Flame-retardant and heat-insulating fabric for fire-fighting clothing and its preparation process

Abstract

The present invention provides a flame-retardant and heat-insulating fabric for fire-fighting clothing and a preparation process thereof, which belongs to the technical field of fire-fighting fabrics; the preparation process includes the following steps: preparing coated modified ammonium polyphosphate; modifying expanded perlite; preparing a flame-retardant outer layer fabric; preparing a heat-insulating core layer fabric; preparing an antibacterial inner layer fabric; and bonding. The flame-retardant and heat-insulating fabric for fire-fighting clothing of the present invention includes a flame-retardant outer layer fabric, a heat-insulating core layer fabric, and an antibacterial inner layer fabric, wherein the ammonium polyphosphate is first dispersed in deionized water, and polyethyleneimine is added under acidic conditions, and the amino groups on the polyethyleneimine are first subjected to an ion exchange reaction with the ammonium ions of the ammonium polyphosphate to preliminarily coat the ammonium polyphosphate, and then a hydroxyethylene diphosphonic acid solution is added to carry out a salt-forming reaction to prepare a coated modified ammonium polyphosphate with a core-shell structure. After the coated modified ammonium polyphosphate is mixed with polyester powder and granulated to prepare the flame-retardant outer layer fabric, the flame retardant properties of the flame-retardant outer layer fabric can be effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of fire-fighting fabrics, and in particular to a flame-retardant and heat-insulating fabric for fire-fighting clothing and a preparation process thereof. Background Art

[0002] Fire is a disaster that poses a serious threat to human life, property and social order. Firefighters need to face extreme high temperature environments during firefighting and rescue. Therefore, the flame retardant and heat-insulating properties of firefighting clothing are crucial.

[0003] Polyester fiber fabrics have excellent thermal insulation, wear resistance, and wrinkle resistance, and can withstand the friction and mechanical stress of firefighting operations. They are also not easily deformed after washing, ensuring that firefighting clothing maintains its long-term structural integrity. Therefore, they can be used in firefighting clothing. Ordinary polyester fibers are flammable and usually require the addition of flame retardants to enhance their flame retardancy. Ammonium polyphosphate is an inorganic phosphorus compound flame retardant containing both P and N elements. It is heat-resistant and flame-retardant, and does not generate harmful gases during combustion. It can replace halogen and organophosphine flame retardants in polymer materials. However, when used alone, ammonium polyphosphate has poor dispersibility, is prone to precipitation, and has poor compatibility with the matrix. Therefore, it is difficult to ensure its flame retardancy by directly adding ammonium polyphosphate to polyester fiber fabrics.

[0004] In addition, cotton fabrics have good moisture absorption and breathability. Using them as the inner material of fire suits can improve the comfort of fire suits. When firefighters are rescuing for a long time, the heat and sweat generated by their own bodies can easily breed bacteria, reducing the comfort of wearing. Cotton fabrics usually do not have antibacterial properties. To make cotton fabrics have antibacterial properties, they usually need to be antibacterial finished. However, the current antibacterial finishing principle of cotton fabrics is that antibacterial agents are adsorbed onto the surface of cotton fabrics through van der Waals forces or hydrogen bonds, but the adsorption amount will be significantly reduced after washing, resulting in poor antibacterial durability of cotton fabrics.

[0005] Based on this, we proposed a flame-retardant and thermal-insulating fabric with antibacterial durability for firefighting clothing and its preparation process to extend the service life of firefighting clothing. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a flame retardant and heat-insulating fabric for firefighting clothing and a preparation process thereof.

[0007] A flame retardant and heat-insulating fabric for fire-fighting clothing, comprising a flame retardant outer layer fabric, a heat-insulating core layer fabric and an antibacterial inner layer fabric;

[0008] The flame retardant outer fabric is woven from modified polyester fiber yarns, wherein the raw materials for preparing the modified polyester fiber yarns include polyester powder, coated modified ammonium polyphosphate, modified expanded perlite and polyester chips;

[0009] The thermal insulation core fabric is blended with synthetic fiber and aramid fiber in a mass ratio of 1:(2-3), wherein the raw materials for preparing the synthetic fiber include polyvinyl chloride, ethylene propylene rubber, sodium stearate, bamboo charcoal powder, sepiolite nanofiber, KH-550 coupling agent, cellulose ester and sodium alginate;

[0010] The antibacterial inner layer fabric is prepared by soaking cotton grey cloth in a modified treatment liquid, wherein the raw materials for preparing the modified treatment liquid include ε-polylysine hydrochloride, epoxidized linseed oil, sodium hydroxide solution, Tween 80, glacial acetic acid, citric acid and deionized water.

[0011] A preparation process of flame-retardant and heat-insulating fabric for fire-fighting clothing, characterized by comprising the following steps:

[0012] S1: Preparation of coated modified ammonium polyphosphate

[0013] The ammonium polyphosphate is dispersed in deionized water, polyethyleneimine is added for preliminary coating, and then a hydroxyethylene diphosphonic acid solution is added for reaction to obtain coated modified ammonium polyphosphate;

[0014] S2: Modified expanded perlite

[0015] Dissolving γ-aminopropyltriethoxysilane in an ethanol solution, adding expanded perlite to react, and then adding dimethyl hydroxymethylphosphonate to react to obtain modified expanded perlite;

[0016] S3: Preparation of flame retardant outer fabric

[0017] The polyester powder, the coated modified ammonium polyphosphate and the modified expanded perlite are mixed and granulated to prepare a modified polyester masterbatch, which is then mixed with polyester chips to prepare modified polyester fiber yarn, which is then plain woven to prepare a flame retardant outer fabric;

[0018] S4: Preparation of thermal insulation core fabric

[0019] Polyvinyl chloride, ethylene propylene rubber, sodium stearate, bamboo charcoal powder and sepiolite nanofibers are mixed uniformly and heated to a molten state, and then KH-550 coupling agent, cellulose ester and sodium alginate are added, mixed uniformly and extruded to obtain synthetic fibers, which are then blended with aramid fibers to obtain a thermal insulation core fabric.

[0020] S5: Preparation of antibacterial inner fabric

[0021] An ε-polylysine hydrochloride solution and an epoxidized linseed oil emulsion are prepared separately, and then mixed and heated to react to obtain modified ε-polylysine hydrochloride. After dissolving, citric acid is added and the cotton fabric is treated to obtain an antibacterial inner layer fabric.

[0022] S6: Bonding

[0023] The flame-retardant outer layer fabric, the heat-insulating core layer fabric and the antibacterial inner layer fabric are sequentially bonded to obtain the flame-retardant heat-insulating fabric.

[0024] Furthermore, S1 specifically includes the following steps:

[0025] S1.1: Add ammonium polyphosphate to deionized water at a solid-liquid ratio of 1 g:(20-30) mL, ultrasonically disperse for 20-30 min, and then add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 5-6 to obtain an ammonium polyphosphate dispersion.

[0026] S1.2: Add polyethyleneimine to the above ammonium polyphosphate dispersion and stir at a constant temperature of 50-60°C for 2-3 hours to obtain a preliminary coated ammonium polyphosphate mixture;

[0027] S1.3: Dissolve hydroxyethylene diphosphonic acid in deionized water at a solid-liquid ratio of 1 g: (30-40) mL to obtain a hydroxyethylene diphosphonic acid solution, then add the hydroxyethylene diphosphonic acid solution to the above-mentioned preliminary coated ammonium polyphosphate mixture, and add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 4-5, then continue to keep warm and stir for 3-4 hours, centrifuge, filter, wash and dry to obtain the coated modified ammonium polyphosphate.

[0028] Furthermore, S2 specifically includes the following steps:

[0029] S2.1: Add γ-aminopropyltriethoxysilane to a 60% ethanol solution at a solid-liquid ratio of 1 g:(10-12) mL, stir thoroughly to dissolve, and then add acetic acid to adjust the pH to 4-5 to obtain a γ-aminopropyltriethoxysilane solution;

[0030] S2.2: Ultrasonic clean the expanded perlite with deionized water and dry to constant weight. Then, add the γ-aminopropyltriethoxysilane solution described above at a solid-to-liquid ratio of 1 g:(5-6) mL. Heat and stir at 70-80°C for 3-4 hours to obtain an amination-treated expanded perlite solution.

[0031] S2.3: Add dimethyl hydroxymethylphosphonate to the above-mentioned amino-modified expanded perlite solution at a solid-liquid ratio of 1 g: (12-16) mL, and add 0.1 mol / L hydrochloric acid to adjust the pH to 2-3. Heat and stir at 80-90°C for 10-12 hours. After cooling, centrifuge and filter, wash until neutral, and dry to obtain modified expanded perlite.

[0032] Furthermore, S3 specifically includes the following steps:

[0033] S3.1: Evenly mix the polyester powder, the coated modified ammonium polyphosphate prepared in step S1.3, and the modified expanded perlite prepared in step S2.3, and granulate the mixture by extrusion through a twin-screw extruder to obtain a modified polyester masterbatch;

[0034] S3.2: The modified polyester masterbatch and polyester chips are mixed in a mass ratio of 1:(5-7) and spun to obtain modified polyester fiber yarn, which is then plain woven to obtain a flame retardant outer fabric.

[0035] Furthermore, S5 specifically includes the following steps:

[0036] S5.1: Add ε-polylysine hydrochloride to deionized water at a solid-liquid ratio of 1 g:(10-20) mL, stir thoroughly to dissolve, and then add 0.1 mol / L sodium hydroxide solution to adjust the pH to 10-11 to obtain an ε-polylysine hydrochloride solution;

[0037] S5.2: Add Tween 80 to deionized water at a mass ratio of 1:(10-15) and stir thoroughly to dissolve. Then, add epoxidized linseed oil having an epoxy value of 6-8% at an oil-to-water ratio of 1:(4-6) and emulsify at 1000-1500 rpm for 20-30 minutes to obtain an epoxidized linseed oil emulsion.

[0038] S5.3: Add the epoxidized linseed oil emulsion to the ε-polylysine hydrochloride solution at a mass ratio of 1:(6-8), heat and stir at 50-60°C for 4-6 hours, then adjust the pH to neutral by adding glacial acetic acid. Purify by dialysis and freeze-dry to obtain modified ε-polylysine hydrochloride.

[0039] S5.4: Dissolve the modified ε-polylysine hydrochloride in deionized water to prepare a 1-3% by weight solution, then add 0.2-0.3 wt% of citric acid catalyst, and stir to mix thoroughly to obtain a modified treatment solution;

[0040] S5.5: Immerse the cotton fabric in the above-mentioned modified treatment solution at a bath ratio of 1:(15-25), and heat and soak it at 50-60°C for 1-2 hours. After taking it out, wash it with water and dry it to obtain the antibacterial inner layer fabric.

[0041] Furthermore, the added amount of polyethyleneimine is 15-20% of the mass of ammonium polyphosphate.

[0042] Furthermore, the added amount of hydroxyethylene diphosphonic acid is 40-50% of the mass of polyethylene imine.

[0043] Furthermore, the mass ratio of the polyester powder, the coated modified ammonium polyphosphate and the modified expanded perlite is (35-45):(3-5):1.

[0044] Furthermore, the raw materials of the synthetic fiber include, by mass, 30-40 parts of polyvinyl chloride, 10-20 parts of ethylene propylene rubber, 2-3 parts of sodium stearate, 3-5 parts of bamboo charcoal powder, 2-4 parts of sepiolite nanofibers, 2-4 parts of KH-550 coupling agent, 1-2 parts of cellulose ester and 1-2 parts of sodium alginate.

[0045] Compared with the prior art, the present invention has at least the following beneficial effects:

[0046] 1. The flame-retardant and heat-insulating fabric for firefighting clothing of the present invention is formed by bonding a flame-retardant outer layer fabric, a heat-insulating core layer fabric, and an antibacterial inner layer fabric. Specifically, ammonium polyphosphate is first dispersed in deionized water, and polyethyleneimine is added under acidic conditions. The amino groups on the polyethyleneimine are first subjected to an ion exchange reaction with the ammonium ions of the ammonium polyphosphate to preliminarily coat the ammonium polyphosphate. Then, a hydroxyethylene diphosphonic acid solution is added to carry out a salt-forming reaction to prepare a coated modified ammonium polyphosphate having a core-shell structure. Since the ammonium polyphosphate is modified by hydroxyethylene diphosphonic acid and polyethyleneimine, the compatibility of the ammonium polyphosphate with the polyester matrix can be effectively improved, and the problem of reduced flame retardant properties of the flame-retardant outer layer fabric due to precipitation of ammonium polyphosphate is improved. Therefore, after the coated modified ammonium polyphosphate is mixed with polyester powder and granulated to prepare the flame-retardant outer layer fabric, the flame retardant properties of the flame-retardant outer layer fabric can be effectively improved.

[0047] 2. In the present invention, the surface of expanded perlite is first modified with γ-aminopropyltriethoxysilane to introduce amino groups onto its surface. Then, dimethyl hydroxymethylphosphonate is added. On the one hand, the phosphonate groups in the dimethyl hydroxymethylphosphonate electrostatically attract the protonated amino groups on the surface of the amino-treated expanded perlite in an acidic environment. On the other hand, the hydroxymethyl groups in the dimethyl hydroxymethylphosphonate form a hydrogen bond network with the hydroxyl groups on the surface of the expanded perlite, thereby grafting the dimethyl hydroxymethylphosphonate onto the surface of the expanded perlite and modifying it. This improves the dispersibility of the expanded perlite in the polyester matrix and prevents agglomeration. Furthermore, mixing the modified expanded perlite with polyester powder and granulating it into modified polyester fiber yarn effectively improves the thermal stability of the modified polyester fiber yarn and further enhances the flame retardancy and thermal insulation properties of the resulting flame-retardant outer fabric.

[0048] 3. In the present invention, an ε-polylysine hydrochloride solution and an epoxidized linseed oil emulsion are first prepared separately, and then the epoxidized linseed oil emulsion is added to the ε-polylysine hydrochloride solution, and the reaction is carried out by heating and stirring. An epoxy group in the epoxidized linseed oil reacts with an amino group of the ε-polylysine hydrochloride to modify the ε-polylysine hydrochloride. After the modified ε-polylysine hydrochloride is subjected to a modification treatment and the cotton grey fabric is treated, the remaining epoxy groups of the epoxidized linseed oil in the modified ε-polylysine hydrochloride react with the hydroxyl groups of the cotton fibers to generate ether bonds and hydroxyl groups, forming a cross-linked network, thereby improving the binding force between the antibacterial ε-polylysine hydrochloride and the cotton grey fabric, thereby achieving the effect of improving the antibacterial durability of the prepared antibacterial inner layer fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable one skilled in the relevant art to make and use the present disclosure.

[0050] Figure 1 This is a flow chart of the preparation process of the flame-retardant and heat-insulating fabric for firefighting clothing used in an embodiment of the present invention. DETAILED DESCRIPTION

[0051] The flame retardant and heat-insulating fabric for firefighting clothing and its preparation process provided by the present invention are described in detail below with reference to the accompanying drawings and specific embodiments.

[0052] Example 1

[0053] A preparation process of flame retardant and heat insulating fabric for fire fighting clothing, such as Figure 1 As shown, the following steps are included:

[0054] S1: Preparation of coated modified ammonium polyphosphate

[0055] S1.1: Add ammonium polyphosphate to deionized water at a solid-liquid ratio of 1 g:20 mL, ultrasonically disperse for 20 min, and then add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 5 to obtain an ammonium polyphosphate dispersion.

[0056] S1.2: Add polyethyleneimine to the above ammonium polyphosphate dispersion and stir at 50°C for 2 hours to obtain a preliminary coated ammonium polyphosphate mixture, wherein the amount of polyethyleneimine added is 15% of the mass of the ammonium polyphosphate;

[0057] S1.3: Dissolve hydroxyethylene diphosphonic acid in deionized water at a solid-liquid ratio of 1 g:30 mL to obtain a hydroxyethylene diphosphonic acid solution, then add the hydroxyethylene diphosphonic acid solution to the preliminary coated ammonium polyphosphate mixture, and adjust the pH to 4 by adding 0.1 mol / L dilute hydrochloric acid. Continue to heat and stir for 3 hours, centrifuge, filter, wash, and dry to obtain a coated modified ammonium polyphosphate, wherein the amount of hydroxyethylene diphosphonic acid added is 40% of the mass of the polyethyleneimine;

[0058] S2: Modified expanded perlite

[0059] S2.1: Add γ-aminopropyltriethoxysilane to a 60% ethanol solution at a solid-liquid ratio of 1 g:10 mL, stir thoroughly to dissolve, and then add acetic acid to adjust the pH to 4 to obtain a γ-aminopropyltriethoxysilane solution.

[0060] S2.2: Ultrasonic clean the expanded perlite with deionized water and dry to constant weight. Then, add the above-mentioned γ-aminopropyltriethoxysilane solution at a solid-liquid ratio of 1 g:5 mL. Heat and stir at 70°C for 3-4 hours to obtain an amination-treated expanded perlite solution.

[0061] S2.3: Add dimethyl hydroxymethylphosphonate to the above-mentioned amino-modified expanded perlite solution at a solid-liquid ratio of 1 g:12 mL, and adjust the pH to 2 by adding 0.1 mol / L hydrochloric acid. Heat and stir the mixture at 80°C for 10 h. After cooling, centrifuge and filter, wash until neutral, and dry to obtain modified expanded perlite.

[0062] S3: Preparation of flame retardant outer fabric

[0063] S3.1: Evenly mix the polyester powder, the coated modified ammonium polyphosphate prepared in step S1.3, and the modified expanded perlite prepared in step S2.3 in a mass ratio of 35:3:1, and extrude and granulate the mixture through a twin-screw extruder to obtain a modified polyester masterbatch;

[0064] S3.2: Mixing the modified polyester masterbatch with polyester chips in a mass ratio of 1:5 and spinning the mixture to obtain modified polyester fiber yarn, which is then plain-woven to obtain a flame-retardant outer fabric.

[0065] S4: Preparation of thermal insulation core fabric

[0066] 30 parts by mass of polyvinyl chloride, 10 parts by mass of ethylene propylene rubber, 2 parts by mass of sodium stearate, 3 parts by mass of bamboo charcoal powder and 2 parts by mass of sepiolite nanofibers are mixed uniformly and heated to a molten state, and then 2 parts by mass of KH-550 coupling agent, 1 part by mass of cellulose ester and 1 part by mass of sodium alginate are added, and the mixture is further mixed uniformly and extruded to obtain synthetic fibers, which are then blended with aramid fibers in a mass ratio of 1:2 to obtain a thermal insulation core fabric;

[0067] S5: Preparation of antibacterial inner fabric

[0068] S5.1: Add ε-polylysine hydrochloride to deionized water at a solid-liquid ratio of 1 g:10 mL, stir thoroughly to dissolve, and then add 0.1 mol / L sodium hydroxide solution to adjust the pH to 10 to obtain an ε-polylysine hydrochloride solution.

[0069] S5.2: Add Tween 80 to deionized water at a mass ratio of 1:10 and stir thoroughly to dissolve. Then, add epoxidized linseed oil with an epoxide value of 6% at an oil-to-water ratio of 1:4 and emulsify at 1000 rpm for 20 minutes to obtain an epoxidized linseed oil emulsion.

[0070] S5.3: Add the epoxidized linseed oil emulsion to the ε-polylysine hydrochloride solution at a mass ratio of 1:6, heat and stir at 50°C for 4 h, then adjust the pH to neutral by adding glacial acetic acid. Purify by dialysis and freeze-dry to obtain modified ε-polylysine hydrochloride.

[0071] S5.4: Dissolve the modified ε-polylysine hydrochloride in deionized water to prepare a 1% solution by weight, then add 0.2% by weight of citric acid as a catalyst, and stir to mix thoroughly to obtain a modified solution;

[0072] S5.5: Immerse the cotton fabric in the modified treatment solution at a bath ratio of 1:15 and heat at 50°C for 1 hour. After removal, wash and dry the fabric to obtain an antibacterial inner layer fabric.

[0073] S6: Bonding

[0074] The flame-retardant outer layer fabric, the heat-insulating core layer fabric and the antibacterial inner layer fabric are sequentially bonded to obtain the flame-retardant heat-insulating fabric.

[0075] Example 2

[0076] A preparation process of flame retardant and heat insulating fabric for fire fighting clothing, such as Figure 1 As shown, the following steps are included:

[0077] S1: Preparation of coated modified ammonium polyphosphate

[0078] S1.1: Add ammonium polyphosphate to deionized water at a solid-liquid ratio of 1 g:25 mL, ultrasonically disperse for 25 min, and then add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 5.5 to obtain an ammonium polyphosphate dispersion.

[0079] S1.2: Add polyethyleneimine to the above ammonium polyphosphate dispersion and stir at 55°C for 2.5 hours to obtain a preliminary coated ammonium polyphosphate mixture, wherein the amount of polyethyleneimine added is 17.5% by weight of the ammonium polyphosphate;

[0080] S1.3: Dissolve hydroxyethylene diphosphonic acid in deionized water at a solid-liquid ratio of 1 g:35 mL to obtain a hydroxyethylene diphosphonic acid solution, then add the hydroxyethylene diphosphonic acid solution to the preliminary coated ammonium polyphosphate mixture, and adjust the pH to 4.5 by adding 0.1 mol / L dilute hydrochloric acid. Then, continue to heat and stir for 3.5 hours, centrifuge, filter, wash, and dry to obtain a coated modified ammonium polyphosphate, wherein the amount of hydroxyethylene diphosphonic acid added is 45% of the mass of the polyethyleneimine;

[0081] S2: Modified expanded perlite

[0082] S2.1: Add γ-aminopropyltriethoxysilane to a 60% ethanol solution at a solid-liquid ratio of 1 g:11 mL, stir thoroughly to dissolve, and then add acetic acid to adjust the pH to 4.5 to obtain a γ-aminopropyltriethoxysilane solution.

[0083] S2.2: Ultrasonic clean the expanded perlite with deionized water and dry to constant weight. Then, add the above-mentioned γ-aminopropyltriethoxysilane solution at a solid-liquid ratio of 1 g:5.5 mL. Heat and stir at 75°C for 3.5 hours to obtain an amination-treated expanded perlite solution.

[0084] S2.3: Add dimethyl hydroxymethylphosphonate to the above-mentioned amino-modified expanded perlite solution at a solid-liquid ratio of 1 g:14 mL, and adjust the pH to 2.5 by adding 0.1 mol / L hydrochloric acid. Heat and stir the mixture at 85°C for 11 h. After cooling, centrifuge and filter, wash until neutral, and dry to obtain modified expanded perlite.

[0085] S3: Preparation of flame retardant outer fabric

[0086] S3.1: Evenly mix the polyester powder, the coated modified ammonium polyphosphate prepared in step S1.3, and the modified expanded perlite prepared in step S2.3 in a mass ratio of 40:4:1, and extrude and granulate the mixture through a twin-screw extruder to obtain a modified polyester masterbatch;

[0087] S3.2: Mixing the modified polyester masterbatch with polyester chips in a mass ratio of 1:6 and spinning the mixture to obtain modified polyester fiber yarn, which is then plain-woven to obtain a flame-retardant outer fabric.

[0088] S4: Preparation of thermal insulation core fabric

[0089] 35 parts by mass of polyvinyl chloride, 15 parts by mass of ethylene propylene rubber, 2.5 parts by mass of sodium stearate, 4 parts by mass of bamboo charcoal powder and 3 parts by mass of sepiolite nanofibers are mixed uniformly and heated to a molten state, and then 3 parts by mass of KH-550 coupling agent, 1.5 parts by mass of cellulose ester and 1.5 parts by mass of sodium alginate are added, and the mixture is continued to be mixed uniformly and extruded to obtain synthetic fibers, and then the synthetic fibers are blended with aramid fibers in a mass ratio of 1:2.5 to obtain a thermal insulation core fabric;

[0090] S5: Preparation of antibacterial inner fabric

[0091] S5.1: Add ε-polylysine hydrochloride to deionized water at a solid-liquid ratio of 1 g:15 mL, stir thoroughly to dissolve, and then add 0.1 mol / L sodium hydroxide solution to adjust the pH to 10.5 to obtain an ε-polylysine hydrochloride solution.

[0092] S5.2: Add Tween 80 to deionized water at a mass ratio of 1:12.5 and stir thoroughly to dissolve. Then, add epoxidized linseed oil with an epoxy value of 7% at an oil-to-water ratio of 1:5 and emulsify at 1250 rpm for 25 minutes to obtain an epoxidized linseed oil emulsion.

[0093] S5.3: Add the epoxidized linseed oil emulsion to the ε-polylysine hydrochloride solution at a mass ratio of 1:7, heat and stir at 55°C for 5 h, then adjust the pH to neutral by adding glacial acetic acid. Purify by dialysis and freeze-dry to obtain modified ε-polylysine hydrochloride.

[0094] S5.4: Dissolve the modified ε-polylysine hydrochloride in deionized water to prepare a 2% solution by weight, then add 0.25% by weight of citric acid as a catalyst, and stir to mix thoroughly to obtain a modified solution.

[0095] S5.5: Immerse the cotton fabric in the modified treatment solution at a bath ratio of 1:20 and heat at 55°C for 1.5 hours. After removal, wash and dry the fabric to obtain an antibacterial inner layer fabric.

[0096] S6: Bonding

[0097] The flame-retardant outer layer fabric, the heat-insulating core layer fabric and the antibacterial inner layer fabric are sequentially bonded to obtain the flame-retardant heat-insulating fabric.

[0098] Example 3

[0099] A preparation process of flame retardant and heat insulating fabric for fire fighting clothing, such as Figure 1 As shown, the following steps are included:

[0100] S1: Preparation of coated modified ammonium polyphosphate

[0101] S1.1: Add ammonium polyphosphate to deionized water at a solid-liquid ratio of 1 g:30 mL, ultrasonically disperse for 30 min, and then add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 6 to obtain an ammonium polyphosphate dispersion.

[0102] S1.2: Add polyethyleneimine to the above ammonium polyphosphate dispersion and stir at 60°C for 3 hours to obtain a preliminary coated ammonium polyphosphate mixture, wherein the amount of polyethyleneimine added is 20% of the mass of the ammonium polyphosphate;

[0103] S1.3: Dissolve hydroxyethylene diphosphonic acid in deionized water at a solid-liquid ratio of 1 g:40 mL to obtain a hydroxyethylene diphosphonic acid solution, then add the hydroxyethylene diphosphonic acid solution to the preliminary coated ammonium polyphosphate mixture, and adjust the pH to 5 by adding 0.1 mol / L dilute hydrochloric acid. Then, continue to insulate and stir for 4 hours, centrifuge, filter, wash, and dry to obtain a coated modified ammonium polyphosphate, wherein the amount of hydroxyethylene diphosphonic acid added is 50% of the mass of the polyethyleneimine;

[0104] S2: Modified expanded perlite

[0105] S2.1: Add γ-aminopropyltriethoxysilane to a 60% ethanol solution at a solid-liquid ratio of 1 g:12 mL, stir thoroughly to dissolve, and then add acetic acid to adjust the pH to 5 to obtain a γ-aminopropyltriethoxysilane solution.

[0106] S2.2: Ultrasonic clean the expanded perlite with deionized water and dry to constant weight. Then, add the above-mentioned γ-aminopropyltriethoxysilane solution at a solid-liquid ratio of 1 g:6 mL. Heat and stir at 80°C for 4 h to obtain an amination-treated expanded perlite solution.

[0107] S2.3: Add dimethyl hydroxymethylphosphonate to the above-mentioned amination-modified expanded perlite solution at a solid-liquid ratio of 1 g:16 mL, and adjust the pH to 3 by adding 0.1 mol / L hydrochloric acid. Heat and stir the mixture at 90°C for 12 h. After cooling, centrifuge and filter, wash until neutral, and dry to obtain modified expanded perlite.

[0108] S3: Preparation of flame retardant outer fabric

[0109] S3.1: Evenly mix the polyester powder, the coated modified ammonium polyphosphate prepared in step S1.3, and the modified expanded perlite prepared in step S2.3 in a mass ratio of 45:5:1, and extrude and granulate the mixture through a twin-screw extruder to obtain a modified polyester masterbatch;

[0110] S3.2: Mixing the modified polyester masterbatch with polyester chips in a mass ratio of 1:7 and spinning the mixture to obtain modified polyester fiber yarn, which is then plain-woven to obtain a flame-retardant outer fabric.

[0111] S4: Preparation of thermal insulation core fabric

[0112] 40 parts by mass of polyvinyl chloride, 20 parts by mass of ethylene propylene rubber, 3 parts by mass of sodium stearate, 5 parts by mass of bamboo charcoal powder and 4 parts by mass of sepiolite nanofibers are mixed uniformly and heated to a molten state, and then 4 parts by mass of KH-550 coupling agent, 2 parts by mass of cellulose ester and 2 parts by mass of sodium alginate are added, and the mixture is further mixed uniformly and extruded to obtain synthetic fibers, which are then blended with aramid fibers in a mass ratio of 1:3 to obtain a thermal insulation core fabric;

[0113] S5: Preparation of antibacterial inner fabric

[0114] S5.1: Add ε-polylysine hydrochloride to deionized water at a solid-liquid ratio of 1 g:20 mL, stir thoroughly to dissolve, and then add 0.1 mol / L sodium hydroxide solution to adjust the pH to 11 to obtain an ε-polylysine hydrochloride solution;

[0115] S5.2: Add Tween 80 to deionized water at a mass ratio of 1:15 and stir thoroughly to dissolve. Then, add epoxidized linseed oil with an epoxide value of 8% at an oil-to-water ratio of 1:6 and emulsify at 1500 rpm for 30 minutes to obtain an epoxidized linseed oil emulsion.

[0116] S5.3: The epoxidized linseed oil emulsion was added to the ε-polylysine hydrochloride solution at a mass ratio of 1:8. The mixture was heated at 60°C with stirring for 6 h. Glacial acetic acid was then added to adjust the pH to neutral. The mixture was purified by dialysis and freeze-dried to obtain modified ε-polylysine hydrochloride.

[0117] S5.4: Dissolve the modified ε-polylysine hydrochloride in deionized water to prepare a 3% solution by weight, then add 0.3% by weight of citric acid as a catalyst, and stir to mix thoroughly to obtain a modified solution.

[0118] S5.5: Immerse the cotton fabric in the modified treatment solution at a bath ratio of 1:25 and heat at 60°C for 2 hours. After removal, wash and dry the fabric to obtain an antibacterial inner layer fabric.

[0119] S6: Bonding

[0120] The flame-retardant outer layer fabric, the heat-insulating core layer fabric and the antibacterial inner layer fabric are sequentially bonded to obtain the flame-retardant heat-insulating fabric.

[0121] Comparative Example 1

[0122] The difference between Comparative Example 1 and Example 1 is that step S1 is removed, and the coated modified ammonium polyphosphate in step S3.1 is replaced by an equal amount of ammonium polyphosphate.

[0123] Comparative Example 2

[0124] The difference between Comparative Example 2 and Example 1 is that step S2 is removed, and the modified expanded perlite in step S3.1 is removed.

[0125] Comparative Example 3

[0126] The difference between Comparative Example 3 and Example 1 is that step S2 is removed, and the modified expanded perlite in step S3.1 is replaced by an equal amount of expanded perlite.

[0127] Comparative Example 4

[0128] The difference between this comparative example 4 and example 1 is that steps S5.1 to 5.3 are removed, and the modified ε-polylysine hydrochloride in step S5.4 is replaced by an equal amount of ε-polylysine hydrochloride.

[0129] Test Case

[0130] Test 1: The limiting oxygen index of the flame retardant outer fabrics prepared in Examples 1-3 and Comparative Examples 1-2 was tested in accordance with GB / T5454-1997. The results are shown in Table 1.

[0131] Table 1: Limiting oxygen index test results of flame retardant outer fabrics

[0132] Limiting oxygen index (%) Example 1 36.2 Example 2 36.1 Example 3 36.4 Comparative Example 1 29.5 Comparative Example 3 33.8

[0133] As shown in Table 1, in Comparative Example 1, after the ammonium polyphosphate was not subjected to surface coating modification, the ammonium polyphosphate was directly added to the polyester powder to prepare a polyester masterbatch, and mixed with the polyester chips for spinning to prepare polyester fiber yarn, and then prepared into a flame-retardant outer layer fabric. The resulting flame-retardant outer layer fabric had a limiting oxygen index much lower than that of Example 1. This shows that the modification of ammonium polyphosphate by hydroxyethylene diphosphonic acid and polyethylene imine can not only effectively improve the compatibility of ammonium polyphosphate with the polyester matrix, but also improve the problem of reduced flame retardant performance of the flame-retardant outer layer fabric due to precipitation of ammonium polyphosphate, and further improve the flame retardant performance of the flame-retardant outer layer fabric.

[0134] In addition, in Comparative Example 3, when the expanded perlite is not modified, the limiting oxygen index of the flame-retardant outer layer fabric obtained is also lower than that of Example 1, indicating that grafting dimethyl hydroxymethylphosphonate onto the surface of the expanded perlite and modifying it can further improve the flame retardant properties of the flame-retardant outer layer fabric obtained.

[0135] Test 2: The dimensional change rates of the flame-retardant outer fabrics prepared in Examples 1-3 and Comparative Example 2 were tested according to GA10-2014 to reflect their thermal stability. The results are shown in Table 2.

[0136] Table 2: Dimensional change test results of flame retardant outer fabric

[0137] Dimensional change rate (%) Example 1 0.76 Example 2 0.74 Example 3 0.73 Comparative Example 2 1.24

[0138] As shown in Table 2, the dimensional change rate of the flame-retardant outer layer fabric prepared in Comparative Example 2 without adding modified expanded perlite is higher than that in Example 1, indicating that the addition of modified expanded perlite can effectively improve the thermal stability of the flame-retardant outer layer fabric.

[0139] Test 3: The Cros values ​​of the flame-retardant and thermal-insulating fabrics prepared in Examples 1-3 and Comparative Examples 2-3 were measured in accordance with GB / T11048-2018. The results are shown in Table 3.

[0140] Table 3: Test results of the Crow value of flame retardant thermal insulation fabrics

[0141] <![CDATA[Cloth Cover Value (m 2 ·C / W)]]> Example 1 1.163 Example 2 1.168 Example 3 1.171 Comparative Example 2 0.903 Comparative Example 3 1.026

[0142] As shown in Table 3, when the modified expanded perlite is not added to the flame-retardant outer layer fabric in Comparative Example 2, the Cro value of the flame-retardant thermal insulation fabric obtained is lower than that in Example 1. This shows that the addition of the modified expanded perlite can improve the thermal insulation performance of the flame-retardant outer layer fabric, thereby improving the thermal insulation performance of the flame-retardant thermal insulation fabric. When the expanded perlite is not modified in Comparative Example 3, the Cro value of the flame-retardant thermal insulation fabric obtained is also lower than that in Example 1, indicating that the modification of the expanded perlite with dimethyl hydroxymethylphosphonate can effectively improve the dispersibility of the expanded perlite, thereby further improving the thermal insulation performance of the flame-retardant thermal insulation fabric.

[0143] Test 4: The initial antibacterial rate and the antibacterial rate after 50 washes of the antibacterial inner layer fabrics prepared in Examples 1-3 and Comparative Example 4 were tested with reference to GB / T20944.3-2008. The test bacteria were Staphylococcus aureus. Each experiment was repeated three times, and the average value was taken. The results are shown in Table 4.

[0144] Table 4: Test results of initial antibacterial rate of antibacterial inner fabric and antibacterial rate after 50 washes

[0145] Initial antibacterial rate (%) Antibacterial rate after 50 washes (%) Example 1 99.89 95.86 Example 2 99.93 95.83 Example 3 99.95 95.91 Comparative Example 4 99.72 58.77

[0146] As shown in Table 4, in Comparative Example 4, after the epoxidized linseed oil was not used to modify the ε-polylysine hydrochloride, the antibacterial rate of the antibacterial inner layer fabric prepared was greatly reduced after 50 water washings, while the antibacterial inner layer fabrics prepared in Examples 1-3 had an antibacterial rate of more than 95% after 50 water washings. This shows that by using epoxidized linseed oil to modify the ε-polylysine hydrochloride and then treating the modified ε-polylysine hydrochloride with the modified linseed oil to treat the cotton fabric, the binding force between the antibacterial ε-polylysine hydrochloride and the cotton fabric can be improved, thereby achieving the effect of improving the antibacterial durability of the antibacterial inner layer fabric.

[0147] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A flame retardant and heat-insulating fabric for fire-fighting clothing, characterized in that: Includes flame-retardant outer fabric, thermal insulating core fabric and antimicrobial inner fabric; The flame-retardant outer fabric is woven from modified polyester filaments; The thermal insulation core fabric is blended from synthetic fiber and aramid fiber in a mass ratio of 1: (2-3); The antibacterial inner layer fabric is made by soaking the cotton fabric in a modified treatment liquid; The preparation process of the flame-retardant and heat-insulating fabric for fire-fighting clothing comprises the following steps: S1: Preparation of coated modified ammonium polyphosphate S1.1: Add ammonium polyphosphate to deionized water at a solid-liquid ratio of 1 g:(20-30) mL, ultrasonically disperse for 20-30 min, and then add 0.1 mol / L dilute hydrochloric acid to adjust the pH to 5-6 to obtain an ammonium polyphosphate dispersion. S1.2: Add polyethyleneimine to the above ammonium polyphosphate dispersion and stir at a constant temperature of 50-60°C for 2-3 hours to obtain a preliminary coated ammonium polyphosphate mixture; S1.3: Dissolve hydroxyethylene diphosphonic acid in deionized water at a solid-liquid ratio of 1 g: (30-40) mL to obtain a hydroxyethylene diphosphonic acid solution. Add the hydroxyethylene diphosphonic acid solution to the preliminary coated ammonium polyphosphate mixture, and adjust the pH to 4-5 by adding 0.1 mol / L dilute hydrochloric acid. Continue to heat and stir for 3-4 hours. Centrifuge, filter, wash, and dry to obtain the coated modified ammonium polyphosphate. S2: Modified expanded perlite S2.1: Add γ-aminopropyltriethoxysilane to a 60% ethanol solution at a solid-liquid ratio of 1 g:(10-12) mL, stir thoroughly to dissolve, and then add acetic acid to adjust the pH to 4-5 to obtain a γ-aminopropyltriethoxysilane solution. S2.2: Ultrasonic clean the expanded perlite with deionized water and dry to constant weight. Then, add the γ-aminopropyltriethoxysilane solution described above at a solid-to-liquid ratio of 1 g:(5-6) mL. Heat and stir at 70-80°C for 3-4 hours to obtain an amination-treated expanded perlite solution. S2.3: Add dimethyl hydroxymethylphosphonate to the above-mentioned amino-modified expanded perlite solution at a solid-liquid ratio of 1 g:(12-16) mL, and adjust the pH to 2-3 by adding 0.1 mol / L hydrochloric acid. Heat and stir the mixture at 80-90°C for 10-12 hours. After cooling, centrifuge, filter, wash until neutral, and dry to obtain modified expanded perlite. S3: Preparation of flame retardant outer fabric The polyester powder, the coated modified ammonium polyphosphate and the modified expanded perlite are mixed and granulated to prepare a modified polyester masterbatch, which is then mixed with polyester chips to prepare modified polyester fiber yarn, which is then plain woven to prepare a flame retardant outer fabric; S4: Preparation of thermal insulation core fabric Polyvinyl chloride, ethylene propylene rubber, sodium stearate, bamboo charcoal powder and sepiolite nanofibers are mixed uniformly and heated to a molten state, and then KH-550 coupling agent, cellulose ester and sodium alginate are added, mixed uniformly and extruded to obtain synthetic fibers, which are then blended with aramid fibers to obtain a thermal insulation core fabric. S5: Preparation of antibacterial inner fabric An ε-polylysine hydrochloride solution and an epoxidized linseed oil emulsion are prepared separately, and then mixed and heated to react to obtain modified ε-polylysine hydrochloride. After dissolving, citric acid is added and the cotton fabric is treated to obtain an antibacterial inner layer fabric. S6: Bonding The flame-retardant outer layer fabric, the heat-insulating core layer fabric and the antibacterial inner layer fabric are sequentially bonded to obtain the flame-retardant heat-insulating fabric.

2. The flame retardant and heat insulating fabric for firefighting clothing according to claim 1, characterized in that: S3 specifically includes the following steps: S3.1: Evenly mix the polyester powder, the coated modified ammonium polyphosphate prepared in step S1.3, and the modified expanded perlite prepared in step S2.3, and granulate the mixture by extrusion through a twin-screw extruder to obtain a modified polyester masterbatch; S3.2: The modified polyester masterbatch and polyester chips are mixed in a mass ratio of 1:(5-7) and spun to obtain modified polyester fiber yarn, which is then plain woven to obtain a flame retardant outer fabric.

3. The flame retardant and heat insulating fabric for firefighting clothing according to claim 2, characterized in that: S5 specifically includes the following steps: S5.1: Add ε-polylysine hydrochloride to deionized water at a solid-liquid ratio of 1 g:(10-20) mL, stir thoroughly to dissolve, and then add 0.1 mol / L sodium hydroxide solution to adjust the pH to 10-11 to obtain an ε-polylysine hydrochloride solution. S5.2: Add Tween 80 to deionized water at a mass ratio of 1:(10-15) and stir thoroughly to dissolve. Then, add epoxidized linseed oil with an epoxy value of 6-8% at an oil-to-water ratio of 1:(4-6) and emulsify at 1000-1500 rpm for 20-30 minutes to obtain an epoxidized linseed oil emulsion. S5.3: Add the epoxidized linseed oil emulsion to the ε-polylysine hydrochloride solution at a mass ratio of 1:(6-8), heat and stir at 50-60°C for 4-6 hours, then add glacial acetic acid to adjust the pH to neutral. Purify by dialysis and freeze-dry to obtain modified ε-polylysine hydrochloride. S5.4: Dissolve the modified ε-polylysine hydrochloride in deionized water to prepare a 1-3% by weight solution, then add 0.2-0.3 wt% of citric acid as a catalyst, and stir to mix thoroughly to obtain a modified treatment solution; S5.5: Immerse the cotton fabric in the above-mentioned modified treatment solution at a bath ratio of 1:(15-25), and heat and soak it at 50-60°C for 1-2 hours. After taking it out, wash it with water and dry it to obtain the antibacterial inner layer fabric.

4. The flame retardant and heat insulating fabric for firefighting clothing according to claim 1, characterized in that: The amount of polyethyleneimine added is 15-20% of the mass of ammonium polyphosphate.

5. The flame retardant and heat insulating fabric for firefighting clothing according to claim 1, characterized in that: The added amount of hydroxyethylene diphosphonic acid is 40-50% of the mass of polyethyleneimine.

6. The flame retardant and heat insulating fabric for firefighting clothing according to claim 2, characterized in that: The mass ratio of polyester powder, coated modified ammonium polyphosphate and modified expanded perlite is (35-45): (3-5):

1.

7. The flame retardant and heat insulating fabric for firefighting clothing according to claim 1, characterized in that: The raw materials of the synthetic fiber include, by mass, 30-40 parts of polyvinyl chloride, 10-20 parts of ethylene propylene rubber, 2-3 parts of sodium stearate, 3-5 parts of bamboo charcoal powder, 2-4 parts of sepiolite nanofiber, 2-4 parts of KH-550 coupling agent, 1-2 parts of cellulose ester and 1-2 parts of sodium alginate.

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