High-flame-retardant heat-insulating multilayer film fabric as well as preparation method and application thereof

Abstract

The invention provides a high-flame-retardant heat-insulating multilayer film fabric as well as a preparation method and application thereof, and belongs to the technical field of chemical protective fabrics. Vinyl siloxane modification is carried out on the surface of the multi-layer film fabric, and vinyl siloxane can be subjected to chemical crosslinking reaction with the polyolefin film and the flame-retardant heat-insulating coating at the same time, so that the adhesive force of the two layers is remarkably improved, and the service life of the chemical protection fabric is further prolonged. The surface of the multilayer film fabric is coated with the flame-retardant heat-insulating coating, and particularly, the heat-insulating filler and the flame-retardant fire-resistant synergist are introduced into the flame-retardant heat-insulating coating, so that the flame-retardant heat-insulating performance of the multilayer film fabric can be remarkably improved on the basis of ensuring high chemical protection and comfort of the multilayer film fabric for chemical protective clothing; therefore, the chemical protective clothing can meet the application requirements of special scenes with high temperature, fires, even detonation threats and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical protective fabrics, and in particular to a highly flame-retardant and heat-insulating multi-layer film fabric, a preparation method thereof, and applications thereof. Background Art

[0002] Firefighters must wear chemical protective suits when fighting fires and conducting rescue operations at fires and accident sites where hazardous chemicals and corrosive substances are present. However, in addition to facing the hazards of various hazardous chemicals, these rescue operations also present the threat of high temperatures, fire, and even deflagration, and often require long hours. Therefore, chemical protective suits must not only provide chemical protection but also possess flame retardancy, heat insulation, and comfort.

[0003] High-grade chemical protective clothing products abroad are mostly made of multi-layer composite materials of rubber-coated fabric. To achieve the purpose of protection, multiple rubber materials need to be combined. They have certain flame retardant and explosion-proof functions, but their comfort is poor. High-grade chemical protective clothing based on polymer multi-layer composite materials is currently a hot research and development hotspot. Their overall comfort is better than that of rubber-coated fabric products. Introducing flame retardants into polymer film materials can also improve the flame retardant properties of the composite materials to a certain extent. However, the improvement in flame retardancy is limited, and the flame retardant and thermal insulation properties cannot meet the needs of actual applications. Therefore, it is of great significance to develop protective fabrics for chemical protective clothing with excellent protection, good comfort, and high flame retardant and thermal insulation properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a highly flame-retardant and heat-insulating multi-layer film fabric and its preparation method and application, which can improve the flame-retardant and heat-insulating properties of protective fabrics for chemical protective clothing and meet its application requirements in special application scenarios.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides a highly flame-retardant and heat-insulating multilayer film fabric, comprising a vinyl siloxane-modified multilayer film fabric and a flame-retardant and heat-insulating coating attached to the vinyl siloxane-modified multilayer film fabric; The raw materials for preparing the flame retardant and heat-insulating coating include, by mass: 100 parts of vinyl-terminated polydimethylsiloxane, 10-15 parts of hydrogenated silicone oil, 0.5-2 parts of platinum catalyst, 0.1-0.5 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 5-30 parts of flux, 10-40 parts of refractory filler, 10-20 parts of heat-insulating filler, and 0.5-5 parts of flame retardant and fire-resistant synergist; The flame retardant and fire resistant synergist is a layered ternary metal hydroxide containing rare earth elements modified by a silane coupling agent; The chemical formula of the rare earth element-containing layered ternary metal hydroxide is [M 2+ 1-x-y M 3+ x M' 3+ y (OH)2] (x+y)+ [A n- (x +y) / n ]·mH2O; Among them, M 2+ 、M 3+ and M' 3+ The corresponding metal elements are three of iron, copper, titanium, cobalt, zinc, nickel, cerium, and lanthanum, and at least one of cerium and lanthanum is contained; A n- CO3 2- ; The M 2+ 、M 3+ and M' 3+ The molar ratio is 4:1:1~5:2:1; the M 2+ 、M 3+ and M' 3+ The total number of moles of A n- The molar ratio is 1:1~2:1.

[0006] Preferably, in the vinyl silicone modified multilayer film fabric, the multilayer film fabric comprises, from the inside to the outside, an inner forming layer, a skeleton layer, a barrier layer and an outer forming layer; the inner forming layer and the outer forming layer are polyolefin films, the skeleton layer is one of aramid fabric, polyester fabric, acrylic fabric and aramid acrylic blended fabric, and the barrier layer is a polyhalogenated olefin film; In the vinylsiloxane modified multilayer film fabric, the vinylsiloxane used is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinylmethyldimethoxysilane.

[0007] Preferably, the preparation method of the vinylsiloxane modified multilayer film fabric comprises the following steps: Vinylsiloxane, an initiator and an ethanol-water mixed solvent are mixed, and the pH is adjusted to 4-5 with hydrochloric acid for hydrolysis to obtain a modified precursor solution; Spraying the modified precursor liquid onto the surface of the multilayer film fabric and performing a drying process to obtain a vinylsiloxane modified multilayer film fabric; The initiator is one of dicumyl peroxide, dibenzoyl peroxide, and tert-butyl peroxycarbonate-2-ethylhexyl ester; The mass ratio of the vinyl silicone to the multilayer film fabric is 1:50-100.

[0008] Preferably, the mass ratio of the ethanol to water is 1-2:1, the mass ratio of the vinyl siloxane to the ethanol-water mixed solvent is 1:50-1:100, and the mass ratio of the vinyl siloxane to the initiator is 20-100:1; the hydrolysis time is 2-4 h; and the drying temperature is 150-180°C.

[0009] Preferably, in the flame retardant and heat-insulating coating, the flux is one or more of boron oxide, glass powder, zinc borate and ammonium polyphosphate; The refractory filler is one or more of kaolin, montmorillonite, organic modified montmorillonite, mica powder, diatomaceous earth, calcium carbonate, talc, sepiolite, halloysite and ceramic fiber; The heat-insulating filler is one or more of hollow glass microspheres, vitrified microspheres, silica aerogel powder, expanded vermiculite and expanded perlite.

[0010] Preferably, the silane coupling agent used in the flame retardant and fire resistant synergist is one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-(triethoxysilyl)-1-propanethiol, γ-mercaptopropyltrimethoxysilane and vinyltrimethoxysilane; The preparation method of the flame retardant and fire resistant synergist comprises the following steps: Add the mixed solution of divalent metal salt and trivalent metal salt corresponding to M and alkali solution dropwise to the n- In an anionic salt solution, a coprecipitation reaction is carried out at a pH value of 8 to 11 to obtain a layered ternary metal hydroxide containing a rare earth element; The silane coupling agent is mixed with an alcohol / water mixed solution, the pH is adjusted to 3-5, a hydrolysis reaction is carried out, the pH is adjusted to 8-10, and a layered ternary metal hydroxide containing a rare earth element is added for modification to obtain a flame retardant and fire resistant synergist; The hydrolysis reaction time is 1 to 4 hours; the modification time is 1 to 2 hours.

[0011] Preferably, the thickness of the flame retardant and heat-insulating coating is 50-200 μm.

[0012] The present invention provides a method for preparing the highly flame-retardant and heat-insulating multi-layer film fabric described in the above technical solution, comprising the following steps: At room temperature, vinyl-terminated polydimethylsiloxane, hydrogenated silicone oil, platinum catalyst, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, flux, refractory filler, thermal insulation filler and flame retardant and fire resistant synergist are mixed, and vacuum degassing is performed to obtain a flame retardant and thermal insulation coating precursor solution; The flame retardant and heat-insulating coating precursor liquid is applied to the outer surface of the vinylsiloxane modified multilayer film fabric and cross-linked to obtain a highly flame retardant and heat-insulating multilayer film fabric.

[0013] Preferably, the cross-linking temperature is 150-200° C., and the cross-linking time is 1-3 h.

[0014] The present invention provides the use of the highly flame-retardant and thermal-insulating multi-layer film fabric described in the above technical solution or the highly flame-retardant and thermal-insulating multi-layer film fabric prepared by the preparation method described in the above technical solution in chemical protective clothing.

[0015] This invention provides a highly flame-retardant and thermally insulating multilayer film fabric. To improve the adhesion between the flame-retardant and thermally insulating layer and the multilayer film fabric, the fabric is modified with vinyl siloxane before the flame-retardant and thermally insulating layer is applied. Under the influence of an initiator and high temperature, the vinyl siloxane chemically crosslinks with the polyolefin film (outer forming layer). The vinyl siloxane also participates in the reaction between the vinyl silicone oil and hydrogenated silicone oil in the flame-retardant and thermally insulating layer, thereby acting as a cross-linker and enhancing adhesion between the two. The flame-retardant synergist is modified with a silane coupling agent to improve its compatibility with the silicone rubber matrix, enhancing its dispersibility and flame-retardant ceramicization efficiency. The flame retardant and fire-resistant synergist used in the present invention is a layered ternary metal hydroxide containing rare earth elements. Transition metal elements and rare earth elements can catalyze the removal of silane side chain organic groups to prevent them from forming defects during the ceramic process and affecting the strength of the ceramic body. After decomposing at high temperature, the flame retardant synergist can also form metal oxides, which participate in the ceramic process and have a reinforcing effect. Therefore, the flame retardant and fire-resistant synergist can promote the ceramic process and improve the flame retardant and fire resistant properties of the silicone rubber foam; the ternary layered metal hydroxide has better structural stability and can form a more regular lamellar structure. At the same time, it was found through experiments that with the introduction of rare earth elements such as cerium and lanthanum, the lamellar structure of the ternary layered metal hydroxide is looser and less likely to agglomerate, which improves its dispersion performance in the silicone rubber foam, increases the contact area with the silicone rubber matrix, and improves the flame retardant ceramic efficiency.

[0016] Compared with the existing technology, the highly flame-retardant and heat-insulating multi-layer film fabric of the present invention has the following advantages: (1) By coating the surface of the multi-layer film fabric with a flame retardant and heat-insulating coating, especially by introducing heat-insulating fillers and flame-retardant and fire-resistant synergists into the flame retardant and heat-insulating coating, it is possible to significantly improve the flame retardant and heat-insulating properties of the multi-layer film fabric while ensuring the high chemical protection and comfort of the chemical protective clothing, thereby enabling the chemical protective clothing to meet the application requirements of special scenarios with high temperature, fire and even explosion threats.

[0017] (2) Before applying the flame retardant and thermal insulation coating on the multilayer film fabric, vinyl siloxane modification is performed on its surface. Vinyl siloxane can simultaneously undergo chemical cross-linking reactions with the polyolefin film and the flame retardant and thermal insulation coating, thereby significantly improving the adhesion of the two layers and further improving the service life of the chemical protective fabric.

[0018] The highly flame-retardant and heat-insulating multi-layer film fabric of the present invention has excellent flame-retardant and heat-protective properties, and can meet the application requirements of special rescue scenarios such as high temperature, fire and even explosion. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 γ-aminopropyltriethoxysilane modified CuFeCe-LDH-CO3 prepared in Example 1 of the present invention -2 TEM image. DETAILED DESCRIPTION

[0020] In the present invention, unless otherwise specified, the required raw materials or reagents are commercially available products well known to those skilled in the art.

[0021] The present invention provides a highly flame-retardant and heat-insulating multilayer film fabric, comprising a vinyl siloxane-modified multilayer film fabric and a flame-retardant and heat-insulating coating attached to the vinyl siloxane-modified multilayer film fabric; The raw materials for preparing the flame retardant and heat-insulating coating include, by mass: 100 parts of vinyl-terminated polydimethylsiloxane, 10-15 parts of hydrogenated silicone oil, 0.5-2 parts of platinum catalyst, 0.1-0.5 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 5-30 parts of flux, 10-40 parts of refractory filler, 10-20 parts of heat-insulating filler, and 0.5-5 parts of flame retardant and fire-resistant synergist; The flame retardant and fire resistant synergist is a layered ternary metal hydroxide containing rare earth elements modified by a silane coupling agent; The chemical formula of the rare earth element-containing layered ternary metal hydroxide is [M 2+ 1-x-y M 3+ x M' 3+ y (OH)2] (x+y)+ [A n- (x +y) / n ]·mH2O; Among them, M 2+ 、M 3+ and M' 3+ The corresponding metal elements are three of iron, copper, titanium, cobalt, zinc, nickel, cerium, and lanthanum, and at least one of cerium and lanthanum is contained; A n- CO3 2- ; The M2+ 、M 3+ and M' 3+ The molar ratio is 4:1:1~5:2:1; the M 2+ 、M 3+ and M' 3+ The total number of moles of A n- The molar ratio is 1:1~2:1.

[0022] In the present invention, in the vinyl silicone modified multilayer film fabric, the multilayer film fabric includes an inner forming layer, a skeleton layer, a barrier layer and an outer forming layer from the inside to the outside; the inner forming layer and the outer forming layer are polyolefin films, the skeleton layer is one of aramid fabric, polyester fabric, acrylic fabric and aramid acrylic blended fabric, and the barrier layer is a polyhalogenated olefin film.

[0023] In the present invention, the polyolefin film is preferably a polypropylene film; the polyhalogenated olefin film is preferably a polyvinylidene fluoride film.

[0024] The present invention has no special limitation on the specific thickness of each layer in the multilayer film fabric, which can be adjusted according to actual needs; the present invention has no special limitation on the source and specifications of the raw materials of each layer, and commercially available products known in the art can be used.

[0025] In the multi-layer film fabric of the present invention, the inner forming layer and the outer forming layer mainly play a shaping role, the skeleton layer mainly provides mechanical strength for the fabric to enable it to have the function of being worn, and the barrier layer mainly plays a role in preventing chemical pollutants from entering.

[0026] In the present invention, the vinyl siloxane-modified multilayer film fabric preferably comprises one of vinyl triethoxysilane, vinyl trimethoxysilane, and vinyl methyl dimethoxysilane. The vinyl siloxane employed in the present invention can chemically crosslink with the polyolefin film (outer forming layer) under the influence of an initiator and high temperature. Furthermore, the vinyl siloxane can participate in the reaction between the vinyl silicone oil and hydrogenated silicone oil in the flame-retardant and thermal-insulating layer, thereby acting as a cross-linker and improving the adhesion between the flame-retardant and thermal-insulating coating and the protective fabric.

[0027] In the present invention, the preparation method of the vinylsiloxane modified multilayer film fabric comprises the following steps: Vinylsiloxane, an initiator and an ethanol-water mixed solvent are mixed, and the pH is adjusted to 4-5 with hydrochloric acid for hydrolysis to obtain a modified precursor solution; The modified precursor liquid is sprayed onto the surface of the multilayer film fabric and dried to obtain the vinylsiloxane modified multilayer film fabric.

[0028] In the present invention, the initiator is preferably one of dicumyl peroxide, dibenzoyl peroxide, and tert-butyl peroxycarbonate-2-ethylhexyl ester; the function of the initiator is to promote the crosslinking reaction between the vinyl silicone and the polyolefin film.

[0029] In the present invention, the mass ratio of the ethanol to water is preferably 1-2:1, more preferably 1:1, the mass ratio of the vinyl siloxane to the ethanol-water mixed solvent is preferably 1:50-1:100, more preferably 1:100, and the mass ratio of the vinyl siloxane to the initiator is preferably 20-100:1, more preferably 50-100:1, and further preferably 100:1.

[0030] In the present invention, the concentration of the hydrochloric acid is not particularly limited; commercially available hydrochloric acid can be used. The hydrolysis time is preferably 2-4 hours (for hydrolysis of the vinyl siloxane), more preferably 2-3 hours. After the hydrolysis, the modified precursor solution is directly sprayed without post-treatment.

[0031] The present invention has no particular limitation on the specific process of the spraying, and it can be carried out in a manner well known in the art.

[0032] In the present invention, the mass ratio of the vinyl silicone to the multilayer film fabric is preferably 1:50-100, more preferably 1:60-100, and even more preferably 1:80-100.

[0033] In the present invention, the temperature of the drying treatment is preferably 150-180°C, more preferably 160-180°C.

[0034] The raw materials for preparing the flame retardant heat-insulating coating of the present invention include 100 parts by mass of vinyl-terminated polydimethylsiloxane. The present invention has no particular limitation on the specific source and specifications of the vinyl-terminated polydimethylsiloxane, and any commercially available product known in the art can be used.

[0035] The raw materials for preparing the flame-retardant and heat-insulating coating include 10 to 15 parts, more preferably 12 to 13 parts, of hydrogenated silicone oil, based on the mass fraction of the vinyl-terminated polydimethylsiloxane. The present invention has no particular limitation on the specific source and specifications of the hydrogenated silicone oil, and any commercially available product known in the art can be used.

[0036] The flame-retardant and heat-insulating coating comprises 0.5 to 2 parts, more preferably 1 to 1.5 parts, of a platinum catalyst, based on the weight of the vinyl-terminated polydimethylsiloxane. The present invention does not specifically limit the specific source and specifications of the platinum catalyst; any commercially available product known in the art can be used.

[0037] Based on the mass fraction of the vinyl-terminated polydimethylsiloxane, the raw materials for preparing the flame retardant and heat-insulating coating include 0.1 to 0.5 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, and more preferably 0.2 to 0.3 parts.

[0038] Based on the mass fraction of the vinyl-terminated polydimethylsiloxane, the raw materials for preparing the flame-retardant and thermal-insulating coating include 5 to 30 parts of flux, more preferably 10 to 20 parts. In the present invention, the flux in the flame-retardant and thermal-insulating coating is preferably one or more of boron oxide, glass powder, zinc borate, and ammonium polyphosphate. When the flux is two or more of the above, the present invention has no special restrictions on the ratio of different types of flux, and any ratio is acceptable. The flux used in the present invention is a low-melting-point compound, the main purpose of which is to reduce the ceramicization temperature.

[0039] Based on the mass fraction of the vinyl-terminated polydimethylsiloxane, the raw materials for preparing the flame-retardant and heat-insulating coating include 10 to 40 parts of refractory fillers, and more preferably 20 to 30 parts. In the present invention, the refractory filler is preferably one or more of kaolin, montmorillonite, organically modified montmorillonite, mica powder, diatomaceous earth, calcium carbonate, talc, sepiolite, halloysite and ceramic fiber; when the refractory filler is more than two of the above, the present invention has no special restrictions on the ratio of different types of refractory fillers, and any ratio is acceptable. The refractory filler used in the present invention is mainly to improve the refractory integrity of the silicone rubber foam at high temperatures.

[0040] Based on the mass fraction of the vinyl-terminated polydimethylsiloxane, the raw materials for preparing the flame-retardant thermal insulation coating include 10 to 20 parts of thermal insulation filler, more preferably 12 to 16 parts, and even more preferably 15 parts. In the present invention, the thermal insulation filler is preferably one or more of hollow glass microspheres, vitrified microspheres, silica aerogel powder, expanded vermiculite, and expanded perlite; when the thermal insulation filler is two or more of the above, the present invention has no special restrictions on the ratio of different types of thermal insulation fillers, and any ratio is acceptable. The present invention utilizes thermal insulation fillers to reduce the thermal conductivity of the material and improve its thermal insulation performance.

[0041] Based on the mass fraction of the vinyl-terminated polydimethylsiloxane, the raw materials for preparing the flame retardant and heat-insulating coating include 0.5 to 5 parts of flame retardant and fire-resistant synergist, more preferably 0.8 to 3 parts, and even more preferably 1 to 2 parts.

[0042] In the present invention, the silane coupling agent used in the flame retardant and fire resistant synergist is preferably one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-(triethoxysilyl)-1-propanethiol, γ-mercaptopropyltrimethoxysilane, and vinyltrimethoxysilane; when the silane coupling agent is two or more of the above, the present invention has no special restrictions on the ratio of different types of silane coupling agents, and any ratio is acceptable. The present invention uses the above-mentioned silane coupling agent to modify the flame retardant synergist to improve its compatibility with the silicone rubber matrix, improve its dispersibility, and improve the flame retardant ceramicization efficiency.

[0043] In the present invention, the preparation method of the flame retardant and fire resistant synergist preferably comprises the following steps: Add the mixed solution of divalent metal salt and trivalent metal salt corresponding to M and alkali solution dropwise to the n- In an anionic salt solution, a coprecipitation reaction is carried out at a pH value of 8 to 11 to obtain a layered ternary metal hydroxide containing a rare earth element; A silane coupling agent is mixed with an alcohol / water mixed solution, the pH is adjusted to 3-5, a hydrolysis reaction is carried out, the pH is adjusted to 8-10, and a layered ternary metal hydroxide containing a rare earth element is added for modification to obtain a flame retardant and fire resistant synergist.

[0044] The present invention is to 2+ 、M 3+ and M' 3+ The corresponding divalent metal salts and trivalent metal salts and A n- The corresponding carbonate species are not particularly limited, and the corresponding salts well known in the art can be used. In the embodiment of the present invention, the nitrate corresponding to M is more preferably used, and A n- The corresponding carbonate is more preferably sodium carbonate.

[0045] The present invention has no special limitation on the range of x, y, m and n in the flame retardant and fire resistant synergist. 2 + 、M 3+ and M' 3+ Metal elements and A n- The type of transition metal element and its valence state can be determined.

[0046] In the present invention, the M 2+ 、M 3+ and M' 3+ The molar ratio of M is 4:1:1 to 5:2:1, more preferably 5:2:1; 2+ 、M 3+ and M' 3+ The total number of moles of A n-The molar ratio of 1:1 to 2:1 is 1:1 to 2:1, more preferably 1.5 to 2:1.

[0047] The present invention controls the concentration of the metal salt in the mixed solution of the divalent metal salt and the trivalent metal salt and the content of A n- There is no particular limitation on the concentration of the anionic salt solution, as long as it is completely dissolved and meets the required molar ratio.

[0048] In the present invention, the alkali solution is preferably a sodium hydroxide solution, and the concentration of the alkali solution is preferably 0.05-0.5 mol / L, more preferably 0.1-0.2 mol / L; the amount of the alkali solution is preferably such that the pH value reaches 8-11, more preferably pH=10.

[0049] In the present invention, the coprecipitation reaction temperature is preferably room temperature, and the time is preferably 2 to 6 h, more preferably 4 h.

[0050] After the coprecipitation reaction, the product is preferably aged for 12 hours, filtered, washed until neutral, dried, ground, and sieved using a 100-800 mesh screen to obtain a rare earth element-containing layered ternary metal hydroxide. The filtration and drying are not particularly limited in the present invention and can be performed according to procedures well known in the art.

[0051] In the present invention, the alcohol in the alcohol / water mixed solution is preferably ethanol; the mass ratio of the alcohol to water is preferably 10:1 to 5:1, more preferably 8 to 10:1.

[0052] In the present invention, acetic acid is preferably used to adjust the pH to 3-5 (more preferably 4), and after a hydrolysis reaction, the pH is adjusted to 8-10 (more preferably 9) using the above-mentioned sodium hydroxide solution. A layered ternary metal hydroxide containing a rare earth element is added, and the mixture is stirred at 500-1000 rpm for modification, filtered, and dried to obtain a flame retardant and fire resistant synergist.

[0053] In the present invention, the hydrolysis reaction time is preferably 1 to 4 hours, more preferably 2 to 3 hours.

[0054] In the present invention, the mass ratio of the silane coupling agent to the rare earth element-containing layered ternary metal hydroxide is preferably 1:10 to 1:20, more preferably 1:10 to 1:15.

[0055] In the present invention, the modification time is preferably 1 to 2 hours, more preferably 2 hours.

[0056] In the present invention, the thickness of the flame retardant and heat-insulating coating is preferably 50-200 μm, more preferably 100 μm.

[0057] The present invention provides a method for preparing the highly flame-retardant and heat-insulating multi-layer film fabric described in the above technical solution, comprising the following steps: At room temperature, vinyl-terminated polydimethylsiloxane, hydrogenated silicone oil, platinum catalyst, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, flux, refractory filler, thermal insulation filler and flame retardant and fire resistant synergist are mixed, and vacuum degassing is performed to obtain a flame retardant and thermal insulation coating precursor solution; The flame retardant and heat-insulating coating precursor liquid is applied to the outer surface of the vinylsiloxane modified multilayer film fabric and cross-linked to obtain a highly flame retardant and heat-insulating multilayer film fabric.

[0058] In the present invention, the mixing is preferably carried out at a stirring speed of 500 to 1200 r / min (more preferably 1000 r / min) for 15 to 30 minutes, more preferably 20 minutes. The vacuum degassing is not particularly limited in the present invention and can be carried out according to processes well known in the art.

[0059] The present invention has no particular limitation on the coating process and coating amount, and the desired coating thickness can be achieved by following a process well known in the art.

[0060] In the present invention, the cross-linking temperature is preferably 150-200° C., more preferably 150-180° C., and the time is preferably 1-3 h, more preferably 2 h; and the cross-linking is preferably performed in a forced air oven.

[0061] The present invention provides the use of the highly flame-retardant and thermally insulating multilayer film fabric described in the above technical solution, or the highly flame-retardant and thermally insulating multilayer film fabric prepared by the preparation method described in the above technical solution, in chemical protective clothing. The present invention does not specifically limit the method of application, and the application can be carried out according to methods well known in the art.

[0062] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited by the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0063] The experimental methods described in the embodiments of the present invention are conventional methods unless otherwise specified; the following reagents and raw materials are commercially available unless otherwise specified.

[0064] Sources of raw materials in the following examples: vinyl-terminated polydimethylsiloxane (viscosity 500 mPa·s, Shandong Dayi Chemical Co., Ltd.); hydrogenated silicone oil (hydrogen content 1.6%); platinum catalyst (5000 ppm, Dongguan Zhongxin Silicone Material Co., Ltd.).

[0065] Example 1

[0066] In this embodiment, the multilayer film fabric is composed of polypropylene film (thickness 100 μm), aramid filament fabric (weight 150 g / m 2 ), polyvinylidene fluoride film (thickness 50 μm), and polypropylene film (thickness 100 μm) were provided by Beijing Bangwei High-tech New Materials Technology Co., Ltd.

[0067] γ-Aminopropyltriethoxysilane modified CuFeCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of copper nitrate, 0.02 mol of ferric nitrate ninehydrate, and 0.01 mol of cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added dropwise. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain CuFeCe-LDH-CO3 -2 ; (3) Add 1 g of γ-aminopropyltriethoxysilane to a mixed solution of 100 g of ethanol and 10 g of water, adjust the pH to 4 with acetic acid, hydrolyze for 2 h, adjust the pH to 9 with sodium hydroxide solution, and add 10 g of CuFeCe-LDH-CO3 -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain γ-aminopropyltriethoxysilane-modified CuFeCe-LDH-CO3 -2 .

[0068] The preparation method of the highly flame-retardant and heat-insulating multi-layer film fabric in this embodiment is as follows: (1) Add 10 g of vinyl triethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 h to obtain a vinyl triethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:50. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150° C. to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane (viscosity 500 mPa·s), 10 g of hydrogenated silicone oil (hydrogen content 1.6%), 0.5 g of platinum catalyst (5000 ppm), 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of montmorillonite, 15 g of hollow glass microspheres and 1 g of γ-aminopropyltriethoxysilane were modified into CuFeCe-LDH-CO3. -2 The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and heat-insulating coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 100 μm, and placed in a blast oven for crosslinking at 150° C. for 2 h to obtain a highly flame retardant and heat-insulating multilayer film fabric for chemical protective clothing.

[0069] Example 2

[0070] The multilayer film fabric in this embodiment is the same as that in embodiment 1; γ-Glycidyloxypropyltrimethoxysilane modified CoFeCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of cobalt nitrate hexahydrate, 0.02 mol of ferric nitrate nonahydrate, and 0.01 mol of cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain CoFeCe-LDH-CO3 -2 ; (3) 1 g of γ-glycidyloxypropyltrimethoxysilane was added to a mixed solution of 100 g of ethanol and 10 g of water, and the pH was adjusted to 4 with acetic acid. The mixture was hydrolyzed for 2 h, and the pH was adjusted to 9 with sodium hydroxide solution. 10 g of CoFeCe-LDH-CO3 was added. -2, stirred at 500 rpm for 2 h, filtered, and dried to obtain γ-glycidyloxypropyltrimethoxysilane-modified CoFeCe-LDH-CO3 -2 .

[0071] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltrimethoxysilane and 0.5 g of dibenzoyl peroxide to a mixed solution of 250 g of ethanol and 250 g of water, adjust the pH to 4 with hydrochloric acid, and stir for 2 hours to obtain a vinyltrimethoxysilane hydrolyzate; (2) spraying vinyl trimethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl trimethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl trimethoxysilane hydrolyzate is placed in a blast oven and dried at 180°C to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 13 g of hydrogenated silicone oil, 1 g of platinum catalyst, 0.3 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 5 g of boron oxide, 10 g of kaolin, 10 g of glass microspheres and 1 g of γ-glycidyloxypropyltrimethoxysilane were modified CoFeCe-LDH-CO3 -2 The mixture was mixed in proportion, stirred at a stirring speed of 1000 r / min for 20 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor liquid; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 100 μm, and placed in a blast oven at 150° C. for 2 hours to crosslink, thereby obtaining a highly flame retardant and thermal insulation multilayer film fabric.

[0072] Example 3

[0073] The multi-layer film fabric in this embodiment is the same as that in Example 1.

[0074] γ-Methacryloxypropyltrimethoxysilane modified CuFeCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of copper nitrate, 0.02 mol of ferric nitrate ninehydrate, and 0.01 mol of cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added dropwise. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain CuFeCe-LDH-CO3 -2 ; (3) 1 g of γ-methacryloyloxypropyltrimethoxysilane was added to a mixed solution of 100 g of ethanol and 10 g of water, the pH was adjusted to 4 with acetic acid, and the mixture was hydrolyzed for 2 h. The pH was adjusted to 9 with sodium hydroxide solution, and 10 g of CuFeCe-LDH-CO3 was added. -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain γ-methacryloxypropyltrimethoxysilane-modified CuFeCe-LDH-CO3 -2 .

[0075] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinylmethyldimethoxysilane and 0.1 g of tert-butylperoxycarbonate-2-ethylhexyl ester to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinylmethyldimethoxysilane hydrolyzate; (2) spraying vinylmethyldimethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinylmethyldimethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinylmethyldimethoxysilane hydrolyzate is placed in a blast oven and dried at 150°C to obtain a vinylsiloxane-modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 15 g of hydrogenated silicone oil, 2 g of platinum catalyst, 0.5 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 30 g of glass powder, 40 g of mica powder, 20 g of silica aerogel powder (Shanghai Xuyun New Materials Technology Co., Ltd., particle size 50 μm) and 1 g of γ-methacryloyloxypropyltrimethoxysilane modified CuFeCe-LDH-CO3 were added. -2 The mixture was mixed in proportion, stirred at a stirring speed of 1200 r / min for 15 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 100 μm, and placed in a blast oven at 150° C. for 2 hours to crosslink, thereby obtaining a highly flame retardant and thermal insulation multilayer film fabric.

[0076] Example 4

[0077] The multi-layer film fabric in this embodiment is the same as that in Example 1.

[0078] 3-(Triethoxysilyl)-1-propanethiol modified ZnFeCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol zinc nitrate, 0.02 mol ferric nitrate nine hydrate, and 0.01 mol cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain ZnFeCe-LDH-CO3 -2 ; (3) 1 g of 3-(triethoxysilyl)-1-propanethiol was added to a mixed solution of 100 g of ethanol and 10 g of water, and the pH was adjusted to 4 with acetic acid. The mixture was hydrolyzed for 2 h, and the pH was adjusted to 9 with sodium hydroxide solution. 10 g of ZnFeCe-LDH-CO3 was added. -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain 3-(triethoxysilyl)-1-propanethiol-modified ZnFeCe-LDH-CO3 -2 .

[0079] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150° C. to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of ammonium polyphosphate, 30 g of diatomaceous earth, 15 g of expanded vermiculite and 0.5 g of 3-(triethoxysilyl)-1-propanethiol were added to modify ZnFeCe-LDH-CO3. -2 The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 100 μm, and placed in a blast oven at 150° C. for crosslinking for 2 h to obtain a highly flame retardant and thermal insulation multilayer film fabric.

[0080] Example 5

[0081] The multi-layer film fabric in this embodiment is the same as that in Example 1.

[0082] γ-Mercaptopropyltrimethoxysilane modified NiFeCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of nickel nitrate hexahydrate, 0.02 mol of ferric nitrate nonahydrate, and 0.01 mol of cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added dropwise. After continuing stirring for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain NiFeCe-LDH-CO3 -2 ; (3) 1 g of γ-mercaptopropyltrimethoxysilane was added to a mixed solution of 100 g of ethanol and 10 g of water, and the pH was adjusted to 4 with acetic acid. The mixture was hydrolyzed for 2 h, and the pH was adjusted to 9 with sodium hydroxide solution. 10 g of NiFeCe-LDH-CO3 was added. -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain γ-mercaptopropyltrimethoxysilane-modified NiFeCe-LDH-CO3 -2 .

[0083] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150° C. to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of calcium carbonate, 15 g of expanded perlite and 5 g of γ-mercaptopropyltrimethoxysilane modified NiFeCe-LDH-CO3 were added. -2 The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 100 μm, and placed in a blast oven at 150° C. for 2 hours to crosslink, thereby obtaining a highly flame retardant and thermal insulation multilayer film fabric.

[0084] Example 6

[0085] The multi-layer film fabric in this embodiment is the same as that in Example 1.

[0086] Vinyltrimethoxysilane modified CoFeLa-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of cobalt nitrate hexahydrate, 0.02 mol of ferric nitrate nonahydrate, and 0.01 mol of lanthanum nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added dropwise. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain CoFeLa-LDH-CO3 -2 ; (3) 1 g of vinyltrimethoxysilane was added to a mixed solution of 100 g of ethanol and 10 g of water, and the pH was adjusted to 4 with acetic acid. The mixture was hydrolyzed for 2 h, and the pH was adjusted to 9 with sodium hydroxide solution. 10 g of CoFeLa-LDH-CO3 was added. -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain vinyltrimethoxysilane-modified CoFeLa-LDH-CO3 -2 .

[0087] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150° C. to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of talc, 15 g of hollow glass microspheres and 1 g of vinyltrimethoxysilane-modified CoFeLa-LDH-CO3 were added. -2The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2) with a coating thickness of 50 μm, and is placed in a blast oven at 150° C. for crosslinking for 2 hours to obtain a highly flame retardant and thermal insulation multilayer film fabric.

[0088] Example 7

[0089] The multi-layer film fabric in this embodiment is the same as that in Example 1.

[0090] Vinyltrimethoxysilane modified CuTiCe-LDH-CO3 -2 The preparation method is: (1) Weigh 0.05 mol of copper nitrate, 0.02 mol of titanium nitrate, and 0.01 mol of cerium nitrate hexahydrate, respectively, and dissolve them in 500 mL of deionized water to prepare a divalent / trivalent metal salt mixed solution; weigh 0.1 mol of sodium hydroxide and dissolve it in 1 L of deionized water to prepare a sodium hydroxide solution; weigh 0.04 mol of sodium carbonate and dissolve it in 500 mL of deionized water to prepare an anion salt solution; (2) Under stirring conditions at room temperature, the divalent / trivalent metal salt mixed solution and sodium hydroxide solution were added dropwise to the anion salt solution, and the pH value was monitored in real time to keep the pH value of the mixed solution constant at 10 until the divalent / trivalent metal salt mixed solution was added. After continuing to stir for 4 h, stirring was stopped and aged for 12 h. The aged solution was filtered, washed to neutrality, dried and ground, and sieved with a 100-800 mesh sieve to obtain CuTiCe-LDH-CO3 -2 ; (3) 1 g of vinyl trimethoxysilane was added to a mixed solution of 100 g of ethanol and 10 g of water by mass ratio, the pH was adjusted to 4 with acetic acid, hydrolyzed for 2 h, the pH was adjusted to 9 with sodium hydroxide solution, and 10 g of CuTiCe-LDH-CO3 was added. -2 , stirred at 500 rpm for 2 h, filtered, and dried to obtain vinyltrimethoxysilane-modified CuTiCe-LDH-CO3 -2 .

[0091] The preparation method of the highly flame-retardant and heat-insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150° C. to obtain a vinyl siloxane modified multilayer film fabric; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of sepiolite, 15 g of hollow glass microspheres and 1 g of vinyltrimethoxysilane-modified CuTiCe-LDH-CO3 were added. -2 The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (4) The flame retardant and thermal insulation coating precursor prepared in step (3) is coated on the outer surface of the vinylsiloxane modified multilayer film fabric that has been completely dried in step (2), with a coating thickness of 200 μm, and placed in a blast oven at 150° C. for crosslinking for 2 h to obtain a highly flame retardant and thermal insulation multilayer film fabric.

[0092] Comparative Example 1

[0093] The multilayer film fabric in Example 1 was used as Comparative Example 1 without coating.

[0094] Comparative Example 2

[0095] The multilayer film fabric used is the same as that in Example 1, and the preparation method of the flame retardant and heat insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150°C; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, and 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane were mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame retardant thermal insulation coating precursor solution; (4) The flame retardant and heat-insulating coating precursor prepared in step (3) is coated on the outer surface of the multilayer film fabric that has been completely dried in step (2) to a thickness of 100 μm, and is placed in a blast oven at 150° C. for cross-linking for 2 hours to obtain a flame retardant and heat-insulating multilayer film fabric.

[0096] Comparative Example 3

[0097] The multilayer film fabric used is the same as that in Example 1, and the preparation method of the flame retardant and heat insulating multilayer film fabric is as follows: (1) Add 10 g of vinyltriethoxysilane and 0.1 g of diisopropylbenzene peroxide to a mixed solution of 500 g of ethanol and 500 g of water, adjust the pH to 5 with hydrochloric acid, and stir for 2 hours to obtain a vinyltriethoxysilane hydrolyzate; (2) spraying vinyl triethoxysilane hydrolyzate onto the surface of the multilayer film fabric, with the mass ratio of vinyl triethoxysilane to the multilayer film fabric being 1:100. After the spraying is complete, the multilayer film fabric sprayed with the vinyl triethoxysilane hydrolyzate is placed in a blast oven and dried at 150°C; (3) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of montmorillonite, and 15 g of hollow glass microspheres were mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to prepare a flame retardant thermal insulation coating precursor solution; (4) The flame retardant and heat-insulating coating precursor prepared in step (3) is coated on the outer surface of the multilayer film fabric that has been completely dried in step (2) to a thickness of 100 μm, and is placed in a blast oven at 150° C. for cross-linking for 2 hours to obtain a flame retardant and heat-insulating multilayer film fabric.

[0098] Comparative Example 4

[0099] The multilayer film fabric in this embodiment is the same as that in embodiment 1; γ-Aminopropyltriethoxysilane modified CuFeCe-LDH-CO3 -2 The preparation method is the same as that of Example 1; The preparation method of the flame retardant and heat-insulating multilayer film fabric is as follows: (1) At room temperature, 100 g of vinyl-terminated polydimethylsiloxane, 10 g of hydrogenated silicone oil, 0.5 g of platinum catalyst, 0.1 g of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 20 g of zinc borate, 30 g of montmorillonite, 15 g of hollow glass microspheres and 1 g of γ-aminopropyltriethoxysilane were modified into CuFeCe-LDH-CO3. -2The mixture was mixed in proportion, stirred at a stirring speed of 500 r / min for 30 minutes, and vacuum-defoamed to obtain a flame-retardant thermal insulation coating precursor solution; (2) The flame retardant and heat insulating coating precursor liquid prepared in step (1) is coated on the outer surface of the multilayer film fabric with a coating thickness of 100 μm, and is placed in a blast oven at 150° C. for crosslinking for 2 h to obtain a flame retardant and heat insulating multilayer film fabric.

[0100] Characterization and performance testing

[0101] 1) Figure 1 γ-aminopropyltriethoxysilane modified CuFeCe-LDH-CO3 prepared in Example 1 of the present invention -2 TEM image of Figure 1 It can be seen that the ternary LDH formed by the introduction of rare earth elements has good overall dispersion and no obvious agglomeration phenomenon occurs.

[0102] 2) The flame retardant and thermal protective properties of the fabrics prepared in Examples 1-7 and Comparative Examples 1-4 were tested. The limiting oxygen index was tested in accordance with GB / T 5454-1997, the TPP value was tested in accordance with GB 8965.1-2020, and the adhesion strength was tested in accordance with GB / T 532-2008. The results are shown in Table 1.

[0103] Table 1 Limiting oxygen index, TPP value and adhesion strength of fabrics prepared in Examples 1 to 7 and Comparative Examples 1 to 4

[0104] From the results in Table 1, it can be seen that the flame retardant and thermal protection properties of the multilayer membrane fabric in Comparative Example 1 that has not been subjected to coating modification treatment are poor; compared with Comparative Example 1, the flame retardant and thermal protection properties of Comparative Example 2 are improved, but the improvement is limited, indicating that the silicone coating without the addition of flame retardant ceramic fillers has limited effect on it; the test results of Comparative Example 3 and Examples 1 to 5 show that the introduction of flux, refractory filler, thermal insulation filler and flame retardant and fire resistant synergist can significantly improve the flame retardant and thermal protection properties of the multilayer membrane fabric, and its flame retardant and thermal protection properties gradually increase with the increase of filler content. This is mainly because the flux and refractory filler can form a ceramic-like dense carbon layer at high temperature, which effectively hinders the spread of flame and heat, and the thermal insulation filler can play a better thermal insulation role. The flame retardant and fire-resistant synergist has the effect of reducing the speed of heat propagation, and the transition metal (including rare earth elements) in the flame retardant and fire-resistant synergist can play the role of catalysis, carbonization, dilution of combustible gas, etc., which can play a synergistic flame retardant role, and further improve the flame retardant and thermal protection properties of the fabric; it can be seen from the test results of Example 1 and Examples 6~7 that with the increase of the thickness of the flame retardant and heat-insulating coating, the flame retardant and thermal protection properties of the multilayer film fabric are also gradually improved. This is mainly because with the increase of thickness, the ceramic-like dense carbon layer formed at high temperature can more effectively prevent fire and insulate heat; it can be seen from the test results of Comparative Example 4 and Example 1 that the sample without modification of the multilayer film fabric has a low adhesion strength, indicating that siloxane modification can significantly improve the adhesion strength of the multilayer film fabric.

[0105] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A highly flame-retardant and heat-insulating multi-layer film fabric, characterized in that: It comprises a vinyl siloxane modified multilayer film fabric and a flame retardant heat-insulating coating attached to the vinyl siloxane modified multilayer film fabric; The raw materials for preparing the flame retardant and heat-insulating coating include, by mass: 100 parts of vinyl-terminated polydimethylsiloxane, 10-15 parts of hydrogenated silicone oil, 0.5-2 parts of platinum catalyst, 0.1-0.5 parts of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 5-30 parts of flux, 10-40 parts of refractory filler, 10-20 parts of heat-insulating filler, and 0.5-5 parts of flame retardant and fire-resistant synergist; The flame retardant and fire resistant synergist is a layered ternary metal hydroxide containing rare earth elements modified by a silane coupling agent; The chemical formula of the rare earth element-containing layered ternary metal hydroxide is [M 2+ 1-x-y M 3+ x M' 3+ y (OH)2] (x+y)+ [A n- (x +y) / n ]·mH2O; Among them, M 2+ 、M 3+ and M' 3+ The corresponding metal elements are three of iron, copper, titanium, cobalt, zinc, nickel, cerium, and lanthanum, and at least one of cerium and lanthanum is contained; A n- CO3 2- ; The M 2+ 、M 3+ and M' 3+ The molar ratio is 4:1:1~5:2:1; the M 2+ 、M 3+ and M' 3+ The total number of moles of A n- The molar ratio is 1:1~2:

1.

2. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 1, characterized in that: In the vinyl silicone modified multilayer film fabric, the multilayer film fabric comprises, from the inside to the outside, an inner forming layer, a skeleton layer, a barrier layer and an outer forming layer; the inner forming layer and the outer forming layer are polyolefin films, the skeleton layer is one of aramid fabric, polyester fabric, acrylic fabric and aramid acrylic blended fabric, and the barrier layer is a polyhalogenated olefin film; In the vinylsiloxane modified multilayer film fabric, the vinylsiloxane used is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinylmethyldimethoxysilane.

3. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 1, characterized in that: The preparation method of the vinylsiloxane modified multilayer film fabric comprises the following steps: Vinylsiloxane, an initiator and an ethanol-water mixed solvent are mixed, and the pH is adjusted to 4-5 with hydrochloric acid for hydrolysis to obtain a modified precursor solution; Spraying the modified precursor liquid onto the surface of the multilayer film fabric and performing a drying process to obtain a vinylsiloxane modified multilayer film fabric; The initiator is one of dicumyl peroxide, dibenzoyl peroxide, and tert-butyl peroxycarbonate-2-ethylhexyl ester; The mass ratio of the vinyl silicone to the multilayer film fabric is 1:50-100.

4. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 3, characterized in that: The mass ratio of ethanol to water is 1-2:1, the mass ratio of vinyl siloxane to ethanol-water mixed solvent is 1:50-1:100, and the mass ratio of vinyl siloxane to initiator is 20-100:1; the hydrolysis time is 2-4 hours; and the drying temperature is 150-180°C.

5. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 1, characterized in that: In the flame retardant and heat-insulating coating, the flux is one or more of boron oxide, glass powder, zinc borate and ammonium polyphosphate; The refractory filler is one or more of kaolin, montmorillonite, organic modified montmorillonite, mica powder, diatomaceous earth, calcium carbonate, talc, sepiolite, halloysite and ceramic fiber; The heat-insulating filler is one or more of hollow glass microspheres, vitrified microspheres, silica aerogel powder, expanded vermiculite and expanded perlite.

6. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 1, characterized in that: The silane coupling agent used in the flame retardant and fire resistant synergist is one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-(triethoxysilyl)-1-propanethiol, γ-mercaptopropyltrimethoxysilane and vinyltrimethoxysilane; The preparation method of the flame retardant and fire resistant synergist comprises the following steps: Add the mixed solution of divalent metal salt and trivalent metal salt corresponding to M and alkali solution dropwise to the n- In an anionic salt solution, a coprecipitation reaction is carried out at a pH value of 8 to 11 to obtain a layered ternary metal hydroxide containing a rare earth element; The silane coupling agent is mixed with an alcohol / water mixed solution, the pH is adjusted to 3-5, a hydrolysis reaction is carried out, the pH is adjusted to 8-10, and a layered ternary metal hydroxide containing a rare earth element is added for modification to obtain a flame retardant and fire resistant synergist; The hydrolysis reaction time is 1 to 4 hours; the modification time is 1 to 2 hours.

7. The highly flame-retardant and heat-insulating multi-layer membrane fabric according to claim 1, characterized in that: The thickness of the flame retardant and heat-insulating coating is 50-200 μm.

8. The method for preparing the highly flame-retardant and heat-insulating multi-layer film fabric according to any one of claims 1 to 7, characterized in that: The following steps are involved: At room temperature, vinyl-terminated polydimethylsiloxane, hydrogenated silicone oil, platinum catalyst, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, flux, refractory filler, thermal insulation filler and flame retardant and fire resistant synergist are mixed, and vacuum degassing is performed to obtain a flame retardant and thermal insulation coating precursor solution; The flame retardant and heat-insulating coating precursor liquid is applied to the outer surface of the vinylsiloxane modified multilayer film fabric and cross-linked to obtain a highly flame retardant and heat-insulating multilayer film fabric.

9. The preparation method according to claim 8, characterized in that The cross-linking temperature is 150-200° C., and the cross-linking time is 1-3 h.

10. Use of the highly flame-retardant and thermal-insulating multilayer film fabric according to any one of claims 1 to 7 or the highly flame-retardant and thermal-insulating multilayer film fabric prepared by the preparation method according to any one of claims 8 to 9 in chemical protective clothing.

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