CN116005465A - A method for preparing puncture-proof, strong acid and alkali resistant aramid fiber composite fabric - Google Patents

Abstract

The invention discloses a method for preparing a puncture-resistant, strong acid and alkali resistant aramid fiber composite fabric, which comprises the following steps: spreading a composite coating solution on the aramid fiber fabric and drying to obtain the aramid fiber composite fabric. The preparation method of the composite coating solution comprises the following steps: uniformly mixing the inorganic particles and absolute ethanol to obtain a solution A; under stirring conditions, uniformly mixing the solution A and ammonia water to obtain a solution B; adding Perfluorooctyltriethoxysilane, stirred at 40-60°C for 4-12 hours, cooled to room temperature, washed, dried to obtain modified inorganic nanoparticles, and added modified inorganic nanoparticles to solution C under stirring conditions , stirred at 40-100°C for 20-25 hours to obtain a composite coating solution, and the aramid fiber fabric can be reinforced with the composite coating solution of the present invention, which can simultaneously have superhydrophobicity, puncture resistance and strong acid and alkali resistance, and the superhydrophobic composite coating Has excellent mechanical stability and chemical robustness.

Description

A method for preparing puncture-proof, strong acid and alkali resistant aramid fiber composite fabric

technical field

The invention belongs to the technical field of textile materials, and in particular relates to a method for preparing a puncture-proof and strong acid-base resistant aramid fiber composite fabric.

Background technique

Medical, military, firefighting and other chemical personnel require special levels of protection when dealing with chemical and other threats in many unique environments. Due to the huge potential danger in the environment, it is necessary to wear protective clothing to protect the whole or a certain part of the human body, avoiding the threat of various harmful gases, liquids, chemicals or sharp knives, so as to effectively protect the human body from sharp knives, etc. damage and reduce the risk of irreversible damage or disease to the skin, etc. Therefore, the development of composite materials that are superhydrophobic, resistant to strong acid and alkali corrosion, and puncture resistant has very high practical value in the fields of fire protection, chemical industry, and personal protection.

At present, the research on improving the anti-stab performance of fabrics mainly focuses on the resin coating and impregnation of fabrics with shear thickening solution. However, the hydrophilic groups on the surface of the coating can maintain firm contact with liquids and accelerate surface corrosion, which greatly limits its application range. In order to make the fabric have acid and alkali corrosion resistance under the premise of excellent puncture resistance, one of the effective strategies is to construct a superhydrophobic surface to control surface wettability. In recent years, superhydrophobic surfaces have been extensively researched and designed due to their unique anti-adhesion properties. However, due to their complex morphology, most of the preparation processes used are relatively complicated, and their mechanical durability and chemical stability are poor. limit its practical application.

Contents of the invention

Aiming at the deficiencies in the prior art, the object of the present invention is to provide a preparation method of a composite coating solution. The preparation method first adopts a chemical grafting method, and uses a silane coupling agent to modify silica nanoparticles to obtain an improved Then use DMF to dissolve thermoplastic polyurethane (TPU) to a certain concentration; then disperse the modified inorganic nanoparticles into the uniformly dissolved TPU to obtain a TPU with excellent mechanical properties, superhydrophobicity and acid and alkali resistance. Composite coating solution.

Another object of the present invention is to provide the composite coating solution obtained by the above preparation method.

Another object of the present invention is to provide a method for preparing a puncture-resistant, strong acid and alkali resistant aramid fiber composite fabric, which is compounded with the aramid fiber fabric by a scraping method.

Another object of the present invention is to provide the aramid composite fabric obtained by the above method.

The purpose of the present invention is achieved through the following technical solutions.

A preparation method of composite coating solution, comprising the following steps:

1) Mix the inorganic particles and absolute ethanol uniformly to obtain solution A, and under stirring conditions, mix the solution A and ammonia water uniformly to obtain solution B, wherein the inorganic particles include silica nanoparticles, and the inorganic particles The ratio of the parts by mass, the parts by volume of absolute ethanol and the parts by volume of the ammonia water is (1～10): (20～80): (4～20), and the unit of the said parts by mass is g , the unit of said parts by volume is mL;

In the step 1), the inorganic particles also include silicon carbide nanoparticles, and the ratio of the silicon dioxide nanoparticles to silicon carbide nanoparticles is (1-40): (1-10 ).

In the step 1), the concentration of the ammonia water is 1-10wt%.

In the step 1), the particle size of the silicon dioxide nanoparticles is 12-600 nm, and the particle size of the silicon carbide nanoparticles is 40-600 nm.

In the step 1), the method for uniformly mixing the inorganic particles and absolute ethanol is: mixing the inorganic particles and absolute ethanol, and ultrasonicating.

2) Add perfluorooctyltriethoxysilane (PFOTS) to the solution B, stir at 40-60°C for 4-12 hours, cool to room temperature, wash, and dry to obtain modified inorganic nanoparticles, wherein the The ratio of the mass fraction of the inorganic particles to the volume fraction of the perfluorooctyltriethoxysilane is (1-10): (0.4-3);

In the step 2), the washing is carried out alternately with absolute ethanol and distilled water.

In the step 2), the drying temperature is 50-130° C., and the drying time is at least 6 hours.

3) Under stirring conditions, add modified inorganic nanoparticles to solution C, and stir at 40-100° C. for 20-25 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) is dissolved in dimethylformamide ( Form the solution C in DMF), in parts by mass, the ratio of the thermoplastic polyurethane and dimethylformamide is 2:12, in parts by mass, the ratio of the modified inorganic nanoparticles and solution C For (0.75～3):14;

In the step 3), the stirring speed at 40-100° C. is 100-500 r/min.

In the step 3), thermoplastic polyurethane (TPU) and dimethylformamide (DMF) are mixed, and stirred at 50-100° C. for 6-8 hours to obtain the solution C.

In the above technical solution, the rotational speed of stirring after mixing thermoplastic polyurethane (TPU) and dimethylformamide (DMF) is 100-600 r/min.

The composite coating solution obtained by the above-mentioned preparation method.

A method for preparing a puncture-proof, strong acid and alkali resistant aramid composite fabric, comprising the following steps: spreading the composite coating solution on the aramid fabric and drying to obtain the aramid composite fabric.

In the above technical solution, the spreading method is doctor blade coating.

The aramid fiber composite fabric obtained by the above method.

The application of the above-mentioned composite coating solution in improving the anti-puncture performance/strong acid and alkali resistance performance/hydrophobic performance of fabrics.

In the above technical solution, the material of the fabric is aramid fiber, polyimide, ultra-high molecular weight polyethylene with an average weight greater than 3 million, polyparaphenylene benzobisoxazole or polyester.

The aramid fiber fabric reinforced with the composite coating solution prepared by the invention can simultaneously have superhydrophobicity, puncture resistance and strong acid and alkali resistance, and has excellent mechanical stability and chemical robustness. In addition, the preparation method is simple and safe .

Description of drawings

Fig. 1 is the SEM of (a) aramid fiber fabric and (b) the obtained aramid fiber composite fabric prepared in embodiment 3;

Fig. 2 is (a) aramid fiber fabric and (b) liquid drop photo on the surface of the aramid fiber composite fabric prepared in embodiment 3;

Fig. 3 is the photo of (a) aramid fiber fabric and (b) embodiment 3 preparation gained aramid fiber composite fabric self-cleaning process;

Fig. 4 is the change curve of contact angle and rolling angle during ten cycles of abrasion of the aramid composite fabric sandpaper prepared in embodiment 3;

Fig. 5 shows the curves of the aramid composite fabric, TPU coated aramid fabric and aramid fabric (blank) (a) cone force value-puncture displacement in the process of cone piercing and (b) maximum cone piercing displacement prepared in Examples 1 to 4 Average value of puncture force;

Figure 6 shows the obtained aramid composite fabric, TPU coated aramid fabric and aramid fabric (blank) prepared in Examples 1-4

(a) The curve of the stab force value-puncture displacement during the stabbing process and (b) the average value of the maximum stabbing force;

Figure 7 is the obtained aramid composite fabric, TPU coated aramid fabric and aramid fabric (blank) prepared in Examples 5-8

(a) The curve of knife penetration force value-puncture displacement during the cone piercing process and (b) the average value of the maximum cone piercing force;

Figure 8 is the weight loss rate of the aramid fabric and the aramid composite fabric prepared in Example 3 at different pH values (a) when soaked for 120 hours and (b) the hydrophobic angle during the 120h soak;

Fig. 9 is the strong acid and alkali resistance effect diagram of the aramid composite fabric prepared in Example 3, wherein, a is the photos when the aramid composite fabric is dripped with sodium hydroxide aqueous solution droplets for 0, 20, 40 and 60 minutes from left to right; b From left to right are photos of the aramid composite fabric dripping with sulfuric acid droplets for 0, 20, 40 and 60 min.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with specific embodiments.

The 1H, 1H, 2H, 2H perfluorododecyltriethoxysilane (PFOTS, 97%) used in the embodiment was purchased from Aladdin, and the particle diameter was 20nm silica nanoparticles (Degussa ( China) Investment Co., Ltd.), thermoplastic polyurethane with a weight average molecular weight of 420,000 (Suzhou Xizhen Plastic Co., Ltd., China), N,N-dimethylformamide (DMF) (Tianjin Jiangtian Chemical Technology Co., Ltd.), aramid The fabric (weight: 200g/square meter, thickness: 0.32mm, the warp and weft density of the aramid fabric is 60 yarns/10cm, and the yarn fineness of the fabric is 1500 denier) is produced by Yixing Carbon Technology Co., Ltd. supply. Deionized water, absolute ethanol 99.7%, sodium hydroxide (96.0%), and sulfuric acid (98%) were obtained from Sinopharm Chemical Reagent Co., Ltd. (China). Silicon carbide nanoparticles with a particle size of 40 nm were purchased from Tianjin Jiangtian Chemical Technology Co., Ltd.

Example 1

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A. Under stirring conditions, mix solution A with a concentration of 4.6wt % ammonia water was mixed, stirred for 0.5h until uniformly mixed to obtain solution B, wherein the ratio of the mass fraction of silica nanoparticles, the volume fraction of absolute ethanol and the volume fraction of ammonia water was 3:80:16, The unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , drying at 60° C. for 12 hours to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 0.75:14 in parts by mass.

Example 2

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A. Under stirring conditions, mix solution A with a concentration of 4.6wt % ammonia water was mixed, stirred for 0.5h until uniformly mixed to obtain solution B, wherein the ratio of the mass fraction of silica nanoparticles, the volume fraction of absolute ethanol and the volume fraction of ammonia water was 3:80:16, The unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , drying at 60° C. for 12 hours to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 1:14 in parts by mass.

Example 3

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A. Under stirring conditions, mix solution A with a concentration of 4.6wt % ammonia water was mixed, stirred for 0.5h until uniformly mixed to obtain solution B, wherein the ratio of the mass fraction of silica nanoparticles, the volume fraction of absolute ethanol and the volume fraction of ammonia water was 3:80:16, The unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , drying at 60° C. for 12 hours to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 1.25:14 in parts by mass.

Example 4

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A. Under stirring conditions, mix solution A with a concentration of 4.6wt % ammonia water was mixed, stirred for 0.5h until uniformly mixed to obtain solution B, wherein the ratio of the mass fraction of silica nanoparticles, the volume fraction of absolute ethanol and the volume fraction of ammonia water was 3:80:16, The unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , drying at 60° C. for 12 hours to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 1.5:14 in parts by mass.

Example 5

A method for preparing a composite coating solution, comprising the following steps: 1) at a room temperature of 20 to 25°C, mixing silicon dioxide nanoparticles with a particle diameter of 20nm, silicon carbide nanoparticles with a particle diameter of 40nm and absolute ethanol , sonicate for 0.5h until uniformly mixed to obtain solution A, under stirring conditions, mix solution A with ammonia water with a concentration of 4.6wt%, and stir for 0.5h until uniformly mixed to obtain solution B, wherein the mass fraction of silicon carbide nanoparticles , The ratio of the mass fraction of silica nanoparticles, the volume fraction of absolute ethanol and the volume fraction of ammonia water is 3:3:80:16, the unit of mass fraction is g, and the unit of volume fraction is mL ;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , dried at 60°C for 12h to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silicon carbide nanoparticles, the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 2.25:14 in parts by mass.

Example 6

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm, silicon carbide nanoparticles with a particle size of 40nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A, and stir Under the conditions, solution A was mixed with ammonia water with a concentration of 4.6wt%, and stirred for 0.5h until uniformly mixed to obtain solution B, wherein, the mass fraction of silicon carbide nanoparticles, the mass fraction of silicon dioxide nanoparticles, and absolute ethanol The ratio of the parts by volume of ammonia water to the parts by volume of ammonia water is 3:3:80:16, the unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , dried at 60°C for 12h to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silicon carbide nanoparticles, the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 2.5:14 in parts by mass.

Example 7

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm, silicon carbide nanoparticles with a particle size of 40nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A, and stir Under the conditions, solution A was mixed with ammonia water with a concentration of 4.6wt%, and stirred for 0.5h until uniformly mixed to obtain solution B, wherein, the mass fraction of silicon carbide nanoparticles, the mass fraction of silicon dioxide nanoparticles, and absolute ethanol The ratio of the parts by volume of ammonia water to the parts by volume of ammonia water is 3:3:80:16, the unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , dried at 60°C for 12h to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silicon carbide nanoparticles, the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 2.75:14 in parts by mass.

Example 8

A preparation method of composite coating solution, comprising the following steps:

1) At a room temperature of 20-25°C, mix silica nanoparticles with a particle size of 20nm, silicon carbide nanoparticles with a particle size of 40nm and absolute ethanol, and sonicate for 0.5h until the mixture is uniform to obtain solution A, and stir Under the conditions, solution A was mixed with ammonia water with a concentration of 4.6wt%, and stirred for 0.5h until uniformly mixed to obtain solution B, wherein, the mass fraction of silicon carbide nanoparticles, the mass fraction of silicon dioxide nanoparticles, and absolute ethanol The ratio of the parts by volume of ammonia water to the parts by volume of ammonia water is 3:3:80:16, the unit of parts by mass is g, and the unit of parts by volume is mL;

2) Add perfluorooctyltriethoxysilane (PFOTS) to solution B, stir at 55°C for 8 hours, cool to room temperature, and wash with absolute ethanol and distilled water alternately (absolute ethanol and distilled water are washed 3 times each) , dried at 60°C for 12h to obtain modified inorganic nanoparticles, wherein the ratio of the mass fraction of silicon carbide nanoparticles, the mass fraction of silica nanoparticles to the volume fraction of perfluorooctyltriethoxysilane is 3:3:1.2;

3) Turn on magnetic stirring, add modified inorganic nanoparticles to solution C under stirring conditions, and stir at 60° C. at a speed of 400 r/min for 24 hours to obtain a composite coating solution, wherein thermoplastic polyurethane (TPU) and two Methylformamide (DMF) was mixed and stirred at 80°C at a speed of 500r/min for 8h, so that thermoplastic polyurethane (TPU) was dissolved in dimethylformamide (DMF) to form solution C, in parts by mass, thermoplastic The ratio of polyurethane to dimethylformamide is 2:12, and the ratio of modified inorganic nanoparticles to solution C is 3:14 in parts by mass.

A method for preparing a puncture-resistant, strong acid-base resistant aramid composite fabric, comprising the following steps: using a scraper to spread one of the composite coating solutions obtained in 5mL of embodiments 1 to 8 on the aramid fabric to make it Fully impregnated between the fibers of the aramid fabric, and dried at room temperature to obtain an aramid composite fabric, wherein the aramid fabric has a grammage of 200g/m ² , a warp/weft density of 60 yarns/10cm, and a fine yarn Aramid plain weave fabric with a density of 1500 denier, the size of which is a square with a side length of 10 cm.

The smooth fiber surface of the aramid fabric can be observed from (a) of Figure 1, and (b) of Figure 1 shows that the surface of the prepared aramid composite fabric has an obvious micro-nano rough structure.

Water droplets, milk droplets, coffee droplets, oil droplets, NaOH aqueous solution (40wt%) droplets and _H2SO4 ( _98wt %) droplets were respectively dropped on the surface of the aramid fabric and the aramid composite fabric prepared in Example 3 , the photo is shown in Figure 2, from Figure 2 (a) it can be observed that the dripping droplets can easily penetrate the untreated aramid fabric. On the contrary, as shown in (b) of Fig. 2, when the droplet falls on the aramid composite fabric prepared in Example 3, deionized water droplet, milk, coffee, oil, NaOH aqueous solution (40wt%) and H ₂ SO ₄ (98wt%), maintaining a stable spherical shape on the aramid composite fabric, because the nano-rough structure formed by the modified inorganic nanoparticles and TPU (thermoplastic polyurethane) traps the air layer on the fabric surface.

Put the aramid fabric and the aramid composite fabric prepared in Example 3 into a glass vessel at a certain angle of inclination, and put carbon black on the surface of the aramid fabric and the aramid composite fabric prepared in Example 3, and drip on the carbon black water for a self-cleaning simulation test. It can be observed from a of Figure 3 that when carbon black is used to simulate pollutants for self-cleaning tests, when water droplets fall on the aramid fabric (Kevlar fabric), the droplets will quickly soak into the fabric, and the carbon black remains on the fabric. surface. In contrast, it can be observed from b of Figure 3 that the carbon black on the aramid composite fabric prepared in Example 3 is completely removed with the rolling of water droplets.

The aramid fiber composite fabric prepared in Example 3 loaded with a weight of 100 g was pulled horizontally and evenly on 400# sandpaper at a certain speed. The surface of the aramid composite fabric is in full contact with the sandpaper. Each time the sample is pulled 1m is recorded as a cycle, and the contact angle and rolling angle of the aramid composite fabric are measured. The contact angle and rolling angle change curves of the obtained aramid composite fabric prepared in Example 3 are shown in Figure 4 during ten cycles of sandpaper wear. It can be observed from Figure 4 that the obtained aramid composite fabric prepared in Example 3 has undergone ten Periodic weight wear cycles remain superhydrophobic.

A preparation method of TPU coated aramid fiber fabric, comprising: dissolving thermoplastic polyurethane (TPU) into N,N-dimethylformamide (DMF), obtaining a TPU solution with a TPU concentration of 15wt%, and applying it by scraping 5mL of the obtained TPU solution was spread on the aramid fabric, so that it was fully impregnated between the fibers of the aramid fabric, and dried at room temperature to obtain a TPU-coated aramid fabric.

Different sample fabrics are fixed on the clamps of the universal strength machine, and the cone thorn test is carried out on the universal strength machine with the speed of 100mm/min by using the cone thorn head in the EN:388 standard. The TPU-coated aramid fabric and the aramid fabric are shown in a of FIG. 5 , and the aramid composite fabric, TPU-coated aramid fabric and aramid fabric prepared in Examples 5-8 are shown in a of FIG. 7 . Carry out cone puncture test 5 times to each sample and seek the average value of maximum cone puncture force (cone puncture force), the maximum cone puncture force (cone puncture force) of the gained aramid composite fabric, TPU coating aramid fabric and aramid fabric prepared in embodiment 1～4 The average value of the piercing force (cone piercing force) is shown in b of Figure 5, and the maximum cone piercing force (cone piercing force) of the aramid composite fabrics, TPU coated aramid fabrics and aramid fabrics prepared in Examples 5 to 8 ) The average value is shown in b of Figure 7. It can be observed from Figure 5 that the aramid composite fabric prepared in Example 3 has the largest cone thrust value, and compared with the blank sample (aramid fabric), the force value is increased by 1367.31%. It can be observed from Figure 7 that the aramid composite fabric prepared in Example 7 has the largest cone thrust value, and compared with the aramid fabric (blank), the force value is increased by 1698.16%.

Fix the different sample fabrics on the fixture of the universal strength machine, use the P1 engineering blade and carry out the knife stab test at a speed of 100mm/min, the aramid composite fabrics, TPU coated aramid fabrics and aramid fibers prepared in Examples 1-4 The stab force value of the fabric is shown in Figure 6a. Carry out the knife stab test 5 times for each sample to find the average value of the maximum knife piercing force (knife thrust), as shown in b of Figure 6 . It can be observed from Fig. 6 that the knife-puncture force value of the aramid composite fabric prepared in Example 3 is the largest compared with the aramid fabric (blank), and the force value is increased by 457.51%.

The aramid fiber fabric and the aramid fiber composite fabric prepared in Example 3 were respectively placed in different pH solutions (different pH solutions were pH=1, 3, 5, 7, 9, 11, 13 and 14, when the pH was less than 7, it was hydrogen Sodium oxide aqueous solution, when the pH is greater than 7 is sulfuric acid, when the pH=7 is water) for 120 hours, take it out and dry it at 80°C for 8 hours and weigh it, and calculate the mass weight loss rate, as shown in a of Figure 8;

Put the aramid fiber fabric and the aramid fiber composite fabric prepared in Example 3 in the solutions of pH=1, 7 and 13 (the solution is sulfuric acid, deionized water and sodium hydroxide aqueous solution) and take out 80°C for drying every 20 minutes. Dry for 8 hours, and measure its hydrophobic angle, as shown in Figure 8b.

It can be observed from Figure 8a that, compared with the aramid fabric (pure aramid fabric in Figure 8a), the weight loss rate of the aramid composite fabric prepared in Example 3 decreases after soaking in different concentrations of acid-base solutions for a period of time. It can be observed from b of Figure 8 that the aramid composite fabric prepared in Example 3 still has superhydrophobicity when soaked in acid-base solutions of different concentrations for 120 hours.

Put the obtained aramid fiber composite fabric prepared in Example 3 on the pH test paper, drip NaOH aqueous solution (40%) and H ₂ SO ₄ (98%) droplets on the aramid fiber composite fabric, and remove it every 20 minutes Observe whether the pH paper is stained. Dropwise adding NaOH aqueous solution (40%) is shown in Figure 9 a, dropwise adding H ₂ SO ₄ (98%) droplets is shown in Figure 9 b, it can be clearly observed from Figure 9 that NaOH aqueous solution (40%) and H ₂ SO ₄ (98%) droplets were dripped on the surface of the aramid composite fabric prepared in Example 3 for 1 hour, but the shape was still spherical and the pH test paper did not change color.

The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention.

Claims (10)

1. a preparation method of composite coating solution, is characterized in that, comprises the following steps: 1) Mix the inorganic particles and absolute ethanol uniformly to obtain solution A, and under stirring conditions, mix the solution A and ammonia water uniformly to obtain solution B, wherein the inorganic particles include silica nanoparticles, and the inorganic particles The ratio of the parts by mass, the parts by volume of absolute ethanol and the parts by volume of the ammonia water is (1～10): (20～80): (4～20), and the unit of the said parts by mass is g , the unit of said parts by volume is mL; 2) Add perfluorooctyltriethoxysilane to the solution B, stir at 40-60°C for 4-12 hours, cool to room temperature, wash and dry to obtain modified inorganic nanoparticles, wherein the inorganic particles The ratio of the mass fraction of the perfluorooctyltriethoxysilane to the volume fraction of the perfluorooctyltriethoxysilane is (1-10): (0.4-3); 3) Under stirring conditions, add modified inorganic nanoparticles to solution C, and stir at 40-100° C. for 20-25 hours to obtain a composite coating solution, wherein thermoplastic polyurethane is dissolved in dimethylformamide to form the Solution C, in parts by mass, the ratio of the thermoplastic polyurethane to dimethylformamide is 2:12, in parts by mass, the ratio of the modified inorganic nanoparticles to solution C is (0.75～3) :14. 2. The preparation method according to claim 1, characterized in that, in the step 1), the inorganic particles also include silicon carbide nanoparticles, and in parts by mass, the silicon dioxide nanoparticles and carbonized The ratio of silicon nanoparticles is (1-40):(1-10). 3. The preparation method according to claim 1 or 2, characterized in that, in the step 1), the concentration of the ammonia water is 1 to 10wt%; In the step 1), the particle size of the silica nanoparticles is 12-600nm, and the particle size of the silicon carbide nanoparticles is 40-600nm; In the step 1), the method for uniformly mixing the inorganic particles and absolute ethanol is: mixing the inorganic particles and absolute ethanol, and ultrasonicating. 4. the preparation method according to claim 1, is characterized in that, in described step 2), described washing adopts dehydrated alcohol and distilled water to carry out alternately; In the step 2), the drying temperature is 50-130° C., and the drying time is at least 6 hours; In the step 3), the stirring speed at 40-100°C is 100-500r/min; In the step 3), the thermoplastic polyurethane and dimethylformamide are mixed and stirred at 50-100° C. for 6-8 hours to obtain the solution C. 5. The preparation method according to claim 4, characterized in that, after mixing the thermoplastic polyurethane and dimethylformamide, the stirring speed is 100-600r/min. 6. The composite coating solution obtained by the preparation method according to any one of claims 1 to 5. 7. A method for preparing a puncture-resistant, strong acid-base resistant aramid composite fabric, comprising the steps of: spreading the composite coating solution according to claim 6 on the aramid fabric, drying to obtain the Aramid composite fabric. 8. the aramid fiber composite fabric that method obtains as claimed in claim 7. 9. The application of the composite coating solution as claimed in claim 6 in improving fabric puncture resistance/strong acid and alkali resistance/hydrophobic performance. 10. The application according to claim 9, wherein the fabric is made of aramid fiber, polyimide, ultra-high molecular weight polyethylene with an average weight greater than 3 million, poly-p-phenylene benzobisoxazole or polyester.

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