve the low-temperature resistance of the fabric by using positive thermal insulation; in the present application, the amino groups of the nano far infrared ceramic powder modified by the amino silane coupling agent are reacted with glutaraldehyde, and then grafted and compounded with the bio-based material chitosan quaternary ammonium salt with good antibacterial and moisture absorption performance, so that the chitosan quaternary ammonium salt is loaded on the surface of the nano far infrared ceramic powder, and then reacted with N-acetyl-L-cysteine to graft thiol functional groups, thereby obtaining a thiolated chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material; the composite material is compounded with water to form a finishing liquid, and the modified single-layer blended fabric is treated by padding, so that the outer layer fabric and the inner layer fabric have improved low-temperature resistance and moisture absorption capacity.

[0043] The modified single-layer blended fabric is prepared from a single-layer blended fabric containing bio-based polypropylene terephthalate fibers and wool fibers after immersion in a reducing agent; in the immersion treatment process, the reducing agent tris (2-carboxyethyl) phosphine can reduce the disulfide bond in the wool fiber macromolecule into a mercapto group, so that the obtained modified single-layer blended fabric contains a mercapto functional group on the surface; after the modified single-layer blended fabric is immersed in a finishing liquid containing a mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material, when dried in an air atmosphere, the mercapto functional group in the finishing liquid and the mercapto functional group in the modified single-layer blended fabric are oxidized by oxygen to form a disulfide bond, so that the chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material is fixed on the surface of the fabric and is not easy to fall off, not only improving the moisture absorption and antibacterial capacity of the fabric and the comfort, but also improving the long-acting low-temperature resistance of the fabric.

[0044] The present application prepares addition type fluorosilicone rubber by anionic ring-opening polymerization reaction of trifluoropropylmethylcyclotrisiloxane and 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, and then the fluorosilicone rubber is grafted on the surface of inorganic carrier silicon carbide by mercapto-alkene click chemistry reaction of 2-mercaptoethanol and mercapto silane coupling agent modified silicon carbide, and a certain amount of hydroxyl is introduced, so that the prepared wear-resistant additive not only has excellent hydrophobicity and low-temperature resistance, but also can participate in the polymerization reaction of polyurethane by using the hydroxyl, thereby improving the compatibility of the wear-resistant additive in the polyurethane-based coating material.

[0045] The present application coats the polyurethane-based coating material on the surface of the outer / inner composite fabric to form a low-temperature-resistant and wear-resistant coating, and prepares the low-temperature-resistant and wear-resistant bio-based composite fabric; the polyurethane in the coating material has excellent low-temperature resistance and still has good comprehensive performance under low-temperature conditions, and cooperates with the fluorosilicone rubber in the wear-resistant additive to improve the low-temperature resistance of the composite fabric; the nano silicon carbide in the wear-resistant additive not only has excellent wear resistance, but also has good light-heat conversion capacity, thereby improving the wear resistance of the composite material and further improving the low-temperature resistance of the composite fabric. BRIEF DESCRIPTION OF DRAWINGS

[0046] Figure 1 It is a process flow chart for preparing the low-temperature-resistant and wear-resistant bio-based composite fabric in the present application;

[0047] Figure 2 It is a structure schematic diagram of the low-temperature-resistant and wear-resistant bio-based composite fabric prepared in the present application;

[0048] Figure 3 It is a warm-keeping rate column chart of the bio-based composite fabric prepared in the examples and the comparative examples in the performance test in the present application;

[0049] Figure 4The temperature difference column chart of the bio-based composite fabric prepared in the examples and the comparative examples in the present application in the performance test;

[0050] In the figure:

[0051] 1, outer / inner composite fabric; 11, inner fabric; 12, outer fabric; 2, coating. DETAILED DESCRIPTION

[0052] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0053] Example 1

[0054] The present embodiment discloses a preparation method of a low-temperature-resistant and wear-resistant bio-based composite fabric, comprising the following steps:

[0055] Step one, preparing an outer / inner composite fabric;

[0056] Step (1), blending bio-based polytrimethylene terephthalate fibers and wool fibers at a mass ratio of 50:50 to obtain blended yarn with a yarn count of 60S in English count; weaving the blended yarn as warp and weft to obtain a single-layer blended fabric with a grammage of 220 g / m 2 ;

[0057] Dipping the single-layer blended fabric in a reducing agent with a bath ratio of 1:40, reacting at room temperature for 4 h, taking out after the reaction, washing three times, and drying at a temperature of 50℃ for 10 h to obtain a modified single-layer blended fabric;

[0058] The reducing agent is prepared by the following steps:

[0059] Mixing tri(2-carboxyethyl)phosphine, water and ethanol at a mass ratio of 1:45:55 uniformly, adding sodium carbonate / sodium bicarbonate buffer solution to adjust the pH value to neutral to obtain the reducing agent;

[0060] Step (2), dipping the modified single-layer blended fabric in a finishing liquid with a bath ratio of 1:20, dipping at room temperature for 20 min, two-dipping and two-rolling with a pick-up rate of 88%, taking out after the dipping, drying in an air atmosphere at room temperature for 24 h to obtain an outer fabric and an inner fabric, respectively;

[0061] The finishing liquid is prepared by the following steps:

[0062] S11, amino nano far infrared ceramic powder, glutaraldehyde, water are mixed in a mass ratio of 1:1:120, stirred and reacted at room temperature for 3h, after the reaction is completed, filtration is performed, the filter cake is taken, 5 times the mass of water of the filter cake is added for washing, and an intermediate product is obtained;

[0063] The intermediate product, chitosan quaternary ammonium salt, and water are mixed in a mass ratio of 1:5:100, and the reaction is continued at room temperature for 2h, after the reaction is completed, filtration is performed, the filter cake is taken, 5 times the mass of water of the filter cake is added for washing, and drying is performed at a temperature of 50 DEG C for 26h to obtain a chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material;

[0064] S12, the chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material, water, N-acetyl-L-cysteine, and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide are mixed in a mass ratio of 7:500:9.5:5.8, 5 mol / L sodium hydroxide aqueous solution is added to adjust the pH value to 5, stirring is performed at room temperature in a dark environment for 3h, after the reaction is completed, a reaction product is obtained, 5 times the mass of ethanol of the reaction product is added, filtration is performed, the filter cake is taken, and drying is performed at a temperature of 50 DEG C for 18h to obtain a thiolated chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material;

[0065] The thiolated chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material is mixed with water in a mass ratio of 5:100 to obtain a finishing liquid;

[0066] Step (3), the outer layer fabric and the inner layer fabric are attached, and are stacked and aligned, the outer layer fabric and the inner layer fabric are sewn by a multi-layer fabric quilting machine using a bio-based polypropylene terephthalate sewing thread to obtain an outer layer / inner layer composite fabric;

[0067] Step two, a polyurethane-based coating material is coated on one side of the outer layer / inner layer composite fabric having the outer layer fabric, after coating, a coating layer with a thickness of 0.8mm is formed, pre-baking is performed at a temperature of 80 DEG C for 20min, baking is performed at a temperature of 100 DEG C for 4min, and an anti-low-temperature wear-resistant bio-based composite fabric is obtained;

[0068] The polyurethane-based coating material is prepared by the following steps:

[0069] S21, trifluoropropylmethylcyclotrisiloxane and 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane are mixed, a catalyst potassium hydroxide is added at a temperature of 50 DEG C, heating is performed, and reaction is performed at a temperature of 125 DEG C for 2h, after the reaction is completed, an addition type fluorosilicone rubber is obtained;

[0070] The mass ratio of trifluoropropylmethylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, and catalyst potassium hydroxide is 71:5.3:0.4;

[0071] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, photoinitiator benzoin dimethyl ether, tetrahydrofuran is mixed uniformly, in the wavelength 365nm ultraviolet environment, room temperature reaction 5min, after the reaction, add mercapto silicon carbide, in the wavelength 365nm ultraviolet environment, continue to react at room temperature for 0.5h, after the reaction, at room temperature, rotary evaporation to remove the solvent tetrahydrofuran, drying at 50℃ temperature for 10h, obtain wear-resistant additive;

[0072] Wherein, the mass ratio of addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, initiator benzoin dimethyl ether, tetrahydrofuran is 10:0.15:5:0.05:40;

[0073] S23, the isophorone diisocyanate, polytetrahydrofuran ether diol, catalyst dibutyltin dilaurate is mixed, in nitrogen atmosphere, 70℃ temperature reaction 4h, after the reaction, add 1,4-butanediol and wear-resistant additive, continue to react at 75℃ temperature for 3h, after the reaction, add acetone dilution, obtain the polyurethane based coating material with solid content of 30wt%;

[0074] Wherein, the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol, 1,4-butanediol is 3:1:1.5, the amount of catalyst dibutyltin dilaurate is 0.5wt% of polytetrahydrofuran ether diol, the amount of wear-resistant additive is 15wt% of polyurethane based coating material.

[0075] Example 2

[0076] The embodiment discloses a preparation method of a low-temperature-resistant wear-resistant bio-based composite fabric, comprising the following steps:

[0077] Step one, preparation of outer / inner composite fabric;

[0078] Step (1), bio-based polytrimethylene terephthalate fiber and wool fiber are blended in a mass ratio of 47:53 to obtain blended yarn with 70S of English count; the blended yarn is used as warp and weft to weave a single-layer blended fabric with a grammage of 230g / m 2 ;

[0079] The single-layer blended fabric is immersed in a reducing agent with a bath ratio of 1:45, and reacted at room temperature for 4h, then taken out, washed three times, and dried at 55℃ for 8h to obtain a modified single-layer blended fabric;

[0080] Wherein, the preparation of the reducing agent is the same as that in example 1;

[0081] Step (2), the modified single-layer blended fabric is immersed in the finishing liquid with a bath ratio of 1:25, immersed for 20 min at room temperature, and two immersions and two rollings are performed with a pick-up rate of 88%. After the immersion, the outer fabric and the inner fabric are taken out and dried in an air atmosphere at room temperature for 26 h to obtain the outer fabric and the inner fabric, respectively.

[0082] The finishing liquid is prepared by the following steps:

[0083] The preparation of the mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite is the same as that in Embodiment 1. The mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite is mixed with water in a mass ratio of 6:100 to obtain the finishing liquid.

[0084] Step (3), the outer fabric and the inner fabric are laminated and aligned, and the outer fabric and the inner fabric are sewn together by using a bio-based polytrimethylene terephthalate sewing thread through a multi-layer fabric quilting machine to obtain an outer / inner composite fabric.

[0085] Step two, a polyurethane-based coating material is coated on one side of the outer / inner composite fabric having the outer fabric, and after the coating is completed, a coating with a thickness of 0.85 mm is formed. The coating is pre-baked at a temperature of 85°C for 20 min and baked at a temperature of 105°C for 4 min to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric.

[0086] The polyurethane-based coating material is prepared by the following steps:

[0087] S21, the preparation of the addition type fluorosilicone rubber is the same as that in Embodiment 1.

[0088] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator benzoin dimethyl ether, and tetrahydrofuran are uniformly mixed and reacted in an ultraviolet environment with a wavelength of 365 nm at room temperature for 5 min. After the reaction is completed, mercapto silicon carbide is added, and the reaction is continued in an ultraviolet environment with a wavelength of 365 nm at room temperature for 0.8 h. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at room temperature, and the mixture is dried at a temperature of 55°C for 10 h to obtain a wear-resistant additive.

[0089] The mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, the initiator benzoin dimethyl ether, and tetrahydrofuran is 10.5:0.15:5.3:0.05:45.

[0090] S23, isophorone diisocyanate, polytetrahydrofuran ether diol, and a catalyst dibutyltin dilaurate are mixed and reacted in a nitrogen atmosphere at a temperature of 75°C for 4 h. After the reaction is completed, 1,4-butanediol and the wear-resistant additive are added, and the reaction is continued at a temperature of 80°C for 3 h. After the reaction is completed, acetone is added for dilution to obtain a polyurethane-based coating material with a solid content of 33 wt%.

[0091] Wherein, the molar ratio of isophorone diisocyanate, polytetramethylene ether glycol, 1,4-butanediol is 3:1.05:1.45, the addition amount of catalyst dibutyltin dilaurate is 0.5wt% of polytetramethylene ether glycol, and the addition amount of wear-resistant additive is 16wt% of polyurethane-based coating material.

[0092] Example 3

[0093] The embodiment discloses a preparation method of a low-temperature-resistant wear-resistant bio-based composite fabric, comprising the following steps:

[0094] Step one, preparing an outer / inner composite fabric;

[0095] Step (1), bio-based polytrimethylene terephthalate fibers and wool fibers are blended at a mass ratio of 45:55 to obtain blended yarn with a yarn count of 70S in English count; the blended yarn is used as warp and weft threads to weave a single-layer blended fabric with a grammage of 230g / m 2 ;

[0096] The single-layer blended fabric is immersed in a reducing agent with a bath ratio of 1:45, and reacted at room temperature for 4.5h; after the reaction is completed, the single-layer blended fabric is taken out, washed with water for three times, and dried at a temperature of 55°C for 8h to obtain a modified single-layer blended fabric;

[0097] Wherein, the preparation of the reducing agent is the same as that in Example 1;

[0098] Step (2), the modified single-layer blended fabric is immersed in a finishing liquid with a bath ratio of 1:25, and immersed at room temperature for 25min; two immersions and two rollings are performed with a pick-up rate of 90%; after the immersion is completed, the outer fabric and the inner fabric are respectively obtained by drying the outer fabric and the inner fabric in an air atmosphere at room temperature for 26h;

[0099] Wherein, the finishing liquid is prepared by the following steps:

[0100] The preparation of the mercapto-chitosan quaternary ammonium salt / nano-far infrared ceramic powder composite material is the same as that in Example 1; the mercapto-chitosan quaternary ammonium salt / nano-far infrared ceramic powder composite material is mixed with water at a mass ratio of 6.5:100 to obtain the finishing liquid;

[0101] Step (3), the outer fabric and the inner fabric are laminated and aligned; the outer fabric and the inner fabric are sewn by a multi-layer fabric quilting machine using a bio-based polytrimethylene terephthalate sewing thread to obtain an outer / inner composite fabric;

[0102] Step two, polyurethane-based coating material is coated on the outer / inner composite fabric with the side of the outer fabric, after coating, a coating with a thickness of 0.9mm is formed, pre-baking at 85℃ for 18min, baking at 105℃ for 3.5min, to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric;

[0103] The polyurethane-based coating material is prepared by the following steps:

[0104] S21, the preparation of addition type fluorosilicone rubber is the same as example 1;

[0105] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, photoinitiator benzoin dimethyl ether, tetrahydrofuran are mixed uniformly, and then reacted in the ultraviolet environment with a wavelength of 365nm at room temperature for 8min; after the reaction is completed, mercapto silicon carbide is added, and the reaction is continued in the ultraviolet environment with a wavelength of 365nm at room temperature for 0.8h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at room temperature, and then dried at 55℃ for 10h to obtain a wear-resistant additive;

[0106] The mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, initiator benzoin dimethyl ether and tetrahydrofuran is 11:0.15:5.5:0.05:45;

[0107] S23, isophorone diisocyanate, polytetrahydrofuran ether diol and catalyst dibutyltin dilaurate are mixed, and then reacted in a nitrogen atmosphere at 75℃ for 3.5h; after the reaction is completed, 1,4-butanediol and the wear-resistant additive are added, and the reaction is continued at 80℃ for 2.5h; after the reaction is completed, acetone is added for dilution to obtain a polyurethane-based coating material with a solid content of 33wt%;

[0108] The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol and 1,4-butanediol is 3:1.1:1.4, the addition amount of catalyst dibutyltin dilaurate is 0.5wt% of polytetrahydrofuran ether diol, and the addition amount of the wear-resistant additive is 18wt% of the polyurethane-based coating material.

[0109] Example 4

[0110] The embodiment discloses a preparation method of a low-temperature-resistant and wear-resistant bio-based composite fabric, which comprises the following steps:

[0111] Step one, preparing an outer / inner composite fabric;

[0112] Step (1), bio-based polytrimethylene terephthalate fibers and wool fibers are blended in a mass ratio of 42:58 to obtain blended yarn with a yarn count of 70S in English system; the blended yarn is used as warp and weft to weave a fabric with a grammage of 230g / m 2a single-layer blended fabric;

[0113] The single-layer blended fabric is immersed in a reducing agent with a bath ratio of 1:45, and reacts at room temperature for 5 hours. After the reaction, it is taken out, washed with water three times, and dried at 55°C for 8 hours to obtain a modified single-layer blended fabric.

[0114] In the preparation of the reducing agent, the preparation method of Example 1 is used.

[0115] Step (2), the modified single-layer blended fabric is immersed in a finishing liquid with a bath ratio of 1:25, and immersed for 30 minutes at room temperature. After the immersion, it is taken out and dried in an air atmosphere at room temperature for 26 hours to obtain an outer fabric and an inner fabric, respectively.

[0116] The finishing liquid is prepared by the following steps:

[0117] The preparation of the mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite is the same as that of Example 1. The mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite is mixed with water in a mass ratio of 7:100 to obtain a finishing liquid.

[0118] Step (3), the outer fabric and the inner fabric are laminated and aligned, and the outer fabric and the inner fabric are sewn together by a multi-layer fabric quilting machine using a bio-based polytrimethylene terephthalate sewing thread to obtain an outer / inner composite fabric.

[0119] Step two, a polyurethane-based coating material is coated on one side of the outer / inner composite fabric with the outer fabric, and after coating, a coating with a thickness of 0.95 mm is formed. Pre-baking is carried out at a temperature of 85°C for 15 minutes, and baking is carried out at a temperature of 105°C for 3 minutes to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric.

[0120] The polyurethane-based coating material is prepared by the following steps:

[0121] S21, the preparation of the addition type fluorosilicone rubber is the same as that of Example 1.

[0122] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator benzoin dimethyl ether, and tetrahydrofuran are uniformly mixed, and reacted in an ultraviolet environment with a wavelength of 365 nm at room temperature for 10 minutes. After the reaction, mercapto silicon carbide is added, and the reaction is continued in an ultraviolet environment with a wavelength of 365 nm at room temperature for 0.8 hours. After the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at room temperature, and dried at a temperature of 55°C for 10 hours to obtain a wear-resistant additive.

[0123] The mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, the initiator benzoin dimethyl ether, and tetrahydrofuran is 11.5:0.15:5.8:0.06:45.

[0124] S23, isophorone diisocyanate, polytetrahydrofuran ether glycol, catalyst dibutyltin dilaurate are mixed, reacted for 4h under nitrogen atmosphere at 75℃, after the reaction is completed, 1, 4-butanediol and wear-resistant additive are added, and the reaction is continued for 3h at 80℃, after the reaction is completed, acetone is added for dilution, and a polyurethane-based coating material with a solid content of 34wt% is obtained;

[0125] The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol and 1, 4-butanediol is 3:1.15:1.35, the addition amount of catalyst dibutyltin dilaurate is 0.5wt% of polytetrahydrofuran ether glycol, and the addition amount of wear-resistant additive is 19wt% of the polyurethane-based coating material.

[0126] Example 5

[0127] The embodiment discloses a preparation method of a low-temperature-resistant wear-resistant bio-based composite fabric, comprising the following steps:

[0128] Step one, preparing an outer / inner composite fabric;

[0129] Step (1), bio-based polytrimethylene terephthalate fibers and wool fibers are blended at a mass ratio of 40:60 to obtain blended yarn with a yarn count of 80S; the blended yarn is used as warp and weft threads to weave a single-layer blended fabric with a grammage of 240g / m 2 ;

[0130] The single-layer blended fabric is immersed in a reducing agent with a bath ratio of 1:50, and reacted at room temperature for 5h, then taken out, washed with water for three times, and dried at 60℃ for 8h to obtain a modified single-layer blended fabric;

[0131] The preparation of the reducing agent is the same as that in Example 1;

[0132] Step (2), the modified single-layer blended fabric is immersed in a finishing liquid with a bath ratio of 1:30, and immersed for 30min at room temperature, two immersions and two rollings are carried out, the pick-up rate is 92%, and after the immersion is completed, the fabric is taken out and dried in air atmosphere at room temperature for 30h to obtain an outer fabric and an inner fabric, respectively;

[0133] The finishing liquid is prepared by the following steps:

[0134] The preparation of the mercapto-chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material is the same as that in Example 1; the mercapto-chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material is mixed with water at a mass ratio of 8:100 to obtain the finishing liquid;

[0135] Step (3), the outer layer fabric and the inner layer fabric are attached, stacked and aligned, and the outer layer fabric and the inner layer fabric are sewn by using a bio-based polytrimethylene terephthalate sewing thread through a multi-layer fabric quilting machine to obtain an outer layer / inner layer composite fabric;

[0136] Step two, a polyurethane-based coating material is coated on one side of the outer layer / inner layer composite fabric having the outer layer fabric, and after coating, a coating layer with a thickness of 1 mm is formed, pre-baking at 90℃ for 15 min, baking at 110℃ for 3 min, to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric;

[0137] The polyurethane-based coating material is prepared by the following steps:

[0138] S21, the preparation of the addition type fluorosilicone rubber is the same as that of Example 1;

[0139] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator benzoin dimethyl ether, and tetrahydrofuran are mixed uniformly, and then reacted in an ultraviolet environment with a wavelength of 365 nm at room temperature for 10 min. After the reaction is completed, mercapto silicon carbide is added, and the reaction is continued in an ultraviolet environment with a wavelength of 365 nm at room temperature for 1 h. After the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at room temperature, and then dried at 60℃ for 8 h to obtain a wear-resistant additive;

[0140] The mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, the initiator benzoin dimethyl ether, and tetrahydrofuran is 12:0.15:6:0.06:50;

[0141] S23, isophorone diisocyanate, polytetrahydrofuran ether diol, and a catalyst dibutyltin dilaurate are mixed, and then reacted in a nitrogen atmosphere at 80℃ for 3 h. After the reaction is completed, 1,4-butanediol and the wear-resistant additive are added, and the reaction is continued at 85℃ for 2 h. After the reaction is completed, acetone is added for dilution to obtain a polyurethane-based coating material with a solid content of 35 wt%.

[0142] The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol, and 1,4-butanediol is 3:1.2:1.3, the addition amount of the catalyst dibutyltin dilaurate is 0.5 wt% of the polytetrahydrofuran ether diol, and the addition amount of the wear-resistant additive is 20 wt% of the polyurethane-based coating material.

[0143] Comparative Example 1

[0144] This comparative example discloses a preparation method of a bio-based composite fabric, including the following steps:

[0145] Step one, preparing an outer layer / inner layer composite fabric;

[0146] Step (1), bio-based polytrimethylene terephthalate fibers and wool fibers are blended at a mass ratio of 50:50 to obtain a blended yarn with a yarn count of 60S in English count; the blended yarn is used as warp and weft threads to weave, respectively obtaining an outer layer fabric and an inner layer fabric with a grammage of 220 g / m 2 ;

[0147] Step (2), the outer layer fabric and the inner layer fabric are laminated and aligned, and the outer layer fabric and the inner layer fabric are stitched by a multi-layer fabric quilting machine using bio-based polytrimethylene terephthalate sewing thread to obtain an outer / inner composite fabric;

[0148] Step two, a polyurethane-based coating material is coated on one side of the outer / inner composite fabric having the outer layer fabric, and after coating, a coating with a thickness of 0.8 mm is formed, and pre-baking is performed at a temperature of 80℃ for 20 min, and baking is performed at a temperature of 100℃ for 4 min to obtain a bio-based composite fabric;

[0149] The polyurethane-based coating material is prepared by the following steps:

[0150] S21, the preparation of the addition type fluorosilicone rubber is the same as that of Example 1;

[0151] S22, the addition type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator benzoin dimethyl ether, and tetrahydrofuran are mixed uniformly, and reacted in an ultraviolet environment with a wavelength of 365 nm at room temperature for 5 min; after the reaction is completed, mercapto silicon carbide is added, and the reaction is continued in an ultraviolet environment with a wavelength of 365 nm at room temperature for 0.5 h; after the reaction is completed, the solvent tetrahydrofuran is removed by rotary evaporation at room temperature, and dried at a temperature of 50℃ for 10 h to obtain a wear-resistant additive;

[0152] The mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, the initiator benzoin dimethyl ether, and tetrahydrofuran is 10:0.15:5:0.05:40;

[0153] S23, isophorone diisocyanate, polytetrahydrofuran ether diol, and a catalyst dibutyltin dilaurate are mixed and reacted at a temperature of 70℃ for 4 h in a nitrogen atmosphere; after the reaction is completed, 1,4-butanediol and the wear-resistant additive are added and the reaction is continued at a temperature of 75℃ for 3 h; after the reaction is completed, dilution is performed with acetone to obtain a polyurethane-based coating material with a solid content of 30wt%;

[0154] The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol, and 1,4-butanediol is 3:1:1.5, the amount of catalyst dibutyltin dilaurate added is 0.5wt% of the polytetrahydrofuran ether diol, and the amount of wear-resistant additive added is 15wt% of the polyurethane-based coating material.

[0155] Comparative Example 2

[0156] The present comparative example discloses a preparation method of a bio-based composite fabric, comprising the following steps:

[0157] Step one, preparation of outer / inner composite fabric;

[0158] Step (1), bio-based polytrimethylene terephthalate fibers and wool fibers are blended at a mass ratio of 50:50 to obtain blended yarn with a yarn count of 60S in English count; the blended yarn is used as warp and weft threads to weave a single-layer blended fabric with a grammage of 220 g / m 2 ;

[0159] The single-layer blended fabric is immersed in a reducing agent with a bath ratio of 1:40, and reacted at room temperature for 4 h. After the reaction is completed, it is taken out and washed with water three times, and dried at a temperature of 50°C for 10 h to obtain a modified single-layer blended fabric;

[0160] wherein the reducing agent is prepared in the same manner as in Example 1;

[0161] Step (2), the modified single-layer blended fabric is immersed in a finishing liquid with a bath ratio of 1:20, and immersed at room temperature for 20 min. Two immersions and two rollings are performed with a pick-up rate of 88%. After the immersion is completed, it is taken out and dried in an air atmosphere at room temperature for 24 h to obtain an outer fabric and an inner fabric, respectively;

[0162] wherein the finishing liquid is prepared by the following steps:

[0163] The preparation of the mercapto-chitosan quaternary ammonium salt / nano-far infrared ceramic powder composite material is the same as in Example 1. The mercapto-chitosan quaternary ammonium salt / nano-far infrared ceramic powder composite material is mixed with water at a mass ratio of 5:100 to obtain the finishing liquid;

[0164] Step (3), the outer fabric and the inner fabric are laminated and aligned, and the outer fabric and the inner fabric are sewn together by a multi-layer fabric quilting machine using bio-based polytrimethylene terephthalate sewing thread to obtain an outer / inner composite fabric;

[0165] Step two, a polyurethane-based coating material is coated on one side of the outer / inner composite fabric having the outer fabric, and after the coating is completed, a coating with a thickness of 0.8 mm is formed. Pre-baking is performed at a temperature of 80°C for 20 min, and baking is performed at a temperature of 100°C for 4 min to obtain a bio-based composite fabric;

[0166] wherein the polyurethane-based coating material is prepared by the following steps:

[0167] Isophorone diisocyanate, polytetrahydrofuran ether diol, and catalyst dibutyl tin dilaurate are mixed and reacted for 4 h at 70 ℃ under a nitrogen atmosphere. After the reaction is completed, 1,4-butanediol is added, and the reaction is continued for 3 h at 75 ℃. After the reaction is completed, dilution is performed with acetone to obtain a polyurethane-based coating material with a solid content of 30 wt.%;

[0168] The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol, and 1,4-butanediol is 3:1:2.1, and the amount of catalyst dibutyl tin dilaurate added is 0.5 wt.% of the polytetrahydrofuran ether diol.

[0169] In the above examples and comparative examples:

[0170] The amino nano far infrared ceramic powder is prepared by surface modification of nano far infrared ceramic powder with γ-aminopropyl triethoxysilane (KH550). The specific preparation process is as follows: nano far infrared ceramic powder, γ-aminopropyl triethoxysilane, ethanol, and water are mixed in a mass ratio of 1:0.2:40:10, ultrasonic dispersion is performed for 30 min, 1 mol / L acetic acid aqueous solution is added to adjust the pH value to 4, and the reaction is performed at 70 ℃ for 3 h. After the reaction, filtration is performed, and drying is performed at 60 ℃ for 10 h to obtain the amino nano far infrared ceramic powder. The nano far infrared ceramic powder is from Fucai Mineral Products Co., Ltd., has a particle size of 20 nm, and is a ceramic powder body of the MgO-Al2O3-TiO2-ZrO2 system.

[0171] The mercapto silicon carbide is prepared by surface modification of nano silicon carbide with γ-mercaptopropyl triethoxysilane (KH580). The specific preparation process is as follows: nano silicon carbide, γ-mercaptopropyl triethoxysilane, and ethanol are mixed in a mass ratio of 1:0.2:50, and the reaction is performed at 65 ℃ for 2 h. After the reaction, filtration is performed, washing is performed, and drying is performed at 80 ℃ for 8 h to obtain the mercapto silicon carbide. The nano silicon carbide is from Qinghe County Chaotai Metal Material Co., Ltd., and has a specification of 50 nm.

[0172] The bio-based polytrimethylene terephthalate fiber has a fineness of 1.63 dtex and an average fiber length of 25 mm, and is prepared by melt spinning, cooling and drawing, and chopping of bio-based polytrimethylene terephthalate polyester chips. The melting temperature is: zone 1, 250 ℃; zone 2, 260 ℃; zone 3, 263 ℃; and zone 4, 265 ℃. The spinning speed is 1200 m / min. The draw ratio is 2 times. The bio-based polytrimethylene terephthalate polyester chips are from DuPont Company, and have a specification of fiber-grade bio-based PTT polyester chips and a characteristic viscosity of 0.95 dL / g.

[0173] The wool fibers are commercially available wool staple fibers with an average fiber length of 38 mm; the tris (2-carboxyethyl) phosphine is from Shanghai Bide Pharmaceutical Technology Co., Ltd., CAS No.: 5961-85-3; the sodium carbonate / sodium bicarbonate buffer is from Shanghai Shangbao Biotechnology Co., Ltd., with a concentration of 0.05 mol / L and a pH value of 9.9; the chitosan quaternary ammonium salt is from Shanghai Macklin Biochemical Technology Co., Ltd., with a degree of substitution of 40%; the N-acetyl-L-cysteine is from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 616-91-1; the trifluoropropylmethylcyclotrisiloxane is from Alfa Aesar (China) Chemical Co., Ltd., CAS No.: 2374-14-3; the 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane is from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 3901-77-7; and the polytetrahydrofuran ether diol is from Shanghai Aladdin Biochemical Technology Co., Ltd., Mn = 2000.

[0174] Test Example

[0175] The bio-based composite fabric prepared in Examples 1-5 and Comparative Examples 1-2 is subjected to comprehensive performance testing. The specific test results are shown in Table 1:

[0176] Table 1

[0177]

[0178] The detection of each index in Table 1 is based on the following standards: the warmth retention rate is determined according to GB / T 11048-1989 “Textile Thermal Performance Test Method”; the light absorption and heat generation performance is represented by the temperature difference, and the test method is as follows: the bio-based composite fabric prepared in Examples 1-5 and Comparative Examples 1-2 is placed on a heat insulation table with the coated side facing up, and an infrared heating lamp is used to heat the bio-based composite fabric, with a heating time of 30 min. After heating, the surface temperature difference of the fabric before and after heating is tested, wherein the power of the infrared heating lamp is 500 W, the peak value is 4 μm, the distance between the infrared heating lamp and the bio-based composite fabric is 50 cm; the abrasion resistance is represented by the number of rubs, and is determined according to GB / T21196.2-2007 “Textile Fabric Abrasion Resistance Determination by the Martindale Method Part 2: Determination of Sample Breakage”.

[0179] According to the test results in Table 1, it can be seen that the composite fabric prepared in the present application has good low-temperature resistance and good abrasion resistance.

[0180] The application of nanometer far infrared ceramic powder in fabric finishing can endow the fabric with the performance of light absorption and heat generation, and improve the low temperature resistance of the fabric by using positive type warm keeping. The finishing liquid prepared in the application is formed by compounding mercapto chitosan quaternary ammonium salt / nanometer far infrared ceramic powder composite material with water. After finishing on the single layer blended fabric, the fabric can be endowed with the ability of light absorption and heat generation, and the warm keeping and low temperature resistance of the fabric can be improved. Moreover, after the single layer blended fabric is treated by a reducing agent, mercapto functional groups are formed. After the fabric is impregnated with the finishing agent and dried, the mercapto functional groups in the finishing liquid and the mercapto functional groups in the modified single layer blended fabric are oxidized by oxygen to form disulfide bonds, so that the functional components are fixed on the surface of the fabric and are not easy to fall off after washing. In the preparation of the outer fabric and the inner fabric in Comparative Example 1, no reducing agent and finishing liquid are impregnated, and the finishing liquid in Comparative Example 1 lacks the effect of improving the light absorption and heat generation performance of the fabric by mercapto chitosan quaternary ammonium salt / nanometer far infrared ceramic powder composite material, so the light absorption and heat generation performance of Comparative Example 1 is lower than that of the embodiment.

[0181] The polyurethane-based coating material prepared in the application has excellent wear resistance due to the addition of wear-resistant additives containing fluorosilicone rubber and silicon carbide. In Comparative Example 2, no wear-resistant additives are added in the preparation of the polyurethane-based coating material, and the wear-resistant filler nanometer silicon carbide lacks the effect of enhancing the wear resistance of the material, so the wear resistance of Comparative Example 2 is not as good as that of the embodiment.

[0182] Although the embodiments of the application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an anti-cold wear-resistant bio-based composite fabric, characterized in that, The method comprises the following steps: Step one, preparing an outer / inner layer composite fabric; Step (1), blending bio-based polytrimethylene terephthalate fibers and wool fibers to obtain blended yarns; weaving the blended yarns as warp and weft to obtain a single-layer blended fabric; immersing the single-layer blended fabric in a reducing agent, reacting, taking out after the reaction, washing, and drying to obtain a modified single-layer blended fabric; Step (2), immersing the modified single-layer blended fabric in a finishing liquid, taking out after the immersion, and drying to obtain an outer layer fabric and an inner layer fabric, respectively; The finishing liquid is prepared by the following steps: mixing the mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material with water to obtain the finishing liquid; Step (3), combining the outer layer fabric and the inner layer fabric to obtain an outer / inner layer composite fabric; Step two, coating a polyurethane-based coating material on the outer / inner layer composite fabric to form a coating layer, and baking to obtain a low-temperature-resistant and wear-resistant bio-based composite fabric; The polyurethane-based coating material is prepared by the following steps: S21, mixing trifluoropropylmethylcyclotrisiloxane and 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, adding a catalyst, and reacting at an elevated temperature; after the reaction is completed, an addition-type fluorosilicone rubber is obtained; S22, uniformly mixing the addition-type fluorosilicone rubber, 2-mercaptoethanol, a photoinitiator, and tetrahydrofuran, reacting, adding mercapto silicon carbide after the reaction is completed, and continuing to react; after the reaction is completed, rotary evaporation and drying are performed to obtain a wear-resistant additive; S23, mixing isophorone diisocyanate, polytetrahydrofuran ether diol, and a catalyst dibutyltin dilaurate, reacting, adding 1,4-butanediol and the wear-resistant additive after the reaction is completed, and continuing to react; after the reaction is completed, dilution is performed to obtain a polyurethane-based coating material.

2. A process for the preparation of a low temperature resistant wear resistant bio-based composite fabric according to claim 1, characterized in that, In the step of preparing the outer / inner layer composite fabric: In step (1), the mass ratio of the bio-based polytrimethylene terephthalate fiber and the wool fiber is 40-50:50-60; the yarn count of the blended yarn is 60-80S in English count; the gram weight of the single-layer blended fabric is 220-240 g / m 2 ; the bath ratio of the single-layer blended fabric to the reducing agent is 1:40-50; and the reaction condition is that the reaction is carried out at room temperature for 4-5 h. In step (2), the bath ratio of the modified single-layer blended fabric to the finishing liquid is 1:20-30; in the finishing liquid, the mass ratio of the mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material to water is 5-8:100; the padding conditions are: immersing for 20-30 min at room temperature, double padding, and the pick-up rate is 88-92%; the drying conditions are: drying for 24-30 h at room temperature in an air atmosphere.

3. The method for preparing a low-temperature resistant and wear-resistant bio-based composite fabric according to claim 1, characterized in that, In the step of preparing the outer / inner layer composite fabric, the reducing agent in step (1) is prepared by the following steps: uniformly mixing tris(2-carboxyethyl)phosphine, water, and ethanol, and adjusting the pH value to neutral to obtain the reducing agent; The mass ratio of tris(2-carboxyethyl)phosphine, water, and ethanol is 1:40-50:50-60.

4. The method for preparing a low-temperature resistant and wear-resistant bio-based composite fabric according to claim 1, characterized in that, In the step of preparing the outer / inner layer composite fabric, the mercapto chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material in step (2) is prepared by the following steps: S11, mixing amino nano far infrared ceramic powder, glutaraldehyde, and water, reacting, filtering after the reaction is completed, and washing to obtain an intermediate product; mixing the intermediate product, chitosan quaternary ammonium salt, and water, continuing to react, filtering after the reaction is completed, washing, and drying to obtain a chitosan quaternary ammonium salt / nano far infrared ceramic powder composite material; S12, the quaternary ammonium salt of chitosan / nano far infrared ceramic powder composite material, water, N-acetyl-L-cysteine, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide are mixed, a pH regulator is added to adjust the pH value, and then reaction is carried out; after the reaction is completed, purification is carried out to obtain the thiolated quaternary ammonium salt of chitosan / nano far infrared ceramic powder composite material.

5. A process for the preparation of a cryoresistant wear-resistant bio-based composite fabric according to claim 4, characterized in that, When the thiolated quaternary ammonium salt of chitosan / nano far infrared ceramic powder composite material in the step (2) is prepared, the following steps are carried out: In S11, the mass ratio of the amino nano far infrared ceramic powder, glutaraldehyde and water is 1:0.8-1:80-120; the reaction condition is that the reaction is carried out at room temperature for 3-4 h; the mass ratio of the intermediate product, the quaternary ammonium salt of chitosan and water is 1:4.5-5:100; the continuous reaction condition is that the reaction is continuously carried out at room temperature for 2-3 h; In S12, the mass ratio of the quaternary ammonium salt of chitosan / nano far infrared ceramic powder composite material, water, N-acetyl-L-cysteine and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide is 7:500-550:9.5-10:5.8-6; the reaction condition is that the reaction is carried out at room temperature for 3-4 h in a dark environment with a pH value of 5-5.

5.

6. The method for preparing a low-temperature resistant and wear-resistant bio-based composite fabric according to claim 1, characterized in that, In the step two, the coating thickness is 0.8-1 mm; the baking operation includes: pre-baking at a temperature of 80-90℃ for 15-20 min, and baking at a temperature of 100-110℃ for 3-4 min.

7. The method for preparing a low-temperature resistant and wear-resistant bio-based composite fabric according to claim 1, characterized in that, When the polyurethane-based coating material in the step two is prepared, the following steps are carried out: In S21, the mass ratio of trifluoropropylmethylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and a catalyst is 70-72:5.1-5.5:0.4-0.5; the reaction condition is that the reaction is carried out at a temperature of 120-130℃ for 1-3 h; In S22, the mass ratio of the addition type fluorosilicone rubber, 2-mercaptoethanol, mercapto silicon carbide, an initiator and tetrahydrofuran is 10-12:0.15:5-6:0.05-0.06:40-50; the reaction condition is that the reaction is carried out at room temperature for 5-10 min in an ultraviolet environment with a wavelength of 365 nm; the continuous reaction condition is that the reaction is continuously carried out at room temperature for 0.5-1 h in an ultraviolet environment with a wavelength of 365 nm.

8. The method for preparing a low-temperature resistant and wear-resistant bio-based composite fabric according to claim 1, characterized in that, When the polyurethane-based coating material in the step two is prepared, the following steps are carried out: In S23, the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether diol and 1,4-butanediol is 3:1-1.2:1.3-1.5; the amount of the catalyst dibutyltin dilaurate added is 0.5wt% of the polytetrahydrofuran ether diol; the amount of the wear-resistant additive added is 15-20wt% of the polyurethane-based coating material; the reaction condition is that the reaction is carried out at a temperature of 70-80℃ for 3-4 h in a nitrogen atmosphere; the continuous reaction condition is that the reaction is continuously carried out at a temperature of 75-85℃ for 2-3 h; the solid content of the polyurethane-based coating material is 30-35wt%.

9. An anti-low-temperature wear-resistant bio-based composite fabric prepared by the preparation method of the anti-low-temperature wear-resistant bio-based composite fabric according to any one of claims 1-8.

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