阅读说明：本技术 高牢度弹力牛仔贴合面料的制备方法 (Preparation method of high-fastness elastic denim attaching fabric ) 是由 彭明喜 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种高牢度弹力牛仔贴合面料的制备方法,所述贴合面料包括预处理底布、面布和TPE膜,所述面布通过热熔胶贴合在预处理底布上,所述TPE膜通过热熔胶贴合在面布上；所述预处理底布由底布、表面改性剂改性制得；所述表面改性剂各组分原料包括：以重量计,阻燃剂5-7份、吸水微球10-12份、六水合氯化铝8-10份、无水乙醇25-30份、甲酰胺4-6份、正硅酸四乙酯4-6份、1,2-环氧丙烷10-14份。本发明公开了一种高牢度弹力牛仔贴合面料及其制备方法,工艺设计合理,操作简单,制备得到具有优异阻燃性能的三层贴合面料,该贴合面料挺括性好,可广泛应用于服装领域,实用性较高。(The invention discloses a preparation method of high-fastness elastic denim attaching fabric, which comprises a pretreated base fabric, a piece of surface fabric and a TPE (thermoplastic elastomer) film, wherein the surface fabric is attached to the pretreated base fabric through hot melt adhesive; the pretreated base fabric is prepared by modifying base fabric and a surface modifier; the surface modifier comprises the following raw materials in parts by weight: 5-7 parts of flame retardant, 10-12 parts of water-absorbing microspheres, 8-10 parts of aluminum chloride hexahydrate, 25-30 parts of absolute ethyl alcohol, 4-6 parts of formamide, 4-6 parts of tetraethyl orthosilicate and 10-14 parts of 1, 2-epoxypropane. The invention discloses a high-fastness elastic jean attaching fabric and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared three-layer attaching fabric with excellent flame retardant property is good in stiffness and smoothness, the attaching fabric can be widely applied to the field of clothes, and the practicability is high.)

1. A preparation method of the high-fastness elastic denim fit fabric is characterized by comprising the following steps: the method comprises the following steps:

s1: preparing materials;

s2: preparing a modified water-absorbing material:

mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide for 20min, heating to 75 ℃, stirring for reacting for 2.5h, adding nitrile rubber after reaction, stirring for reacting for 80min at 80 ℃, washing with absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain modified rubber;

mixing vinyl silicone oil, white carbon black and aluminum hydroxide, stirring for 3.5h, continuously heating to 210 ℃ under a vacuum condition, stirring for 2.2h, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring for 30min, and carrying out compression molding at 145 ℃ for 20min to obtain silicone rubber;

plasticating nitrile rubber and modified rubber for 7min, adding silicon rubber and graphene oxide, mixing for 7min, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing for 25min, thinly passing, vulcanizing on a flat vulcanizing machine, and vulcanizing at 165 ℃ for 3min to obtain a water absorbent material;

dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion for 40min, adding 3-aminopropyltrimethoxysiloxane, reacting for 6.2h, cooling to room temperature, washing with alcohol for 3 times, washing with water for 3 times, freeze-drying, grinding, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

s3: preparation of water-absorbing microspheres:

dissolving catechol and hexamethylenediamine in deionized water, stirring for 30min, adding silicon dioxide microspheres, continuously stirring for 20min, reacting for 38h at room temperature, centrifugally separating, washing, placing in an etching solution, stirring for 35min, centrifugally separating, washing, and vacuum drying for 24h at 40 ℃ to obtain modified microspheres; the etching liquid comprises hydrofluoric acid and ammonium fluoride, and the volume ratio of the hydrofluoric acid to the ammonium fluoride is 1: 1;

dissolving the modified water-absorbing material with hydrochloric acid, stirring for 10min, filtering, and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring for 10min, filtering and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring for 20min, filtering, washing, and vacuum drying at 40 ℃ to obtain water-absorbing microspheres;

s4: preparation of surface modifier:

heating phosphoric acid to 220 ℃, reacting for 35min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 115 ℃, reacting for 3.2h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 18min, adding tetraethyl orthosilicate, stirring for 26h, adding a flame retardant and water-absorbing microspheres, continuing stirring for 15min, adding 1, 2-epoxypropane, and stirring for 5min to obtain a surface modifier;

s5: taking a base fabric, cleaning with anhydrous ether for 6 hours, cleaning with deionized water, drying, then placing in a sodium hydroxide solution, soaking for 1 hour, washing with deionized water, drying, then placing in a surface modifier for soaking for 5min, taking out the base fabric, standing for 24 hours at room temperature, aging and drying to obtain a pretreated base fabric;

s6: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing for 45 hours to obtain pretreated surface cloth; taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 45 hours, drying at 120 ℃ for 40 seconds, heating to 160 ℃, and baking for 3min to obtain an attached fabric;

the surface modifier comprises the following raw materials in parts by weight: by weight, 7 parts of flame retardant, 12 parts of water-absorbing microspheres, 10 parts of aluminum chloride hexahydrate, 30 parts of absolute ethyl alcohol, 6 parts of formamide, 6 parts of tetraethyl orthosilicate and 14 parts of 1, 2-propylene oxide;

the water absorbing material comprises the following raw materials: 100 parts of nitrile rubber, 40 parts of modified rubber, 30 parts of silicon rubber, 8 parts of graphene oxide, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an anti-aging agent, 4 parts of an accelerator, 10 parts of carbon black, 35 parts of sodium polyacrylate and 3 parts of sulfur; the particle size of the silicon dioxide microspheres is 0.1 mm.

Technical Field

The invention relates to the technical field of fabric preparation, in particular to a preparation method of high-fastness elastic denim attaching fabric.

Background

Denim, also called Denim, is a thick yarn-dyed warp-faced twill, with deep warp yarn, usually indigo, and light weft yarn, usually light grey or scoured grey yarn. The jean starts in the western United states, is famous for grazing personnel to make clothes and trousers, and has compact and thick texture, bright color and clear texture; is suitable for male and female jeans, jeans tops, jean vests, jean skirts and the like.

Nowadays, the jean fabric is widely applied to our lives because of the characteristics of practical wear resistance, but the existing jean fabric has single function, the texture and the hand feeling of a single-layer fabric are poor, and the flame retardant property of the jean fabric cannot meet our requirements.

Aiming at the problem, a high-fastness elastic denim attaching fabric and a preparation method thereof are designed, which are one of the technical problems to be solved urgently.

Disclosure of Invention

The invention aims to provide a high-fastness elastic denim attaching fabric and a preparation method thereof, and aims to solve the problems in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme:

the high-fastness elastic denim attaching fabric comprises a pretreated base fabric, a piece of face fabric and a TPE film, wherein the face fabric is attached to the pretreated base fabric through a hot melt adhesive, and the TPE film is attached to the face fabric through the hot melt adhesive; the pretreated base fabric is prepared by modifying base fabric and a surface modifier;

the surface modifier comprises the following raw materials in parts by weight: 5-7 parts of flame retardant, 10-12 parts of water-absorbing microspheres, 8-10 parts of aluminum chloride hexahydrate, 25-30 parts of absolute ethyl alcohol, 4-6 parts of formamide, 4-6 parts of tetraethyl orthosilicate and 10-14 parts of 1, 2-epoxypropane.

According to an optimized scheme, the water-absorbing microspheres are prepared from modified microspheres, a modified water-absorbing material and absolute ethyl alcohol; the flame retardant is prepared from phosphoric acid, glacial acetic acid and anhydrous piperazine.

According to an optimized scheme, the modified water-absorbing material is prepared from a water-absorbing material, 3-aminopropyl trimethoxy siloxane and absolute ethyl alcohol, wherein the water-absorbing material comprises the following raw materials: by weight, 90-100 parts of nitrile rubber, 30-40 parts of modified rubber, 20-30 parts of silicone rubber, 6-8 parts of graphene oxide, 4-5 parts of zinc oxide, 1-2 parts of stearic acid, 2-3 parts of an anti-aging agent, 3-4 parts of an accelerator, 8-10 parts of carbon black, 30-35 parts of sodium polyacrylate and 2-3 parts of sulfur.

According to an optimized scheme, the modified rubber is prepared from tert-butyl hydroperoxide, molybdenum trioxide and nitrile rubber; the silicone rubber is prepared from vinyl silicone oil, white carbon black, aluminum hydroxide, a platinum catalyst and hydrogen-containing silicone oil.

According to an optimized scheme, the modified microspheres are prepared from catechol, hexamethylene diamine and silicon dioxide microspheres.

In an optimized scheme, the shell fabric is formed by mixing 95% -98% of cotton and 2% -5% of spandex jeans; the base fabric is nylon mesh fabric.

According to an optimized scheme, the particle size of the silicon dioxide microspheres is 0.08-0.1 mm.

According to an optimized scheme, the preparation method of the high-fastness elastic denim fit fabric comprises the following steps:

1) preparing materials;

2) preparing a modified water-absorbing material:

a) mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide, heating to 70-75 ℃, stirring for reaction, adding nitrile rubber after reaction, stirring for reaction at 60-80 ℃, washing, and drying in vacuum to obtain modified rubber;

b) mixing and stirring vinyl silicone oil, white carbon black and aluminum hydroxide, continuously heating to the temperature of 200 ℃ and 210 ℃ under the vacuum condition, stirring, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring, and performing compression molding at the temperature of 140 ℃ and 145 ℃ to obtain silicon rubber;

c) plasticating nitrile rubber and modified rubber, adding silicon rubber and graphene oxide, mixing, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing, thinly passing, and vulcanizing on a flat vulcanizing machine to obtain a water absorbing material;

d) dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion, adding 3-aminopropyl trimethoxy siloxane, reacting, cooling to room temperature, washing with alcohol, washing with water, freeze-drying, grinding, crushing, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

3) preparation of water-absorbing microspheres:

a) dissolving catechol and hexamethylenediamine in deionized water, stirring, adding silicon dioxide microspheres, continuously stirring, reacting at room temperature, centrifugally separating, washing, placing in an etching solution, stirring, centrifugally separating, washing, and vacuum drying to obtain modified microspheres;

b) dissolving the modified water-absorbing material in hydrochloric acid, stirring, filtering and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring, filtering and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring, filtering, washing, and drying in vacuum to obtain water-absorbing microspheres;

4) preparation of surface modifier:

a) heating phosphoric acid to 200-220 ℃ for reaction, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 110-115 ℃, continuing the reaction, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

b) stirring aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, adding tetraethyl orthosilicate, stirring, adding a flame retardant and water-absorbing microspheres, continuing stirring, adding 1, 2-epoxypropane, and stirring to obtain a surface modifier;

5) taking a base fabric, cleaning, drying, soaking in a sodium hydroxide solution, washing with deionized water, drying, soaking in a surface modifier, taking out the base fabric, standing at room temperature, aging and drying to obtain a pretreated base fabric;

6) taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing to obtain pretreated surface cloth; and then taking the pretreated base fabric, attaching the pretreated surface fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber compression roller, evaporating and curing, drying at the temperature of 100-160 ℃, heating to the temperature of 140-160 ℃, and baking to obtain the attached fabric.

The optimized scheme comprises the following steps:

1) preparing materials;

2) preparing a modified water-absorbing material:

a) mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide for 10-20min, heating to 70-75 ℃, stirring for reacting for 2-2.5h, adding nitrile rubber after reaction, stirring for reacting for 30-80min at 60-80 ℃, washing with absolute ethanol, and vacuum drying at 40 ℃ to obtain modified rubber;

b) mixing and stirring vinyl silicone oil, white carbon black and aluminum hydroxide for 3-3.5h, continuously heating to 210 ℃ under a vacuum condition, stirring for 2-2.2h, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring for 20-30min, and performing compression molding at 145 ℃ under 140 ℃ for 15-20min to obtain silicone rubber;

c) plasticating nitrile rubber and modified rubber for 5-7min, adding silicon rubber and graphene oxide, mixing for 5-7min, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing for 15-25min, thinly passing, vulcanizing on a flat vulcanizing machine, and vulcanizing at the temperature of 160-165 ℃ for 2-3min to obtain a water absorbing material;

d) dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion for 30-40min, adding 3-aminopropyltrimethoxysiloxane, reacting for 6-6.2h, cooling to room temperature, washing with alcohol for 2-3 times, washing with water for 2-3 times, freeze-drying, grinding, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

3) preparation of water-absorbing microspheres:

a) dissolving pyrocatechol and hexamethylenediamine in deionized water, stirring for 20-30min, adding silicon dioxide microspheres, continuously stirring for 10-20min, reacting for 36-38h at room temperature, centrifugally separating, washing, placing in an etching solution, stirring for 25-35min, centrifugally separating, washing, and vacuum drying for 24h at 40 ℃ to obtain modified microspheres;

b) dissolving the modified water-absorbing material in hydrochloric acid, stirring for 5-10min, filtering, and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring for 5-10min, filtering, and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring for 10-20min, filtering, washing, and vacuum drying at 40 deg.C to obtain water-absorbing microspheres;

4) preparation of surface modifier:

a) heating phosphoric acid to 200-220 ℃, reacting for 25-35min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 110-115 ℃, reacting for 3-3.2h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

b) taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 15-18min, adding tetraethyl orthosilicate, stirring for 24-26h, adding a flame retardant and water-absorbing microspheres, continuing stirring for 10-15min, then adding 1, 2-epoxypropane, and stirring for 4-5min to obtain a surface modifier;

5) taking a base fabric, cleaning with anhydrous ether for 5-6h, cleaning with deionized water, drying, placing in a sodium hydroxide solution, soaking for 0.8-1h, washing with deionized water, drying, placing in a surface modifier, soaking for 3-5min, taking out the base fabric, standing for 20-24h at room temperature, aging, and drying to obtain a pretreated base fabric;

6) taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing for 40-45h to obtain pretreated surface cloth; and then taking the pretreated base fabric, attaching the pretreated surface fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber compression roller, evaporating and curing for 40-45h, drying at the temperature of 100-120 ℃ for 30-40s, heating to the temperature of 140-160 ℃, and baking for 2-3min to obtain the attached surface fabric.

According to an optimized scheme, in the step a) of the step 3), the etching solution comprises hydrofluoric acid and ammonium fluoride, and the volume ratio of the hydrofluoric acid to the ammonium fluoride is 1: 1.

compared with the prior art, the invention has the beneficial effects that:

during preparation, step 2) is firstly carried out to prepare the modified water-absorbing material, during preparation, tert-butyl hydroperoxide is used as an oxidant, molybdenum trioxide is used as a catalyst to carry out epoxidation reaction on nitrile rubber to prepare modified rubber (epoxidized nitrile rubber), then components such as platinum catalyst, aluminum hydroxide and vinyl silicone oil are utilized to prepare silicone rubber with excellent flame retardant effect, during the preparation process, the aluminum hydroxide is used as a flame retardant to improve the flame retardant property of the silicone rubber, and the addition of the silicone rubber is beneficial to improving the flame retardant property of the water-absorbing material; according to the invention, the water-absorbing expansion rubber material (namely the water-absorbing material) is prepared by taking the nitrile rubber, the modified rubber and the silicone rubber as main rubber materials and adding the components such as the graphene oxide and the carbon black, and the like.

After the water absorbing material is prepared, the water absorbing material is aminated by absolute ethyl alcohol and 3-aminopropyl trimethoxy siloxane, the 3-aminopropyl trimethoxy siloxane can perform nucleophilic reaction with epoxy bonds on the surface of graphene oxide and is grafted with amino groups to obtain a modified water absorbing material, and the modified water absorbing material can perform amino protonation reaction in an acidic environment to generate the modified water absorbing material with positive charges.

And then, the water-absorbing microspheres are prepared in the step 3), silicon dioxide microspheres with the particle size of 0.08-0.1mm are selected in the preparation process, the silicon dioxide microspheres are used as templates, the silicon dioxide microspheres are polymerized through the reaction of catechol and hexamethylene diamine and coated on the surfaces of the silicon dioxide microspheres to form a polyphenylamine core-shell structure, the polyphenylamine core-shell structure is placed in etching liquid for etching to remove the silicon dioxide microspheres in the capsules, the modified microspheres are obtained after centrifugal separation, the modified microspheres contain a large amount of amino and phenolic hydroxyl groups, amino protonation is carried out in an acidic environment, the modified microspheres are enabled to have positive charges, and the phenolic hydroxyl groups are enabled to have deprotonation effect in an alkaline environment, so that the modified microspheres can have negative charges.

Based on the property, after the modified microsphere is prepared, the modified microsphere is placed in a sodium hydroxide solution to enable the modified microsphere to have negative charges due to the deprotonation effect of phenolic hydroxyl groups, then the modified water-absorbing material is placed in a hydrochloric acid solution to enable the modified water-absorbing material to have positive charges, and the modified water-absorbing material is adsorbed into the modified microsphere under the electrostatic action, so that the water-absorbing microsphere with excellent water absorption effect is obtained; in the preparation process, the modified water-absorbing material is ground and sieved by a 200-mesh sieve, so that the particle size of the modified water-absorbing material is smaller than 0.07mm, and the size of the internal cavity of the modified microsphere is 0.08-0.1mm, so that the modified water-absorbing material can be effectively adsorbed into the modified microsphere, and the smooth preparation of the water-absorbing microsphere is ensured.

Preparing a surface modifier in step 4), namely, taking phosphoric acid and anhydrous piperazine as raw materials, dehydrating the phosphoric acid at a high temperature environment to generate pyrophosphoric acid, and reacting the pyrophosphoric acid with the anhydrous piperazine to prepare piperazine pyrophosphate (a flame retardant); after the flame retardant is prepared, a sol-gel method is adopted, aluminum chloride hexahydrate is used as an aluminum source, tetraethyl orthosilicate is used as a silicon source, 1, 2-epoxypropane is used as a gel network inducer to generate silica gel, in the preparation process, because the base fabric is nylon 22D mesh fabric, the surface of the base fabric contains a large number of amido bonds, after the base fabric is treated by sodium hydroxide, the amido bonds on the surface of the base fabric are damaged and have negative charges, colloidal particles in the silica gel system have positive charges, not only can the absorption microspheres be adsorbed in the gel system, but also the colloidal particles with the positive charges can be firmly adsorbed on the surface of the base fabric through electrostatic action, the condensation polymerization is further carried out under the action of the 1, 2-epoxypropane, so that a gel film layer which is uniformly coated is formed on the surface of the base fabric, and after the aging and drying steps are, the pretreated base fabric is obtained, and the absorbing microspheres and the fire retardant are adsorbed in the aerogel layer.

After the pretreated base fabric is prepared, hot melting and laminating of the surface fabric and the TPE film are carried out to obtain laminated fabric; when the flame is burnt, the piperazine pyrophosphate in the pretreated base fabric begins to decompose along with the rise of temperature, a large amount of non-combustible gas is generated, the concentration of oxygen can be diluted, and oxygen transmission and heat transfer are inhibited; acid substances such as phosphoric acid, metaphosphoric acid or polyphosphoric acid and the like are generated during decomposition, the acid-washing substance has an excellent dehydration effect, can be dehydrated to promote carbon formation, and simultaneously, the whole pretreated base fabric is in an acid environment, the amino groups of the modified microspheres are protonated to carry positive charges under the environment, the modified water-absorbing material is separated from the modified microspheres under the electrostatic action, and the modified water-absorbing material absorbs water and expands, so that the dehydration and carbon formation efficiency of a system can be improved, and the carbon layer can be filled with the particles after water absorption and expansion, thereby effectively improving the compactness of the carbon layer, insulating heat and isolating oxygen; meanwhile, in the process, the aluminum hydroxide on the surface of the pretreated base fabric can be absorbed and thermally decomposed to generate aluminum oxide, so that the heat loss and the heat transfer resistance of the pretreated base fabric are increased, and the heat insulation and flame retardant properties are further improved.

The invention discloses a high-fastness elastic jean attaching fabric and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared three-layer attaching fabric with excellent flame retardant property is good in stiffness and smoothness, the attaching fabric can be widely applied to the field of clothes, and the practicability is high.

Detailed Description

The technical solutions in the examples of the present invention will be described clearly and completely below, and it is obvious that the described examples are only a part of examples of the present invention, but not all examples. All other examples, which can be obtained by a person skilled in the art without making any creative effort based on the examples in the present invention, belong to the protection scope of the present invention.

Example 1:

s1: preparing materials;

s2: preparing a modified water-absorbing material:

mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide for 10min, heating to 70 ℃, stirring for reacting for 2h, adding nitrile rubber after reaction, stirring and reacting for 30min at 60 ℃, washing with absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain modified rubber;

mixing and stirring vinyl silicone oil, white carbon black and aluminum hydroxide for 3h, continuously heating to 200 ℃ under a vacuum condition, stirring for 2h, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring for 20min, and performing compression molding at 140 ℃ for 15min to obtain silicone rubber;

plasticating nitrile rubber and modified rubber for 5min, adding silicon rubber and graphene oxide, mixing for 5min, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing for 15min, thinly passing, vulcanizing on a flat vulcanizing machine, and vulcanizing at 160 ℃ for 2min to obtain a water absorbent material;

dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion for 30min, adding 3-aminopropyltrimethoxysiloxane, reacting for 6h, cooling to room temperature, performing alcohol washing for 2 times, performing water washing for 2 times, performing freeze drying, grinding and crushing, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

s3: preparation of water-absorbing microspheres:

dissolving pyrocatechol and hexamethylenediamine in deionized water, stirring for 20min, adding silicon dioxide microspheres, continuously stirring for 10min, reacting for 36h at room temperature, centrifugally separating, washing, placing in an etching solution, stirring for 25min, centrifugally separating, washing, and vacuum drying for 24h at 40 ℃ to obtain modified microspheres; the etching liquid comprises hydrofluoric acid and ammonium fluoride, and the volume ratio of the hydrofluoric acid to the ammonium fluoride is 1: 1;

dissolving the modified water-absorbing material with hydrochloric acid, stirring for 5min, filtering, and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring for 5min, filtering, and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring for 10min, filtering, washing, and vacuum drying at 40 ℃ to obtain water-absorbing microspheres;

s4: preparation of surface modifier:

heating phosphoric acid to 200 ℃, reacting for 25min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 110 ℃, reacting for 3h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 15min, adding tetraethyl orthosilicate, stirring for 24h, adding a flame retardant and water-absorbing microspheres, continuing stirring for 10min, then adding 1, 2-epoxypropane, and stirring for 4min to obtain a surface modifier;

s5: taking a base fabric, washing with anhydrous ether for 5 hours, washing with deionized water, drying, then placing in a sodium hydroxide solution, soaking for 0.8 hour, washing with deionized water, drying, then placing in a surface modifier for soaking for 3min, taking out the base fabric, standing for 20 hours at room temperature, aging and drying to obtain a pretreated base fabric;

s6: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing for 40 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 40 hours, drying at 100 ℃ for 30s, heating to 140 ℃, and baking for 2min to obtain the attached face fabric.

In the present embodiment, the surface modifier comprises the following raw materials: by weight, 5 parts of flame retardant, 10 parts of water-absorbing microspheres, 8 parts of aluminum chloride hexahydrate, 25 parts of absolute ethyl alcohol, 4 parts of formamide, 4 parts of tetraethyl orthosilicate and 10 parts of 1, 2-propylene oxide.

The water absorbing material comprises the following raw materials: by weight, 90 parts of nitrile rubber, 30 parts of modified rubber, 20 parts of silicon rubber, 6 parts of graphene oxide, 4 parts of zinc oxide, 1 part of stearic acid, 2 parts of an anti-aging agent, 3 parts of an accelerator, 8 parts of carbon black, 30 parts of sodium polyacrylate and 2 parts of sulfur; the particle size of the silicon dioxide microspheres is 0.08 mm.

Example 2:

s1: preparing materials;

s2: preparing a modified water-absorbing material:

mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide for 15min, heating to 72 ℃, stirring for reacting for 2.3h, adding nitrile rubber after reaction, stirring for reacting for 60min at 70 ℃, washing with absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain modified rubber;

mixing vinyl silicone oil, white carbon black and aluminum hydroxide, stirring for 3.2h, continuously heating to 205 ℃ under a vacuum condition, stirring for 2.1h, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring for 25min, and carrying out compression molding at 143 ℃ for 18min to obtain silicone rubber;

plasticating nitrile rubber and modified rubber for 6min, adding silicon rubber and graphene oxide, mixing for 6min, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing for 20min, thinly passing, vulcanizing on a flat vulcanizing machine, and vulcanizing at 163 ℃ for 2.5min to obtain a water absorbent material;

dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion for 35min, adding 3-aminopropyltrimethoxysiloxane, reacting for 6.1h, cooling to room temperature, washing with alcohol for 2 times, washing with water for 2 times, freeze-drying, grinding, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

s3: preparation of water-absorbing microspheres:

dissolving catechol and hexamethylenediamine in deionized water, stirring for 25min, adding silicon dioxide microspheres, continuously stirring for 15min, reacting for 37h at room temperature, centrifugally separating, washing, placing in an etching solution, stirring for 30min, centrifugally separating, washing, and vacuum drying for 24h at 40 ℃ to obtain modified microspheres; the etching liquid comprises hydrofluoric acid and ammonium fluoride, and the volume ratio of the hydrofluoric acid to the ammonium fluoride is 1: 1;

dissolving the modified water-absorbing material with hydrochloric acid, stirring for 8min, filtering, and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring for 8min, filtering, and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring for 15min, filtering, washing, and vacuum drying at 40 ℃ to obtain water-absorbing microspheres;

s4: preparation of surface modifier:

heating phosphoric acid to 210 ℃, reacting for 30min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 113 ℃, reacting for 3.1h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 16min, adding tetraethyl orthosilicate, stirring for 25h, adding a flame retardant and water-absorbing microspheres, continuing stirring for 12min, then adding 1, 2-epoxypropane, and stirring for 4.5min to obtain a surface modifier;

s5: taking a base fabric, cleaning with anhydrous ether for 5.5h, cleaning with deionized water, drying, placing in a sodium hydroxide solution, soaking for 0.9h, cleaning with deionized water, drying, placing in a surface modifier, soaking for 4min, taking out the base fabric, standing at room temperature for 22h, aging and drying to obtain a pretreated base fabric;

s6: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing the surface cloth for 43 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 42 hours, drying at 110 ℃ for 35 seconds, heating to 150 ℃, and baking for 2.5min to obtain the attached face fabric.

In the present embodiment, the surface modifier comprises the following raw materials: 6 parts of flame retardant, 11 parts of water-absorbing microspheres, 9 parts of aluminum chloride hexahydrate, 28 parts of absolute ethyl alcohol, 5 parts of formamide, 5 parts of tetraethyl orthosilicate and 12 parts of 1, 2-propylene oxide.

The water absorbing material comprises the following raw materials: by weight, 95 parts of nitrile rubber, 35 parts of modified rubber, 25 parts of silicon rubber, 7 parts of graphene oxide, 4.5 parts of zinc oxide, 1.5 parts of stearic acid, 2.5 parts of an anti-aging agent, 3.5 parts of a promoter, 9 parts of carbon black, 32 parts of sodium polyacrylate and 2.5 parts of sulfur; the particle size of the silicon dioxide microspheres is 0.09 mm.

Example 3:

s1: preparing materials;

s2: preparing a modified water-absorbing material:

mixing and stirring tert-butyl hydroperoxide and molybdenum trioxide for 20min, heating to 75 ℃, stirring for reacting for 2.5h, adding nitrile rubber after reaction, stirring for reacting for 80min at 80 ℃, washing with absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain modified rubber;

mixing vinyl silicone oil, white carbon black and aluminum hydroxide, stirring for 3.5h, continuously heating to 210 ℃ under a vacuum condition, stirring for 2.2h, adding a platinum catalyst and hydrogen-containing silicone oil, continuously stirring for 30min, and carrying out compression molding at 145 ℃ for 20min to obtain silicone rubber;

plasticating nitrile rubber and modified rubber for 7min, adding silicon rubber and graphene oxide, mixing for 7min, sequentially adding zinc oxide, stearic acid, an anti-aging agent, an accelerator, carbon black, sodium polyacrylate and sulfur, mixing for 25min, thinly passing, vulcanizing on a flat vulcanizing machine, and vulcanizing at 165 ℃ for 3min to obtain a water absorbent material;

dissolving a water absorbing material in absolute ethyl alcohol, performing ultrasonic dispersion for 40min, adding 3-aminopropyltrimethoxysiloxane, reacting for 6.2h, cooling to room temperature, washing with alcohol for 3 times, washing with water for 3 times, freeze-drying, grinding, and sieving with a 200-mesh sieve to obtain a modified water absorbing material;

s3: preparation of water-absorbing microspheres:

dissolving catechol and hexamethylenediamine in deionized water, stirring for 30min, adding silicon dioxide microspheres, continuously stirring for 20min, reacting for 38h at room temperature, centrifugally separating, washing, placing in an etching solution, stirring for 35min, centrifugally separating, washing, and vacuum drying for 24h at 40 ℃ to obtain modified microspheres; the etching liquid comprises hydrofluoric acid and ammonium fluoride, and the volume ratio of the hydrofluoric acid to the ammonium fluoride is 1: 1;

dissolving the modified water-absorbing material with hydrochloric acid, stirring for 10min, filtering, and washing to obtain a material A; dissolving the modified microspheres in a sodium hydroxide solution, stirring for 10min, filtering and washing to obtain a material B; dissolving the material B in absolute ethyl alcohol, adding the material A, stirring for 20min, filtering, washing, and vacuum drying at 40 ℃ to obtain water-absorbing microspheres;

s4: preparation of surface modifier:

heating phosphoric acid to 220 ℃, reacting for 35min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 115 ℃, reacting for 3.2h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 18min, adding tetraethyl orthosilicate, stirring for 26h, adding a flame retardant and water-absorbing microspheres, continuing stirring for 15min, adding 1, 2-epoxypropane, and stirring for 5min to obtain a surface modifier;

s5: taking a base fabric, cleaning with anhydrous ether for 6 hours, cleaning with deionized water, drying, then placing in a sodium hydroxide solution, soaking for 1 hour, washing with deionized water, drying, then placing in a surface modifier for soaking for 5min, taking out the base fabric, standing for 24 hours at room temperature, aging and drying to obtain a pretreated base fabric;

s6: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing for 45 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 45 hours, drying at 120 ℃ for 40 seconds, heating to 160 ℃, and baking for 3min to obtain the attached face fabric.

In the present embodiment, the surface modifier comprises the following raw materials: by weight, 7 parts of flame retardant, 12 parts of water-absorbing microspheres, 10 parts of aluminum chloride hexahydrate, 30 parts of absolute ethyl alcohol, 6 parts of formamide, 6 parts of tetraethyl orthosilicate and 14 parts of 1, 2-propylene oxide.

The water absorbing material comprises the following raw materials: 100 parts of nitrile rubber, 40 parts of modified rubber, 30 parts of silicon rubber, 8 parts of graphene oxide, 5 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an anti-aging agent, 4 parts of an accelerator, 10 parts of carbon black, 35 parts of sodium polyacrylate and 3 parts of sulfur; the particle size of the silicon dioxide microspheres is 0.1 mm.

Comparative example 1: (lack of Water-absorbing microspheres)

S1: preparing materials;

s2: preparation of surface modifier:

heating phosphoric acid to 210 ℃, reacting for 30min, adding glacial acetic acid and anhydrous piperazine, adjusting the temperature to 113 ℃, reacting for 3.1h, performing suction filtration, and performing vacuum drying to obtain a flame retardant;

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 16min, adding tetraethyl orthosilicate, stirring for 25h, adding a flame retardant, continuing stirring for 12min, adding 1, 2-propylene oxide, and stirring for 4.5min to obtain a surface modifier;

s3: taking a base fabric, cleaning with anhydrous ether for 5.5h, cleaning with deionized water, drying, placing in a sodium hydroxide solution, soaking for 0.9h, cleaning with deionized water, drying, placing in a surface modifier, soaking for 4min, taking out the base fabric, standing at room temperature for 22h, aging and drying to obtain a pretreated base fabric;

s4: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing the surface cloth for 43 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 42 hours, drying at 110 ℃ for 35 seconds, heating to 150 ℃, and baking for 2.5min to obtain the attached face fabric.

In the present embodiment, the surface modifier comprises the following raw materials: 6 parts of flame retardant, 9 parts of aluminum chloride hexahydrate, 28 parts of absolute ethyl alcohol, 5 parts of formamide, 5 parts of tetraethyl orthosilicate and 12 parts of 1, 2-propylene oxide.

Comparative example 2: (lack of Water-absorbing microspheres, flame retardant)

S1: preparing materials;

s2: preparation of surface modifier:

taking aluminum chloride hexahydrate, absolute ethyl alcohol, deionized water and formamide, stirring for 16min, adding tetraethyl orthosilicate, stirring for 25h, adding 1, 2-propylene oxide, and stirring for 4.5min to obtain a surface modifier;

s3: taking a base fabric, cleaning with anhydrous ether for 5.5h, cleaning with deionized water, drying, placing in a sodium hydroxide solution, soaking for 0.9h, cleaning with deionized water, drying, placing in a surface modifier, soaking for 4min, taking out the base fabric, standing at room temperature for 22h, aging and drying to obtain a pretreated base fabric;

s4: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing the surface cloth for 43 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 42 hours, drying at 110 ℃ for 35 seconds, heating to 150 ℃, and baking for 2.5min to obtain the attached face fabric.

In the present embodiment, the surface modifier comprises the following raw materials: by weight, 9 parts of aluminum chloride hexahydrate, 28 parts of absolute ethyl alcohol, 5 parts of formamide, 5 parts of tetraethyl orthosilicate and 12 parts of 1, 2-propylene oxide.

Comparative example 3: (lack of Water-absorbing microspheres, flame retardant, surface modifier)

S1: preparing materials;

s2: taking a base fabric, washing with anhydrous ether for 5.5h, washing with deionized water, drying, placing in a sodium hydroxide solution, soaking for 0.9h, washing with deionized water, and drying to obtain a pretreated base fabric;

s3: taking the surface cloth, attaching a TPE film on the surface of the surface cloth through a hot melt adhesive, pressing the surface cloth by a rubber compression roller, and evaporating and curing the surface cloth for 43 hours to obtain pretreated surface cloth; and taking the pretreated base fabric, attaching the pretreated face fabric to the surface of the pretreated base fabric, pressing and attaching by a rubber press roller, evaporating and curing for 42 hours, drying at 110 ℃ for 35 seconds, heating to 150 ℃, and baking for 2.5min to obtain the attached face fabric.

Experiment:

the flame retardant performance of the laminated fabrics prepared in examples 1-3 and comparative examples 1-3 was measured according to GB/T5455-1997 vertical textile flammability test, and the test data are shown in the following table:

item	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2	Comparative example 3
							Time of continuous combustion(s)	0	0	0	0	0	2
Smoldering time(s)	0	0	0	0	0	2
							Radial damage length (mm)	33.1	32.4	32.6	43.9	69.6	87.4
Length of weft damage (mm)	32.7	31.9	32.8	44.1	68.3	87.9

As can be seen from the above table, the examples 1 to 3 respectively form a contrast experiment with the comparative examples 1 to 3, and the experiment can prove that the flame retardant and the water-absorbing microspheres can effectively improve the flame retardant property of the laminated fabric.

And (4) conclusion: the method has the advantages of reasonable process design and simple operation, and the prepared three-layer laminated fabric with excellent flame retardant property is good in stiffness, can be widely applied to the field of clothes and is high in practicability.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present examples are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.