Thermal insulation fabric and method of making same

Abstract

The application discloses a kind of thermal insulation fabric and preparation method thereof, it is related to fabric technical field.The thermal insulation fabric prepared by the application is made of modified polyurethane, modified conjugated porous microspheres are obtained by wet spinning process Fiber is woven into fabric to obtain, the modified polyurethane is quaternary ammonium salt type polyurethane;The conjugated porous microspheres are with silica as template, triphenylamine-4,4',4"-triboron, 4,7-dibromo-2,1,3-benzothiadiazole, 3,5-dibromostyrene polymerization, then remove template, graft phosphite ester finally acidolysis obtained;The thermal insulation fabric prepared by the application has good thermal insulation, antibacterial, antioxidant performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fabrics, in particular to a thermal insulation fabric and a preparation method thereof. BACKGROUND

[0002] The advantage of polyurethane as a fabric lies in its excellent elasticity and deformation recovery capability, which can quickly rebound to the original state after stretching or bending, ensuring that the garment or product remains flat and wrinkle-free during dynamic use, especially suitable for tight-fitting sports wear, medical bandages and other scenarios with extremely high fit requirements; the thermal insulation fabric is a functional textile that effectively blocks heat transfer through special materials or structural design, its core function is to reduce the temperature influence of external high or low temperature environment on the wearer or covered object, and it is widely used in fire protection clothing, outdoor sports equipment, building insulation materials, automotive interiors and aerospace fields.

[0003] Polyurethane (PU) is the preferred material for thermal insulation fabric, which benefits from its unique microporous closed-cell structure, which can form a large number of stationary air layers inside the material, significantly reducing heat conduction and convection, while also having excellent flexibility, compression resistance and durability, adapting to complex shape processing requirements, and allowing density and thermal insulation performance to be adjusted through foaming process to achieve performance customization.

[0004] However, in practical applications, thermal insulation fabrics often face the dual challenges of microbial growth and oxidative aging. In high temperature and humidity environments, moisture and organic residues inside the fabric can accumulate, providing a breeding ground for bacteria and fungi, not only producing odors and causing skin allergies, but also possibly degrading the material structure and shortening the service life; at the same time, the urethane bonds and ether bonds in the polyurethane molecular chain are prone to chain scission reactions under long-term exposure to ultraviolet light, ozone or high-temperature oxidation environments, leading to material hardening, embrittlement or discoloration, and significant decreases in mechanical properties and thermal insulation efficiency, especially in outdoor equipment or automotive interiors that are used for long periods of time, the synergistic effect of sunlight radiation and oxidizing agents in the air accelerates material aging. In summary, polyurethane fabrics with high thermal insulation, antibacterial and antioxidant properties, through material modification and structural innovation, are continuously driving the technological upgrading of protective equipment, smart textiles and green buildings. SUMMARY

[0005] The purpose of the present application is to provide a thermal insulation fabric and a preparation method thereof to solve the problems in the prior art.

[0006] In order to solve the above technical problems, the present application provides the following technical solutions:

[0007] A preparation method of a thermal insulation fabric, comprising the following preparation steps:

[0008] (1) reacting 3-methylamino-1,2-propanediol and decyl bromide to obtain a diol monomer;

[0009] (2) reacting polytetrahydrofuran, isophorone diisocyanate, dihydric alcohol monomer, hydroxyethyl methacrylate and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxide to obtain modified polyurethane;

[0010] (3) reacting silica nanospheres, triphenylamine-4,4',4"-triboronic acid, 3,5-dibromostyrene and 4,7-dibromo-2,1,3-benzothiadiazole to obtain conjugated microspheres, and etching the conjugated microspheres with hydrofluoric acid to obtain conjugated porous microspheres;

[0011] (4) reacting the conjugated porous microspheres with dimethyl phosphite to obtain pre-modified conjugated porous microspheres, and acidolysis of the pre-modified conjugated porous microspheres to obtain modified conjugated porous microspheres;

[0012] (5) mixing the modified polyurethane, the modified conjugated porous microspheres, a photoinitiator and N,N-dimethylformamide to obtain a spinning solution, and wet spinning to obtain modified polyurethane fibers, and twisting and weaving the modified polyurethane fibers to prepare a plain fabric.

[0013] As an optimization, the preparation method of the dihydric alcohol monomer in step (1) is as follows: 3-methylamino-1,2-propanediol, decyl bromide and potassium carbonate are dissolved in acetonitrile at a molar ratio of 1:(1.2-1.4):(2.5-3.5), the mass of acetonitrile is 10-15 times the mass of potassium carbonate, the temperature is raised to 80-90°C for reflux reaction, the reaction progress is monitored by TLC (developing agent: V ethyl acetate: V methanol = 3:1), after the reaction is completed, the temperature is cooled to room temperature, and potassium carbonate is removed by filtration; the filtrate is concentrated under reduced pressure to obtain a crude product, which is distilled under reduced pressure at 40-50°C, recrystallized from 50-60°C ethanol, cooled to 0°C for crystallization, and filtered to obtain the dihydric alcohol monomer.

[0014] As an optimization, the preparation method of the modified polyurethane in step (2) is as follows: polytetrahydrofuran is dissolved in acetone, isophorone diisocyanate is added, dibutyltin dilaurate is added, and the reaction is carried out at 50-60°C for 2-3h, the temperature is raised to 60-70°C, the dihydric alcohol monomer is added and the reaction is continued for 1-2h, hydroxyethyl methacrylate is added and the reaction is carried out for 2-3h, 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxide is added, and the reaction is continued at 70-80°C for 6-8h to obtain the modified polyurethane.

[0015] As optimization, the molar ratio of polytetrahydrofuran, isophorone diisocyanate, dihydric alcohol monomer, hydroxyethyl methacrylate is 1: (2.0-2.5): (0.8-1.2): (0.25-0.35); the molar ratio of dihydric alcohol monomer, 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl is 1: (1.2-1.4); the mass of dibutyltin dilaurate is 0.001-0.002 times of the total mass of isophorone diisocyanate and polytetrahydrofuran; the mass of acetone is 10-15 times of the total mass of isophorone diisocyanate and polytetrahydrofuran.

[0016] As optimization, the preparation method of the conjugated porous microspheres in step (3) is as follows: the conjugated microspheres, hydrofluoric acid, methanol and pure water are mixed in a mass ratio of 1: (3-4): (10-15): (5-10) for 4-5 h to obtain the conjugated porous microspheres.

[0017] As optimization, the preparation method of the conjugated microspheres is as follows: the silica nanospheres, triphenylamine-4,4',4"-triboron, 3,5-dibromostyrene, 4,7-dibromo-2,1,3-benzothiadiazole, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution and tetrahydrofuran are refluxed at 70-80℃ for 8-10 h under nitrogen protection to obtain the conjugated microspheres.

[0018] As optimization, the mass ratio of the silica nanospheres, triphenylamine-4,4',4"-triboron, 4,7-dibromo-2,1,3-benzothiadiazole, 3,5-dibromostyrene, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution and tetrahydrofuran is 1: (0.1-0.2): (0.2-0.3): (0.1-0.2): (0.5-0.7): (2-3): (20-30).

[0019] As optimization, the preparation and method of the modified conjugated porous microspheres in step (4) are as follows: the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran are uniformly mixed, dimethyl phosphite is added, and the mixture is stirred at 30-40℃ for 8-10 h to obtain the pre-modified conjugated porous microspheres; the mass ratio of the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran and dimethyl phosphite is 1: (0.2-0.3): (0.01-0.02): (20-30): (0.2-0.3).

[0020] 1: (0.2-0.3): (0.01-0.02): (20-30): (0.2-0.3); the pre-modified conjugated porous microspheres and 1-3M hydrochloric acid solution are mixed in a mass ratio of 1: (10-20), the mixture is refluxed at 80-90℃ for 1-2 h to obtain the modified conjugated porous microspheres.

[0021] As optimization, the mass ratio of the modified polyurethane, the modified conjugated porous microspheres, the photoinitiator, and N,N-dimethylformamide in step (5) is 1:(0.1-0.2):(0.01-0.02):(5-6).

[0022] As optimization, the wet spinning process is as follows: a needle with a type number of 16G (an inner diameter of 1.15 mm and an outer diameter of 1.6 mm) is used, the advancing speed of the wet spinning device is set to 0.5 mm / s, the spinning solution is introduced into the coagulation bath (V 水 :V 乙醇 =7:3) through a rubber tube connected with the needle to be cooled and coagulated for 40-60 min, a 365 nm LED ultraviolet lamp with a power of 50 mW / cm 2 is arranged above the coagulation bath to perform light irradiation, and the distance between the light source and the coagulation bath is 15 cm.

[0023] The application further provides a thermal insulation fabric prepared by the preparation method of the thermal insulation fabric.

[0024] Compared with the prior art, the application has the following beneficial effects:

[0025] The thermal insulation fabric prepared by the application is prepared by weaving fibers obtained by a wet spinning process of modified polyurethane and modified conjugated porous microspheres, the modified polyurethane is a quaternary ammonium salt type polyurethane, and the conjugated porous microspheres are obtained by polymerizing triphenylamine-4,4',4"-triboron, 4,7-dibromo-2,1,3-benzothiadiazole, and 3,5-dibromostyrene with silica as a template, removing the template, grafting phosphite, and finally acidolysis.

[0026] Firstly, a dihydric alcohol containing a tertiary amine is added to the polymerization of the polyurethane as a chain extender, a hydroxyethyl methacrylate containing a double bond is used as an end-capping agent to cap the polyurethane, the bromomethyl of the polyurethane and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl react, and a dihydro tetramethyl pyrrole structure with an antioxidant function is introduced while generating a quaternary ammonium salt, so that the fabric can be endowed with good antibacterial and antioxidant functions at the same time;

[0027] Secondly, triphenylamine-4,4',4"-triboron, 3,5-dibromostyrene, and 4,7-dibromo-2,1,3-benzothiadiazole are coupled on the surface of silica to generate a conjugated polymer and introduce a vinyl group, and then the silica is removed by acid to obtain a porous conjugated microsphere, the still air in the internal pores of the microsphere can effectively block heat conduction and enhance the thermal insulation performance of the fabric, and the benzothiadiazole-triphenylamine conjugated skeleton can be used as a photosensitive group to generate singlet active oxygen under light irradiation to achieve a sterilization effect, so that the material is endowed with good antibacterial performance.

[0028] The phosphorus-hydrogenation reaction of the double bond and the phosphite on the porous conjugated microspheres, so that the phosphorus element with flame-retardant performance is loaded in the cavity structure, can endow the material with good flame-retardant performance, and the phosphoric acid ester is hydrolyzed into negatively charged phosphoric acid by acid;

[0029] Finally, the modified polyurethane and the modified conjugated porous microspheres are obtained by a wet spinning process to form a fabric, and when the modified polyurethane and the modified conjugated porous microspheres are blended to form a spinning solution, the positive charge of the quaternary ammonium salt on the polyurethane and the negative charge of the phosphoric acid on the conjugated porous microspheres interact through electrostatic attraction, so that the dispersibility of the microspheres in the polyurethane can be improved, and in the process of curing in the coagulation bath, the double bond at the end of the polyurethane is crosslinked by the ultraviolet light and the photoinitiator, so that the mechanical properties of the fiber are enhanced. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to 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.

[0031] The molecular weight of the polytetrahydrofuran in the following examples and comparative examples is 1000; the silica nanosphere particle size is 100 nm, which is purchased from Shanghai Bumi Applied Material Technology Co., Ltd.

[0032] Example 1:

[0033] A preparation method of a thermal insulation fabric, the preparation method of the thermal insulation fabric comprises the following preparation steps:

[0034] (1) 3-methylamino-1,2-propanediol, decyl bromide and potassium carbonate are dissolved in acetonitrile according to a molar ratio of 1:1.2:2.5, the mass of acetonitrile is 10 times the mass of potassium carbonate, and the reaction is refluxed at 90°C, the reaction progress is monitored by TLC (developing agent: V 乙酸乙酯 :V 甲醇 = 3:1), after the reaction is completed, it is cooled to room temperature, and the potassium carbonate is removed by filtration; the filtrate is concentrated under reduced pressure to obtain a crude product, which is distilled under reduced pressure at 50°C, recrystallized from 60°C ethanol, cooled to 0°C to crystallize, and filtered to obtain a diol monomer;

[0035] (2) polytetrahydrofuran is dissolved in acetone, isophorone diisocyanate is added, dibutyltin dilaurate is added, and the mixture is reacted at 60°C for 3h, then the temperature is raised to 70°C, dihydric alcohol monomer is added, and the reaction is continued for 2h, then hydroxyethyl methacrylate is added and the reaction is continued for 3h, then 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl is added, and the reaction is continued at 80°C for 8h, and then the modified polyurethane is obtained by precipitation with pure water, washing and drying; the molar ratio of polytetrahydrofuran, isophorone diisocyanate, dihydric alcohol monomer and hydroxyethyl methacrylate is 1:2.0:0.8:0.25; the molar ratio of dihydric alcohol monomer and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl is 1:1.2; the mass of dibutyltin dilaurate is 0.001 times the total mass of isophorone diisocyanate and polytetrahydrofuran; and the mass of acetone is 10 times the total mass of isophorone diisocyanate and polytetrahydrofuran;

[0036] (3) silica nanospheres, triphenylamine-4,4',4"-triboronic acid, 3,5-dibromostyrene, 4,7-dibromo-2,1,3-benzothiadiazole, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution and tetrahydrofuran are mixed under nitrogen protection, the temperature is raised to 80°C and refluxed for 10h, then the reaction is completed, the mixture is filtered and washed with acetone, chloroform, deionized water and methanol to obtain conjugated microspheres; the mass ratio of silica nanospheres, triphenylamine-4,4',4"-triboronic acid, 4,7-dibromo-2,1,3-benzothiadiazole, 3,5-dibromostyrene, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution and tetrahydrofuran is 1:0.1:0.2:0.1:0.5:2:20; the conjugated microspheres, hydrofluoric acid, methanol and pure water are mixed at a mass ratio of 1:3:10:5 for 5h, then the mixture is filtered and washed with acetone, chloroform, deionized water and methanol to obtain conjugated porous microspheres;

[0037] (4) the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran are mixed, dimethyl phosphite is added dropwise at a rate of 0.6mL / min, and the mixture is stirred at 40°C for 10h, then the mixture is filtered, washed and dried to obtain pre-modified conjugated porous microspheres; the mass ratio of the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran and dimethyl phosphite is 1:0.2:0.01:20:0.2; the pre-modified conjugated porous microspheres and 3M hydrochloric acid solution are mixed at a mass ratio of 1:10, the temperature is raised to 90°C and refluxed for 2h, then the mixture is filtered, washed and dried to obtain modified conjugated porous microspheres;

[0038] (5) ultrasonic mixing modified polyurethane, modified conjugated porous microspheres, photoinitiator 1-hydroxycyclohexyl phenyl ketone, N,N-dimethylformamide according to the mass ratio 1:0.1:0.01:5 to obtain a spinning solution, and then wet spinning to obtain modified polyurethane fibers; the wet spinning process is as follows: using a needle with a type of 16G (the inner diameter of the needle is 1.15 mm, and the outer diameter is 1.6 mm), setting the advancing speed of the wet spinning device to 0.5 mm / s, connecting the spinning solution to the needle through a rubber tube, and then leading the spinning solution to the coagulation bath (V 水 :V 乙醇 =7:3) to cool and coagulate for 60 min, setting a 365 nm LED ultraviolet lamp with a power of 50 mW / cm 2 above the coagulation bath to perform light irradiation, and the distance between the light source and the coagulation bath is 15 cm; twisting and weaving the modified polyurethane fibers to prepare a plain fabric.

[0039] Example 2

[0040] A preparation method of a thermal insulation fabric, the preparation method of the thermal insulation fabric comprises the following preparation steps:

[0041] (1) 3-methylamino-1,2-propanediol, decyl bromide, and potassium carbonate are dissolved in acetonitrile according to a molar ratio of 1:1.3:3, the mass of acetonitrile is 12 times the mass of potassium carbonate, the temperature is increased to 85°C to reflux, the reaction process is monitored by TLC (developing agent: V 乙酸乙酯 :V 甲醇 =3:1), after the reaction is completed, the temperature is cooled to room temperature, and potassium carbonate is removed by filtration; the filtrate is concentrated under reduced pressure to obtain a crude product, which is distilled under reduced pressure at 45°C, recrystallized from ethanol at 55°C, cooled to 0°C to crystallize, and then filtered to obtain a diol monomer;

[0042] (2) polytetrahydrofuran is dissolved in acetone, then isophorone diisocyanate is added, dibutyltin dilaurate is added, the temperature is increased to 55°C to react for 2.5 h, the temperature is increased to 65°C, the diol monomer is added to continue to react for 1.5 h, then hydroxyethyl methacrylate is added to react for 2.5 h, 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl is added, and the temperature is increased to 75°C to continue to react for 7 h, then the modified polyurethane is precipitated and washed with pure water and dried; the molar ratio of polytetrahydrofuran, isophorone diisocyanate, diol monomer, and hydroxyethyl methacrylate is 1:2.3:1:0.3; the molar ratio of the diol monomer and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl is 1:1.3; the mass of dibutyltin dilaurate is 0.001 times the total mass of isophorone diisocyanate and polytetrahydrofuran; and the mass of acetone is 13 times the total mass of isophorone diisocyanate and polytetrahydrofuran;

[0043] (3) mixing silica nanospheres, triphenylamine-4, 4', 4"-triboronic acid, 3, 5-dibromostyrene, 4, 7-dibromo-2, 1, 3-benzothiadiazole, tetrakis (triphenylphosphine) palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran under nitrogen protection, heating to 75℃ and refluxing for 9h, after the reaction is completed, filtering and washing with acetone, chloroform, deionized water and methanol to obtain conjugated microspheres; the mass ratio of silica nanospheres, triphenylamine-4, 4', 4"-triboronic acid, 4, 7-dibromo-2, 1, 3-benzothiadiazole, 3, 5-dibromostyrene, tetrakis (triphenylphosphine) palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran is 1:0.15:0.25:0.15:0.6:2.5:25; mixing conjugated microspheres, hydrofluoric acid, methanol and pure water according to a mass ratio of 1:3.5:13:7 for 4.5h, filtering and washing with acetone, chloroform, deionized water and methanol to obtain conjugated porous microspheres;

[0044] (4) mixing conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran, adding dimethyl phosphite dropwise at a rate of 0.5mL / min, stirring at 35℃ for 9h, filtering, washing and drying to obtain pre-modified conjugated porous microspheres; the mass ratio of conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran and dimethyl phosphite is 1:0.25:0.015:25:0.25; mixing pre-modified conjugated porous microspheres and 2M hydrochloric acid solution according to a mass ratio of 1:15, heating to 85℃ and refluxing for 5.5h, filtering, washing and drying to obtain modified conjugated porous microspheres;

[0045] (5) mixing modified polyurethane, modified conjugated porous microspheres, photoinitiator 1-hydroxycyclohexyl phenyl ketone and N, N-dimethylformamide according to a mass ratio of 1:0.15:0.015:5.5 to obtain a spinning solution, and wet spinning the spinning solution to obtain modified polyurethane fibers; the wet spinning process is as follows: using a needle with a type of 16G (the inner diameter of the needle is 1.15mm, and the outer diameter is 1.6mm), setting the advancing speed of the wet spinning device to 0.5mm / s, connecting a rubber tube with the needle to guide the spinning solution out to the coagulation bath (V 水 :V 乙醇 =7:3) to cool and coagulate for 50min, setting a 365nm LED ultraviolet lamp above the coagulation bath for light irradiation, and the distance between the light source and the coagulation bath is 15cm, twisting and weaving the modified polyurethane fibers to prepare a plain fabric.

[0046] Example 3:

[0047] A preparation method of a thermal insulation fabric, the preparation method of the thermal insulation fabric comprises the following preparation steps:

[0048] (1) 3-methylamino-1,2-propanediol, decyl bromide, potassium carbonate were dissolved in acetonitrile according to the molar ratio of 1:1.4:3.5, the mass of acetonitrile was 15 times of the mass of potassium carbonate, and the reaction was carried out at 80°C under reflux, the reaction process was monitored by TLC (developing agent: V 乙酸乙酯 :V 甲醇 =3:1), after the reaction was completed, it was cooled to room temperature, and potassium carbonate was removed by filtration; the filtrate was concentrated under reduced pressure to obtain a crude product, which was distilled under reduced pressure at 40°C, recrystallized from ethanol at 50°C, cooled to 0°C to crystallize, and filtered to obtain a diol monomer;

[0049] (2) polytetrahydrofuran was dissolved in acetone, isophorone diisocyanate was added, and dibutyltin dilaurate was added, and the reaction was carried out at 50°C for 2h, then the temperature was raised to 60°C, the diol monomer was added and the reaction was continued for 1h, then hydroxyethyl methacrylate was added and the reaction was continued for 2h, then 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl was added, and the reaction was continued at 70°C for 6h, and then the modified polyurethane was obtained by precipitation and washing with pure water and drying; the molar ratio of polytetrahydrofuran, isophorone diisocyanate, diol monomer, and hydroxyethyl methacrylate was 1:2.5:1.2:0.35; the molar ratio of diol monomer and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl was 1:1.4; the mass of dibutyltin dilaurate was 0.002 times of the total mass of isophorone diisocyanate and polytetrahydrofuran; the mass of acetone was 15 times of the total mass of isophorone diisocyanate and polytetrahydrofuran;

[0050] (3) silica nanospheres, triphenylamine-4,4',4"-triboronic, 3,5-dibromostyrene, 4,7-dibromo-2,1,3-benzothiadiazole, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran were mixed under nitrogen protection, and the reaction was carried out at 70°C under reflux for 8h, then the reaction was completed, and the conjugated microspheres were obtained by filtration and washing with acetone, chloroform, deionized water, and methanol and drying; the mass ratio of silica nanospheres, triphenylamine-4,4',4"-triboronic, 4,7-dibromo-2,1,3-benzothiadiazole, 3,5-dibromostyrene, tetrakis(triphenylphosphine)palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran was 1:0.2:0.3:0.2:0.7:3:30; the conjugated porous microspheres were obtained by mixing the conjugated microspheres, hydrofluoric acid, methanol, and pure water according to the mass ratio of 1:4:15:10 for 4h, and then filtering and washing with acetone, chloroform, deionized water, and methanol and drying;

[0051] (4) mixing the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide and tetrahydrofuran uniformly, adding dimethyl phosphite dropwise at a rate of 0.4 mL / min, stirring at 30℃ for 8h, and then filtering, washing and drying to obtain pre-modified conjugated porous microspheres; the mass ratio of the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran and dimethyl phosphite is 1:0.3:0.02:30:0.3; mixing the pre-modified conjugated porous microspheres and 1M hydrochloric acid solution according to a mass ratio of 1:20, heating to 80℃ to reflux for 1h, and then filtering, washing and drying to obtain modified conjugated porous microspheres;

[0052] (5) mixing the modified polyurethane, modified conjugated porous microspheres, photoinitiator 1-hydroxycyclohexyl phenyl ketone and N,N-dimethylformamide according to a mass ratio of 1:0.2:0.02:6 to obtain a spinning solution by ultrasonic mixing, and then obtaining modified polyurethane fibers by wet spinning; the wet spinning process is as follows: using a needle with a type number of 16G (the inner diameter of the needle is 1.15mm and the outer diameter is 1.6mm), setting the advancing speed of the wet spinning device to 0.5mm / s, introducing the spinning solution into a coagulation bath (V 水 :V 乙醇 =7:3) through a rubber tube connected with the needle to cool and coagulate for 40min, setting a 365nm LED ultraviolet lamp with a power of 50mW / cm 2 above the coagulation bath to perform light irradiation, the distance between the light source and the coagulation bath is 15cm, and then twisting and weaving the modified polyurethane fibers to prepare a plain fabric.

[0053] Comparative Example 1

[0054] The preparation method of the thermal insulation fabric of Comparative Example 1 is different from that of Example 2 in that it does not contain 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl, and specifically, step (2) is modified as follows: dissolving polytetrahydrofuran in acetone, then adding to isophorone diisocyanate, adding dibutyltin dilaurate, reacting at 55℃ for 2.5h, increasing the temperature to 65℃, adding a dihydric alcohol monomer to continue reacting for 1.5h, then adding hydroxyethyl methacrylate to react for 2.5h, and then precipitating, washing and drying to obtain modified polyurethane; the remaining steps are the same as those of Example 2.

[0055] Comparative Example 2

[0056] The preparation method of the thermal insulation fabric of Comparative Example 2 is different from that of Example 2 in that it does not contain modified conjugated porous microspheres, specifically: step (5) is modified as follows: the modified polyurethane, a photoinitiator 1-hydroxycyclohexyl phenyl ketone, and N,N-dimethylformamide are ultrasonically mixed at a mass ratio of 1:0.015:5.5 to obtain a spinning solution, and the modified polyurethane fiber is obtained by wet spinning; the wet spinning process is as follows: a needle with a type number of 16G (a needle inner diameter of 1.15 mm and a needle outer diameter of 1.6 mm) is used, the advancing speed of the wet spinning device is set to 0.5 mm / s, the spinning solution is introduced into a coagulation bath (V 水 :V 乙醇 = 7:3) through a rubber tube connected to the needle to cool and coagulate for 50 min, a 365 nm LED ultraviolet lamp is arranged above the coagulation bath for light irradiation, the light source is 15 cm away from the coagulation bath, and the modified polyurethane fiber is prepared into a plain fabric through twisting and weaving. The remaining steps are the same as those of Example 2.

[0057] Comparative Example 3:

[0058] The preparation method of the thermal insulation fabric of Comparative Example 3 is different from that of Example 2 in that it does not contain a photoinitiator; specifically, step (5) is modified as follows: the modified polyurethane, conjugated porous microspheres, and N,N-dimethylformamide are ultrasonically mixed at a mass ratio of 1:0.15:5.5 to obtain a spinning solution, and the modified polyurethane fiber is obtained by wet spinning; the wet spinning process is as follows: a needle with a type number of 16G (a needle inner diameter of 1.15 mm and a needle outer diameter of 1.6 mm) is used, the advancing speed of the wet spinning device is set to 0.5 mm / s, the spinning solution is introduced into a coagulation bath (V 水 :V 乙醇 = 7:3) through a rubber tube connected to the needle to cool and coagulate for 50 min, a 365 nm LED ultraviolet lamp is arranged above the coagulation bath for light irradiation, the light source is 15 cm away from the coagulation bath, and the modified polyurethane fiber is prepared into a plain fabric through twisting and weaving. The remaining steps are the same as those of Example 2.

[0059] Test Example 1:

[0060] Test of antibacterial performance:

[0061] Test method: The modified polyurethane fibers prepared in the examples and comparative examples are tested for antibacterial rate according to the antibacterial test method specified in GB / T20944.3-2008 “Evaluation of the antibacterial performance of textiles Part 3: shaking method”; the experimental bacteria are Staphylococcus aureus, the weight of the cut sample is 0.75 g, and a white light lamp with a power of 40 mWcm -2 is arranged above the sample. The results are shown in Table 1.

[0062] Table 1

[0063] Antibacterial rate (%) Antibacterial rate (%) Example 1 97.8 Comparative Example 1 82.3 Example 2 98.2 Comparative Example 2 85.7 Example 3 98.5 Comparative Example 3 92.4

[0064] From the experimental data comparison of examples 1-3 and comparative examples 1-3 in table 1, it can be found that the material prepared by the present application has good antibacterial performance.

[0065] The antibacterial performance of examples 1-3 is better than that of comparative examples 1-2, which shows that firstly, the dihydric alcohol containing tertiary amine is added as a chain extender to the polymerization of polyurethane, then the hydroxyethyl methacrylate containing double bond is used as a capping agent to cap the polyurethane, the bromomethyl of the polyurethane and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxyl react to generate quaternary ammonium salt, which endows the fabric with good antibacterial function; secondly, the triphenylamine-4,4',4"-triboron, 3,5-dibromostyrene and 4,7-dibromo-2,1,3-benzothiadiazole are coupled on the surface of silica to generate a conjugated polymer, and the benzothiadiazole-triphenylamine conjugated skeleton is used as a photosensitive group which can generate singlet active oxygen under light to achieve the effect of sterilization, thereby endowing the material with good antibacterial performance.

[0066] Test example 2:

[0067] Test method: the tensile properties of the modified polyurethane fibers prepared in examples and comparative examples were tested according to the standard of ASTM D3822; the test length was 20 mm and the tensile speed was 100 mm / min. The results are shown in table 2.

[0068] Test method: the tensile properties of the modified polyurethane fibers prepared in examples and comparative examples were tested according to the standard of ASTM D3822; the test length was 20 mm and the tensile speed was 100 mm / min. The results are shown in table 2.

[0069] Test method: the tensile properties of the modified polyurethane fibers prepared in examples and comparative examples were tested according to the standard of ASTM D3822; the test length was 20 mm and the tensile speed was 100 mm / min. The results are shown in table 2.

[0070] Test method: the tensile properties of the modified polyurethane fibers prepared in examples and comparative examples were tested according to the standard of ASTM D3822; the test length was 20 mm and the tensile speed was 100 mm / min. The results are shown in table 2.

[0071] Table 2

[0072] Breaking strength (CN) Breaking strength retention rate (%) Example 1 279 85.4 Example 2 284 87.2 Example 3 308 87.9 Comparative Example 1 271 58.9 Comparative Example 2 204 75.8 Comparative Example 3 227 83.3

[0073] From the experimental data comparison of examples 1-3 and comparative examples 1-3 in table 2, it can be found that the material prepared by the present application has good mechanical properties and anti-aging performance.

[0074] The mechanical properties of Examples 1-3 are better than those of the comparative examples, and the anti-aging properties of Examples 1-3 are better than those of the comparative examples; it is shown that first, the dihydric alcohol containing a tertiary amine is added as a chain extender to the polymerization of the polyurethane, then the hydroxyethyl methacrylate containing a double bond is used as a capping agent to cap the polyurethane, the bromomethyl of the polyurethane and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrole-1-oxyl react, and the dihydrotetramethylpyrrole structure with antioxidant function is introduced, which can impart good antioxidant function to the fabric. Finally, the modified polyurethane and the modified conjugated porous microspheres are obtained by a wet spinning process to form fibers, and then the fibers are woven into a fabric, the modified polyurethane and the modified conjugated porous microspheres are blended to form a spinning solution, and in the process of solidification in the coagulation bath, the double bond on the end of the polyurethane is crosslinked by the ultraviolet light and the photoinitiator, and the mechanical properties of the fiber are enhanced.

[0075] Test Example 3:

[0076] Test of thermal insulation performance:

[0077] Test method: the modified polyurethane fibers prepared in the examples and the comparative examples are woven into plain fabrics, the warp and weft density is 20x20 roots / cm, and the fabric size is 5x5x0.5cm 3 , and the thermal conductivity is tested by using a Hot Disk thermal conductivity instrument. The test results are shown in Table 3.

[0078] Table 3

[0079] Thermal conductivity (W / m-K) Thermal conductivity (W / m-K) Example 1 0.110 Comparative Example 1 0.117 Example 2 0.107 Comparative Example 2 0.135 Example 3 0.105 Comparative Example 3 0.121

[0080] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 3, it can be found that the material prepared by the present application has good thermal insulation performance; the thermal conductivity of Examples 1-3 is less than that of the comparative examples; it is shown that the conjugated polymer is generated on the surface of the silica by coupling reaction of triphenylamine-4,4',4"-triboron, 3,5-dibromostyrene and 4,7-dibromo-2,1,3-benzothiadiazole, and vinyl is introduced; and the porous conjugated microspheres can be obtained by removing the silica through acid, and the still air in the internal pores of the microspheres can effectively block heat conduction and enhance the thermal insulation performance of the fabric.

[0081] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the examples should be regarded as exemplary and non-limiting in any respect, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application. Any mark in the claims should not be regarded as limiting the involved claims.

Claims

1. A method of making a thermal insulation fabric, characterized in that, The preparation steps include: (1) reacting 3-methylamino-1,2-propanediol and decyl bromide to obtain a diol monomer; (2) reacting polytetrahydrofuran, isophorone diisocyanate, the diol monomer, hydroxyethyl methacrylate and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxide to obtain a modified polyurethane containing a dihydro tetramethyl pyrrole structure; (3) reacting silica nanospheres, triphenylamine-4,4',4"-triboron, 3,5-dibromostyrene and 4,7-dibromo-2,1,3-benzothiadiazole to obtain conjugated microspheres with a benzothiadiazole-triphenylamine conjugated skeleton; etching the conjugated microspheres with hydrofluoric acid to obtain conjugated porous microspheres; (4) reacting the conjugated porous microspheres with dimethyl phosphite to obtain pre-modified conjugated porous microspheres; acidolysis of the pre-modified conjugated porous microspheres to obtain modified conjugated porous microspheres; (5) mixing the modified polyurethane, the modified conjugated porous microspheres, a photoinitiator and N,N-dimethylformamide to obtain a spinning solution; wet spinning to obtain a modified polyurethane fiber; twisting and weaving the modified polyurethane fiber to prepare a fabric.

2. The method of claim 1, wherein the thermal insulation fabric is prepared by the steps of: The diol monomer is prepared by dissolving 3-methylamino-1,2-propanediol, decyl bromide and potassium carbonate in acetonitrile in a molar ratio of 1:(1.2-1.4):(2.5-3.5), wherein the mass of acetonitrile is 10-15 times the mass of potassium carbonate, and the reaction is carried out at 80-90°C under reflux.

3. The method of claim 1, wherein the thermal insulation fabric is prepared by the steps of: The modified polyurethane is prepared by dissolving polytetrahydrofuran in acetone, adding isophorone diisocyanate, adding dibutyltin dilaurate, and reacting at 50-60°C for 2-3h, then increasing the temperature to 60-70°C, adding the diol monomer and continuing to react for 1-2h, then adding hydroxyethyl methacrylate and reacting for 2-3h, then adding 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxide and continuing to react at 70-80°C for 6-8h to obtain the modified polyurethane.

4. The method of claim 3, wherein the heat-insulating fabric is prepared by the steps of: The molar ratio of polytetrahydrofuran, isophorone diisocyanate, the diol monomer and hydroxyethyl methacrylate is 1:(2.0-2.5):(0.8-1.2):(0.25-0.35); the molar ratio of the diol monomer and 3-bromomethyl-2,5-dihydro-2,2,5,5-tetramethyl-1H-pyrrol-1-oxide is 1:(1.2-1.4); the mass of dibutyltin dilaurate is 0.001-0.002 times the total mass of isophorone diisocyanate and polytetrahydrofuran; and the mass of acetone is 10-15 times the total mass of isophorone diisocyanate and polytetrahydrofuran.

5. The method of claim 1, wherein the thermal insulation fabric is prepared by the steps of: The conjugated porous microspheres are prepared by mixing the conjugated microspheres, hydrofluoric acid, methanol and pure water in a mass ratio of 1:(3-4):(10-15):(5-10) for 4-5h to obtain the conjugated porous microspheres.

6. The method of claim 5, wherein the heat-protective fabric is prepared by the steps of: The preparation method of the conjugated microspheres is as follows: under nitrogen protection, the silica nanospheres, triphenylamine-4, 4', 4"-triboron, 3, 5-dibromostyrene, 4, 7-dibromo-2, 1, 3-benzothiadiazole, tetrakis (triphenylphosphine) palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran are mixed and heated to 70-80℃ to reflux for 8-10h to obtain the conjugated microspheres.

7. The method of claim 6, wherein the method further comprises the step of applying a coating to the surface of the fabric. The mass ratio of the silica nanospheres, triphenylamine-4, 4', 4"-triboron, 4, 7-dibromo-2, 1, 3-benzothiadiazole, 3, 5-dibromostyrene, tetrakis (triphenylphosphine) palladium, 10wt% potassium carbonate aqueous solution, tetrahydrofuran is 1: (0.1-0.2) : (0.2-0.3) : (0.1-0.2) : (0.5-0.7) : (2-3) : (20-30).

8. The method of claim 1, wherein the thermal insulation fabric is prepared by the steps of: The preparation method of the modified conjugated porous microspheres in step (4) is as follows: the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran are uniformly mixed, dimethyl phosphite is added, and after stirring at 30-40℃ for 8-10h, the pre-modified conjugated porous microspheres are obtained; the mass ratio of the conjugated porous microspheres, potassium carbonate, tetrabutylammonium bromide, tetrahydrofuran, dimethyl phosphite is 1: (0.2-0.3) : (0.01-0.02) : (20-30) : (0.2-0.3) ; the pre-modified conjugated porous microspheres and 1-3M hydrochloric acid solution are mixed in a mass ratio of 1: (10-20), heated to 80-90℃ to reflux for 1-2h to obtain the modified conjugated porous microspheres.

9. The method of claim 1, wherein the thermal insulation fabric is prepared by the steps of: The mass ratio of the modified polyurethane, modified conjugated porous microspheres, photoinitiator, N, N-dimethylformamide in step (5) is 1: (0.1-0.2) : (0.01-0.02) : (5-6) ; the coagulation bath in the wet spinning process is provided with ultraviolet light.

10. A thermal insulation fabric prepared by the preparation method of the thermal insulation fabric according to any one of claims 1-9.