Wear-resistant and tear-resistant foam flame composite fabric and preparation method thereof

Abstract

The invention relates to the field of textile fabrics, in particular to a wear-resistant and tear-resistant foam flame composite fabric and a preparation method thereof.The wear-resistant and tear-resistant foam flame composite fabric is prepared from, by mass, 35-45 parts of modified high-strength polyester fibers, 20-30 parts of a modified polyurethane film and 30-40 parts of modified polyurethane foam, and 3-5 parts of a polyurethane hot melt adhesive. Through collaborative design of innovative material modification and a staged composite process, compared with the prior art, through combination of flame activation and a low-temperature composite process, the interface bonding strength and durability of the fabric are remarkably improved, and meanwhile, the fabric has outstanding advantages in the aspect of green manufacturing; the composite material can be widely applied to high-value-added fields such as outdoor sports equipment, automotive trim and industrial protective clothing, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the field of textile fabrics, and in particular to a wear-resistant and tear-resistant foam flame composite fabric and a preparation method thereof. Background Art

[0002] In the textile industry, wear-resistant and tear-resistant composite fabrics are widely used in outdoor equipment, automotive interiors, industrial protective clothing and other fields due to their high durability requirements in extreme environments. Traditional composite fabrics are mostly made of polyester fiber and polyurethane foam or film through hot pressing or adhesive bonding processes. However, with the diversification of application scenarios, existing technologies have exposed a series of key defects.

[0003] In the existing technology, traditional foam composite fabrics are usually based on polyester fiber as the base material, combined with polyurethane foam or film, and compounded by hot pressing or adhesive bonding process. The interface bonding strength is low and delamination or edge tearing is prone to occur after long-term use. At the same time, although silane coupling agent treatment can improve interface compatibility, its short-chain structure is easily hydrolyzed and ineffective. Although carbon fiber reinforced polyurethane film can improve mechanical properties, the interface compatibility between carbon fiber and polyurethane matrix is poor, and stress concentration points are prone to occur, resulting in insufficient peel strength.

[0004] Therefore, according to the above-mentioned related technologies, there is an urgent need to develop a wear-resistant and tear-resistant foam flame composite fabric and a preparation method thereof. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to propose a wear-resistant and tear-resistant foam flame composite fabric and a preparation method thereof to solve the problems of low interface bonding strength, weak tear resistance and poor interface compatibility between carbon fiber and polyurethane matrix in the prior art.

[0006] Based on the above objectives, the present invention provides a wear-resistant and tear-resistant foam flame composite fabric and a preparation method thereof.

[0007] A wear-resistant and tear-resistant foam flame composite fabric comprises the following components in parts by weight: 35-45 parts of modified high-strength polyester fiber, 20-30 parts of modified polyurethane film, 30-40 parts of modified polyurethane foam, and 3-5 parts of polyurethane hot-melt adhesive.

[0008] A method for preparing a wear-resistant and tear-resistant foam flame composite fabric, the preparation steps being as follows:

[0009] Step S1: burning the modified polyurethane foam with a propane-oxygen mixed flame, raising the temperature to 800-1000° C., with a flame sweep time of 1-3 seconds per time and a melting depth of ≤0.1 mm, to obtain a flame-activated foam;

[0010] Step S2: Coat the modified high-strength polyester fiber with polyurethane hot melt adhesive, then align the modified polyurethane film and place it on the hot press roller. Heat up to 110 - 130 °C, with a pressure of 0.5 - 1 MPa and a roller speed of 3 - 5 m / min to obtain a pre-compounded fabric;

[0011] Step S3: Align and bond the flame-activated foam with the pre-compounded fabric, let it stand for 3 - 5 s, then place it on the hot press roller. Heat up to 30 - 50 °C, with a pressure of 1.5 - 2 MPa and a roller speed of 5 - 10 m / min to obtain a wear-resistant and tear-resistant foam flame composite fabric;

[0012] The modified high-strength polyester fiber is a triazine-modified high-strength polyester fiber;

[0013] The modified polyurethane film is a carbon fiber-modified polyurethane film;

[0014] The modified polyurethane foam is a silane long-chain modified polyurethane foam.

[0015] Preferably, the preparation method of the triazine-modified high-strength polyester fiber is as follows:

[0016] Step A1: Add cyanuric chloride, 4-(oxiran-2-ylmethyl)benzene-1,2-diol, sodium hydroxide, and deionized water into acetone solvent, stir and react for 3 - 5 h, filter, and perform vacuum distillation to obtain intermediate 1;

[0017] Step A2: Add intermediate 1 into tetrahydrofuran solvent, mix evenly, then add 6-amino-1-hexanol, heat up to 20 - 30 °C, stir and react for 10 - 14 h. After the reaction is completed, perform vacuum distillation to obtain intermediate 2;

[0018] Step A3: Mix intermediate 2 with terephthalic acid, heat up to 220 - 240 °C, react for 2 - 4 h, add the catalyst tetrabutyl titanate, evacuate to 40 - 50 Pa, heat up to 250 - 260 °C, react for 1 - 2 h, then heat up to 270 - 280 °C, react for 3 - 5 h. After the reaction is completed, cool and pelletize to obtain polyester chips;

[0019] Step A4: Dry the polyester chips, put them into a spinning machine, heat up to 300 - 320 °C, filter, with a twin-screw extrusion pressure of 4 - 5 MPa and a winding rate of 700 - 900 m / min, then stretch with a stretching machine, with a total stretching multiple of 4 - 5, and perform weaving with an air-jet loom. The weaving process is as follows: the reed count is 100, the number of warp ends per reed is 2, the warp and weft density on the loom is 220 ends / 10 cm × 210 ends / 10 cm, the loom reed width is 210 cm, and the total number of warp ends is 7000 to obtain the triazine-modified high-strength polyester fiber.

[0020] The triazine-modified high-strength polyester fiber introduces a triazine ring structure through the reaction of cyanuric chloride with epoxy groups to form an ultraviolet absorption barrier, avoiding fiber aging caused by long-term light exposure. At the same time, the rigid structure of the triazine ring enhances the tensile strength of the fiber and significantly improves the tear resistance of the fabric.

[0021] Preferably, the mass ratio of cyanuric chloride, 4-(oxiran-2-ylmethyl)benzene-1,2-diol, sodium hydroxide, and deionized water in step A1 is 1:4 - 4.2:1.2 - 1.4:5.5 - 6;

[0022] The mass ratio of intermediate 1 to 6-amino-1-hexanol in step A2 is 1.8 - 2:1;

[0023] The mass ratio of intermediate 2 to terephthalic acid in step A3 is 4 - 5:1.

[0024] Preferably, the preparation method of the carbon fiber-modified polyurethane film is as follows:

[0025] Step B1: Add carbon fiber into acetone solvent, heat up to 50 - 60 °C, react for 10 - 14 h, after the reaction is completed, perform ultrasonic treatment for 3 - 7 min, and dry to obtain degummed carbon fiber;

[0026] Step B2: Add the degummed carbon fiber into 65% concentrated nitric acid solution, heat up to 80 - 100 °C, react for 110 - 130 min, adjust the pH to 7, add cyclotriphosphazene-modified silane coupling agent, heat up to 90 - 110 °C, react for 1 - 3 h, and rinse with boiling water to obtain cyclotriphosphazene-modified silane coupling agent-modified carbon fiber;

[0027] Step B3: Mix polyether polyols YD-4110, YD-889, YD-204, and YD-380 evenly, add foam stabilizer and antioxidant, and stir for 20 - 40 min to obtain component A;

[0028] Step B4: Add polymethylene polyphenyl polyisocyanate into a beaker, heat up to 50 - 70 °C, and preheat for 50 - 70 min to obtain component B;

[0029] Step B5: Add component A and component B into a beaker, heat up to 30 - 50 °C, react for 2 - 4 min, stir for 1 - 3 min, then add cyclotriphosphazene-modified silane coupling agent-modified carbon fiber, heat up to 50 - 60 °C, cure for 50 - 70 min, cool down to 20 - 30 °C, and stand for 22 - 26 h to obtain the carbon fiber-modified polyurethane film.

[0030] The cyclotriphosphazene-modified silane coupling agent is adopted. Its multiple active sites can bond with the hydroxyl groups on the carbon fiber surface and the polyurethane matrix simultaneously, enhancing the interfacial peel strength. In addition, the synthesis process of this coupling agent does not require toxic solvents, has a high reaction efficiency, reduces the VOCs emissions, and meets the requirements of green manufacturing.

[0031] Preferably, the mass ratio of the degummed carbon fiber, concentrated nitric acid solution and cyclotriphosphazene-modified silane coupling agent in step B2 is 1:9 - 11:0.02 - 0.04;

[0032] The mass ratio of the polyether polyol YD-4110, YD-889, YD-204, YD-380, foam stabilizer and antioxidant in step B3 is 5.8 - 6.2:2.8 - 3.2:1:1.4 - 1.6:0.35 - 0.45:0.023 - 0.27;

[0033] The mass ratio of component A, component B and cyclotriphosphazene-modified silane coupling agent-modified carbon fiber in step B5 is 1:1.0 - 1.2:0.02 - 0.04.

[0034] Preferably, the preparation method of the cyclotriphosphazene-modified silane coupling agent is as follows:

[0035] Step C1: Under an argon atmosphere, add hexachlorocyclotriphosphazene and hydroquinone into a tetrahydrofuran solvent, stir and mix evenly, add triethylamine, heat up to 65 - 75 °C, stir and react for 45 - 50 h. After the reaction is completed, cool down, filter, distill under reduced pressure, and recrystallize to obtain intermediate 3;

[0036] Step C2: Add paraformaldehyde into a tetrahydrofuran solvent, add CaH2, heat up to 20 - 30 °C, react for 20 - 40 min, then heat up to 50 - 70 °C, add N-[3-(trimethoxysilyl)propyl]ethylenediamine, heat up to 75 - 85 °C, add intermediate 3, react for 2 - 4 h, filter, distill under reduced pressure to obtain the cyclotriphosphazene-modified silane coupling agent.

[0037] Preferably, the mass ratio of hexachlorocyclotriphosphazene, hydroquinone and triethylamine in step C1 is 1:0.33 - 0.37:0.80 - 0.83;

[0038] The mass ratio of paraformaldehyde, CaH2, N-[3-(trimethoxysilyl)propyl]ethylenediamine and intermediate 3 in step C2 is 0.43 - 0.47:0.45 - 0.49:1.65 - 1.70:1.

[0039] Preferably, the preparation of the modified polyurethane foam is as follows:

[0040] Step D1: Add tetrakis(hydroxymethyl)phosphonium sulfate to diethylene glycol dimethyl ether solvent, raise the temperature to 20-25°C, add n-octadecyltrichlorosilane, raise the temperature to 50-60°C, react for 50-70 minutes, raise the temperature to 120-140°C, react for 8-10 hours, cool, crystallize, and filter to obtain a caged quaternary phosphonium salt long-chain organosilicate;

[0041] Step D2: Under a nitrogen atmosphere, hexamethylene diisocyanate and polyether polyol LY-4110 are heated to 70-80°C, reacted for 1-3 hours, cooled to 50-60°C, and a chain extender, diethylene glycol, and catalysts, stannous octoate and dibutyl dilaurate, are added and reacted for 3-5 hours. Isocyanate trimer, caged quaternary phosphonium salt long-chain organosilicate and chemical foaming microspheres are added and stirred evenly. The temperature is raised to 110-130°C and reacted for 1-3 hours to obtain silane long-chain modified polyurethane foam.

[0042] By modifying the polyurethane foam with long-chain silane, its long-chain structure can penetrate into the polyurethane matrix to form physical entanglement, while the terminal silanol groups chemically bond with the fiber and film surface, significantly improving the interfacial bonding strength; the hydrophobicity and hydrolysis resistance of long-chain silane effectively resist erosion in humid and hot environments, making it suitable for outdoor high-humidity scenes.

[0043] Cage-shaped quaternary phosphate long-chain organic silicate is evenly distributed in the foam. When exposed to fire, it decomposes to form a phosphate barrier layer, which increases the limiting oxygen index of the fabric. At the same time, the long-chain organic silicone structure of the quaternary phosphate can inhibit the attachment of microorganisms, making it suitable for scenarios with strict hygiene requirements such as medical protection and automotive interiors.

[0044] Preferably, the mass ratio of tetrakis(hydroxymethyl)phosphonium sulfate to n-octadecyltrichlorosilane in step D1 is 1:0.50-0.53;

[0045] The mass ratio of hexamethylene diisocyanate, polyether polyol LY-4110, diethylene glycol, stannous octoate, dibutyl dilaurate, isocyanate trimer, caged quaternary phosphonium salt long-chain organic silicate and chemical foaming microspheres in step D2 is 1:12-14:1.3-1.5:0.1-0.3:0.1-0.2:2-4:0.5-0.7:0.7-0.9.

[0046] Beneficial effects of the present invention:

[0047] The present invention adopts a flame activation process to carry out surface treatment on silane long-chain modified polyurethane foam, and significantly improves the interface bonding strength between the foam and polyester fiber and polyurethane film through high-temperature short-time burning. At the same time, the triazine-modified high-strength polyester fiber and the carbon fiber-modified polyurethane film are combined, and the interface peeling strength and wear resistance of the composite fabric are finally improved.

[0048] The present invention adopts a staged hot pressing process, adopts low temperature in the pre-compounding stage and further reduces the temperature in the final compounding stage, combined with precise roller speed control, to effectively avoid the collapse of the foam closed-cell structure and reduce the risk of thermal damage to the surface carbon fiber film.

[0049] The flame activation and step-by-step hot pressing process of the present invention does not require complex equipment, has mild reaction conditions, reduces energy consumption, improves raw material utilization, and reduces overall costs during large-scale production.

[0050] The present invention is collaboratively designed through innovative material modification and staged composite process. Compared with the existing technology, it significantly improves the interfacial bonding strength and durability of the fabric through the combination of flame activation and low-temperature composite process. At the same time, it has outstanding advantages in achieving green manufacturing. It can be widely used in high-value-added fields such as outdoor sports equipment, automotive interiors, industrial protective clothing, etc., and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0052] Figure 1 The following is a preparation route for the high-strength polyurethane fiber of the present invention;

[0053] Figure 2 This is a preparation route for carbon fiber modified with a silane coupling agent modified with cyclotrinitrile in the present invention. DETAILED DESCRIPTION

[0054] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to specific embodiments.

[0055] Embodiment 1:

[0056] S1: 100 g of cyanuric chloride, 400 g of 4-(oxiran-2-ylmethyl)benzene-1,2-diol, 130 g of sodium hydroxide, and 550 g of deionized water were added to acetone solvent, stirred for 4 h, filtered, and distilled under reduced pressure to obtain intermediate 1;

[0057] S2: 180 g of intermediate 1 was added to 100 mL of tetrahydrofuran solvent, mixed evenly, and then 100 g of 6-amino-1-hexanol was added. The temperature was raised to 25°C, and the mixture was stirred for 12 h. After the reaction was complete, the mixture was distilled under reduced pressure to obtain intermediate 2;

[0058] S3: 450 g of intermediate 2 was mixed with 100 g of terephthalic acid, the temperature was raised to 230°C, and the reaction was carried out for 3 h. 5.5 g of tetrabutyl titanate catalyst was added, the mixture was evacuated to 45 Pa, the temperature was raised to 255°C, the reaction was carried out for 1-2 h, and the temperature was further raised to 275°C, the reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled and granulated to obtain polyester chips.

[0059] S4: The polyester chips were dried, placed in a spinning machine, heated to 310°C, filtered, and extruded with a twin-screw extruder at a pressure of 4 MPa and a winding rate of 800 m / min. The chips were then stretched with a stretching machine with a total stretching ratio of 4.5. The chips were woven with an air-jet loom. The weaving process was as follows: the reed number was 100, the number of insertions per reed was 2, the warp and weft density on the machine was 220 threads / 10 cm × 210 threads / 10 cm, the reed width on the machine was 210 cm, and the total number of warps was 7000, thereby obtaining triazine-modified high-strength polyester fiber.

[0060] Embodiment 2:

[0061] S1: Add 100 g of carbon fiber to 100 mL of acetone solvent, heat to 60 ° C, react for 12 hours, and after the reaction is complete, ultrasonicate for 5 minutes and dry to obtain debonded carbon fiber;

[0062] S2: 100 g of debonded carbon fiber was added to 1000 g of 65% concentrated nitric acid solution, the temperature was raised to 100° C., the reaction was carried out for 130 min, the pH was adjusted to 7, a cyclotriphosphazene-modified silane coupling agent was added, the temperature was raised to 100° C., the reaction was carried out for 3 h, and the mixture was rinsed with boiling water to obtain a cyclotriphosphazene-modified silane coupling agent-modified carbon fiber;

[0063] S3: 580g of polyether polyol YD-4110, 280g of YD-889, 100g of YD-204, and 150g of YD-380 were mixed evenly, 35g of foam stabilizer DX-931 and 2.5g of antioxidant 1135 were added, and stirred for 20-40min to obtain component A;

[0064] S4: Add 100 g of polymethylene polyphenyl polyisocyanate into a beaker, raise the temperature to 70°C, and preheat for 60 minutes to obtain component B;

[0065] S5: Add 100g of component A and 100g of component B into a beaker, heat to 40°C, react for 3min, stir for 2min, then add 3g of cyclotriphosphazene-modified silane coupling agent to modify the carbon fiber, heat to 50°C, cure for 70min, cool to 20°C, and let stand for 24h to obtain a carbon fiber modified polyurethane film.

[0066] Embodiment 3:

[0067] S1: Under an argon atmosphere, 100 g of hexachlorocyclotriphosphazene and 35 g of hydroquinone are added to 150 mL of tetrahydrofuran solvent, stirred and mixed evenly, 80 g of triethylamine is added, the temperature is raised to 70 °C, stirred and reacted for 50 h, the reaction is completed, cooled, filtered, distilled under reduced pressure, and recrystallized to obtain intermediate 3;

[0068] S2: 45 g of paraformaldehyde is added to 200 mL of tetrahydrofuran solvent, 45 g of CaH2 is added, the temperature is raised to 20 °C, reacted for 30 min, then the temperature is raised to 60 °C, 165 g of N-[3-(trimethoxysilyl)propyl]ethylenediamine is added, the temperature is raised to 80 °C, 100 g of intermediate 3 is added, reacted for 3 h, filtered, and distilled under reduced pressure to obtain a cyclotriphosphazene-modified silane coupling agent.

[0069] Example 4:

[0070] S1: 100 g of phosphonium tetramethylol sulfate is added to 150 mL of diethylene glycol dimethyl ether solvent, the temperature is raised to 25 °C, 50 g of n-octadecyltrichlorosilane is added, the temperature is raised to 60 °C, reacted for 60 min, then the temperature is raised to 130 °C, reacted for 9 h, cooled, crystallized, and filtered to obtain a cage-like quaternary phosphonium salt long-chain organosilicate;

[0071] S2: Under a nitrogen atmosphere, 100 g of hexamethylene diisocyanate and 1200 g of polyether polyol LY-4110 are heated to 80 °C and reacted for 1.5 h. The temperature is lowered to 60 °C, 130 g of chain extender diethylene glycol, 10 g of catalyst stannous octoate and 20 g of dibutyltin dilaurate are added, and reacted for 4 h. 200 g of isocyanate trimer, 60 g of cage-like quaternary phosphonium salt long-chain organosilicate and 80 g of chemical foaming microspheres are added, stirred evenly, heated to 120 °C, and reacted for 2 h to obtain a silane long-chain modified polyurethane foam.

[0072] Example 5:

[0073] S1: Burn 30 g of modified polyurethane foam with a propane-oxygen mixed flame, heat up to 800 °C, the flame sweeping time is 3 s / time, and the melting depth ≤ 0.1 mm to obtain a flame-activated foam;

[0074] S2: Coat 3 g of polyurethane hot melt adhesive on 35 g of modified high-strength polyester fiber, then align 20 g of modified polyurethane film, place it on a hot press roller, heat up to 110 °C, pressure 1 MPa, and roller speed 3 m / min to obtain a pre-compounded fabric;

[0075] S3: Align and bond 30 g of flame-activated foam with 58 g of pre-compounded fabric, let stand for 3 s, then place it on a hot press roller, heat up to 50 °C, pressure 1.5 MPa, and roller speed 10 m / min to obtain a wear-resistant and tear-resistant foam flame composite fabric.

[0076] Example 6

[0077] S1: Burn 35 g of modified polyurethane foam with a propane-oxygen mixed flame, heat up to 900 °C, the flame sweeping time is 2 s / time, and the melting depth ≤ 0.1 mm to obtain flame-activated foam;

[0078] S2: Coat 4 g of polyurethane hot melt adhesive on 40 g of modified high-strength polyester fiber, then align 25 g of modified polyurethane film and place it on a hot pressing roller, heat up to 120 °C, the pressure is 0.8 MPa, and the roller speed is 4 m / min to obtain a pre-compounded fabric;

[0079] S3: Align and bond 35 g of flame-activated foam with 69 g of pre-compounded fabric, let it stand for 4 s, then place it on a hot pressing roller, heat up to 40 °C, the pressure is 1.8 MPa, and the roller speed is 7 m / min to obtain a wear-resistant and tear-resistant foam flame composite fabric.

[0080] Example 7

[0081] S1: Burn 40 g of modified polyurethane foam with a propane-oxygen mixed flame, heat up to 1000 °C, the flame sweeping time is 1 s / time, and the melting depth ≤ 0.1 mm to obtain flame-activated foam;

[0082] S2: Coat 5 g of polyurethane hot melt adhesive on 45 g of modified high-strength polyester fiber, then align 30 g of modified polyurethane film and place it on a hot pressing roller, heat up to 130 °C, the pressure is 0.5 MPa, and the roller speed is 5 m / min to obtain a pre-compounded fabric;

[0083] S3: Align and bond 40 g of flame-activated foam with 80 g of pre-compounded fabric, let it stand for 5 s, then place it on a hot pressing roller, heat up to 30 °C, the pressure is 2 MPa, and the roller speed is 5 m / min to obtain a wear-resistant and tear-resistant foam flame composite fabric.

[0084] Comparative Example 1:

[0085] Compared with Example 5, this comparative example does not use the flame activation process and directly uses the conventional hot pressing process to compound the foam and the fabric. The remaining steps and parameters are the same. This comparative example will not be repeated here. Finally, a wear-resistant and tear-resistant foam composite fabric is obtained.

[0086] Comparative Example 2:

[0087] Compared with Example 5, this comparative example only replaces "ordinary polyester fiber" with "triazine-modified high-strength polyester fiber", and the remaining steps and parameters are the same. This comparative example will not be repeated here. Finally, a wear-resistant and tear-resistant foam flame composite fabric is obtained.

[0088] Comparative Example 3

[0089] Compared with Example 5, this comparative example only replaces the "ordinary polyurethane film" with the "carbon fiber modified polyurethane film", and the remaining steps and parameters are the same. This comparative example will not be repeated, and finally a wear-resistant and tear-resistant foam flame composite fabric is obtained.

[0090] Comparative Example 4

[0091] Compared with Example 5, this comparative example only replaces "ordinary polyurethane foam" with "silane long-chain modified polyurethane foam", and the remaining steps and parameters are the same. This comparative example will not be repeated, and finally a wear-resistant and tear-resistant foam flame composite fabric is obtained.

[0092] Comparative Example 5

[0093] Compared with Example 5, this comparative example only replaces the "silane coupling agent KH-550" with the "cyclotriphosphazene modified silane coupling agent", and the remaining steps and parameters are the same. This comparative example will not be repeated, and finally a wear-resistant and tear-resistant foam flame composite fabric is obtained.

[0094] Performance Testing:

[0095] Wear resistance testing

[0096] Referring to the test standard GB / T21196.3-2007 "Martindale Abrasion Resistance Test for Textiles", the wear resistance of Examples 5-7 and Comparative Examples 1-5 was tested and analyzed using a Martindale abrasion tester;

[0097] The mass of the sample holder is 200g, and the mass of the weight is 395g. The effective diameter of the friction head is 38.0±0.5mm, and the abrasive is standard wool abrasive. Before the test, the sample is placed in the test environment in a relaxed state for more than 18 hours, and then three groups of 50×50mm 2 The samples of Examples 5-7 and Comparative Examples 1-5 were placed in a holder and subjected to wear resistance tests. During the test, the test was paused every 1000 wear resistance cycles, the holder was removed, and debris on the surface of the sample and the abrasive was gently cleaned with a brush. The test was then continued until obvious holes appeared in the sample. The value on the reading disk at this time was recorded, and the average value of the three groups of samples was taken as the wear resistance cycle number of the sample.

[0098] Interfacial peel strength test

[0099] With reference to the test standard GB / T2792-2014 "Test method for peel strength of adhesives", the interfacial peel strength of the composite materials of Examples 5-7 and Comparative Examples 1-5 was tested using an AG-1 universal material testing machine using a 180° peel method. The measurement was performed at a clamping distance of 100 mm, a tensile speed of 100 mm / min, a sample width of 25 mm, and the maximum peel force (N) was recorded.

[0100] Tear resistance test

[0101] Refer to GB / T3917.3-2009 "Tear properties of textiles - Part 3: Determination of tear strength of trapezoidal specimens" test standard, using a universal material testing machine;

[0102] Chuck distance: 50 mm, sample length: 120 mm, sample width: 50 mm, tensile speed: 100 mm / min, warp and weft tests were performed on Examples 5-7 and Comparative Examples 1-5, at least 5 valid data were obtained for each piece, and the data used for analysis was its average value.

[0103] Table 1 Test data of Examples 5-7 and Comparative Examples 1-5

[0104]

[0105]

[0106] Limiting Oxygen Index (LOI) Test

[0107] Referring to the test standard GB / T5455-1997 "Textile Combustion Performance Test - Oxygen Index Method", the limiting oxygen index was measured using a limiting oxygen index instrument HC-2C. The combustion performance of Examples 5-7 and Comparative Examples 1-5 was measured and analyzed, and the average of five measurement results was taken.

[0108] Table 2 Limiting oxygen index test data of Examples 5-7 and Comparative Examples 1-5

[0109] project LOI (%) Example 5 33.2 Example 6 33.3 Example 7 34.0 Comparative Example 1 29.5 Comparative Example 2 28.6 Comparative Example 3 28.0 Comparative Example 4 26.0 Comparative Example 5 27.5

[0110] Performance test after damp heat aging

[0111] Cut the samples of Examples 5-7 and Comparative Examples 1-5 into 15cm×15cm, ensuring that there are no creases or damages. Hang the samples in an ESPEC model constant temperature and humidity test chamber to avoid contact with each other. Set the temperature to 70°C and the humidity to 95% RH. Continue the treatment for 72 hours. After the treatment, take out the samples, equilibrate them in the laboratory environment for 24 hours, and then test the peel strength test and tear resistance test.

[0112] Table 3 Mechanical test data of Examples 5-7 and Comparative Examples 1-5 after aging

[0113] project Maximum peeling force (N) Tear strength (warp) (N) Tear strength (weft) (N) Example 5 41.5 293 288 Example 6 43.2 300 295 Example 7 44.8 307 302 Comparative Example 1 12.1 122 118 Comparative Example 2 23.8 174 170 Comparative Example 3 20.5 155 150 Comparative Example 4 15.3 135 130 Comparative Example 5 13.0 126 120

[0114] Antibacterial testing

[0115] Refer to the Textile Industry Standard of the People's Republic of China: Fz / r01021-1992 Test method for antibacterial properties of fabrics;

[0116] Directly drop the experimental bacterial solution onto the fabric to be tested, allowing the bacteria to fully contact and expose on the fabric for a certain period of time, then cover it with a culture medium to allow the remaining bacteria to grow. Compare the percentage decrease in the amount of bacteria in the antibacterial sample to judge its antibacterial ability. Use a magnifying glass to count the colony forming units.

[0117] The operation steps are as follows:

[0118] 1. Bacterial solution preparation: Take the fresh broth culture of Escherichia coli for 24 hours, shake well and let it stand for 20 minutes, then dilute it into a bacterial solution with a bacterial count of 10 5 -10 6 CFU / mL;

[0119] 2. Bacterial infection: Put the samples of Examples 5-7 and Comparative Examples 1-5 with a size of 5.0 cm × 5.0 cm into a sterile petri dish with a diameter of 9 cm, evenly drop 1.5 mL of the bacterial solution, so that it is evenly distributed and completely absorbed on the samples. Repeat 6 pieces for each sample, and place them in an incubator at 37°C for 1 hour to dry;

[0120] 3. Place the dried and bacterially infected samples flat on the surface of a nutrient agar plate, and then evenly cover the surface of the bacterially infected samples with semi-solid nutrient agar with an appropriate thickness. Place it in an incubator at 37% for 48 hours, and set up a blank control group;

[0121] 4. Observe the results: Drop the safranin staining solution onto the above semi-solid nutrient agar and stain for 1 hour. Use a magnifying glass to count the number of colonies on each cloth sample, calculate the average value of the number of colonies on 6 cloth samples and record it;

[0122] 5. Calculate the antibacterial rate: Repeat the above experiment 3 times, take the average value, and calculate the antibacterial rate using the following formula:

[0123]

[0124] In the formula: A is the average number of colonies on the control cloth sample;

[0125] B is the average number of colonies on the antibacterial cloth sample.

[0126] Table 4 Antibacterial property detection data of Examples 5-7 and Comparative Examples 1-5

[0127] project A (CFU / mL) B (CFU / mL) Antibacterial rate (%) Example 5 <![CDATA[1.2×10 5 > <![CDATA[2.8×10 3 > 76.8 Example 6 <![CDATA[1.2×10 5 > <![CDATA[2.7×10 3 > 77.1 Example 7 <![CDATA[1.2×10 5 > <![CDATA[2.7×10 3 > 77.3 Comparative Example 1 <![CDATA[1.2×10 5 > <![CDATA[1.1×10 5 ]]> 8.3 Comparative Example 2 <![CDATA[1.2×10 5 > <![CDATA[9.8×10 4 ]]> 18.3 Comparative Example 3 <![CDATA[1.2×10 5 > <![CDATA[8.5×10 4 > 29.2 Comparative Example 4 <![CDATA[1.2×10 5 > <![CDATA[7.2×10 4 ]]> 40.0 Comparative Example 5 <![CDATA[1.2×10 5 ]]> <![CDATA[6.0×10 4 > 50.0

[0128] Data analysis:

[0129] As can be seen from Tables 1-4, the wear-resistant, tear-resistant, flame-retardant, anti-humid and heat-aged, and antibacterial foam flame composite fabric prepared by the present invention has better wear resistance, tear resistance, flame retardancy, anti-humid and heat-aged properties, and antibacterial properties;

[0130] In Comparative Example 1, the lack of the flame activation process led to a decrease in wear resistance, weak interfacial bonding, and a significant decrease in mechanical properties after hydrothermal aging. The reason is that flame activation can improve the durability of the fabric, and in the case of unactivated foam, moisture is likely to enter the bonding interface in a hydrothermal environment, resulting in easy delamination. At the same time, the flame activation process causes the surface of the foam to melt, forming stronger physical entanglement with polyester fibers and carbon fiber films.

[0131] In Comparative Example 2, the use of ordinary polyester fibers led to a decrease in tear resistance. The reason is that the rigid ring structure of the triazine-modified fibers disperses stress and avoids local tearing, and the physical entanglement of the silane long-chain foam enhances the overall toughness.

[0132] In Comparative Example 3, the use of ordinary polyurethane film led to a decrease in peel strength. The reason is that the cyclotriphosphazene-modified silane coupling agent bonds carbon fiber and polyurethane matrix through multiple active sites, significantly enhancing the interfacial bonding, and the flame activation further optimizes the adhesion between the foam and the fabric.

[0133] In Comparative Example 4, the use of ordinary foam led to a decrease in LOI and antibacterial rate. The reason is that the cage-like quaternary phosphonium salt in the silane long-chain foam decomposes when encountering fire to generate a phosphate barrier layer, which synergistically enhances the flame retardancy with carbon fibers, and the quaternary phosphonium salt structure enhances the antibacterial persistence.

[0134] In Comparative Example 5, the use of silane coupling agent KH-550 led to a decrease in peel strength and antibacterial rate. The reason is that the cage-like quaternary phosphonium salt long-chain organosilicate inhibits microbial attachment, its quaternary phosphonium salt structure enhances the antibacterial persistence, and the long chain can enhance the cross-linking between the bonding interfaces.

[0135] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and the steps can be implemented in any order. There are many other variations in different aspects of the present invention as described above, and they are not provided in detail for the sake of brevity.

[0136] The present invention aims to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A wear-resistant and tear-resistant foam flame composite fabric, characterized in that: It comprises the following components in parts by mass: 35-45 parts of modified high-strength polyester fiber, 20-30 parts of modified polyurethane film, 30-40 parts of modified polyurethane foam, and 3-5 parts of polyurethane hot melt adhesive.

2. A method for preparing a wear-resistant and tear-resistant foam flame composite fabric, characterized in that, The preparation steps are as follows: Step S1: Burn the modified polyurethane foam with a propane-oxygen mixed flame, heat up to 800-1000 °C, the flame sweeping time is 1-3 s / time, and the melting depth ≤ 0.1 mm to obtain a flame-activated foam. Step S2: Coat the modified high-strength polyester fiber with polyurethane hot melt adhesive, then align the modified polyurethane film, place it on a hot press roller, heat up to 110-130 °C, the pressure is 0.5-1 MPa, and the roller speed is 3-5 m / min to obtain a pre-compounded fabric. Step S3: Align and bond the flame-activated foam with the pre-compounded fabric, let it stand for 3-5 s, then place it on a hot press roller, heat up to 30-50 °C, the pressure is 1.5-2 MPa, and the roller speed is 5-10 m / min to obtain a wear-resistant and tear-resistant foam flame composite fabric. The modified high-strength polyester fiber is a triazine-modified high-strength polyester fiber. The modified polyurethane film is a carbon fiber-modified polyurethane film. The modified polyurethane foam is a silane long-chain modified polyurethane foam.

3. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 2, characterized in that, The preparation method of the triazine-modified high-strength polyester fiber is as follows: Step A1: Add cyanuric chloride, 4-(oxiran-2-ylmethyl)benzene-1,2-diol, sodium hydroxide, and deionized water into an acetone solvent, stir and react for 3-5 h, filter, and perform vacuum distillation to obtain intermediate 1. Step A2: Add intermediate 1 into a tetrahydrofuran solvent, mix evenly, then add 6-amino-1-hexanol, heat up to 20-30 °C, stir and react for 10-14 h, after the reaction is completed, perform vacuum distillation to obtain intermediate 2. Step A3: Mix intermediate 2 with terephthalic acid, heat up to 220-240 °C, react for 2-4 h, add tetrabutyl titanate as a catalyst, evacuate to 40-50 Pa, heat up to 250-260 °C, react for 1-2 h, then heat up to 270-280 °C, react for 3-5 h, after the reaction is completed, cool and pelletize to obtain polyester chips. Step A4: Dry the polyester chips, put them into a spinning machine, heat up to 300-320 °C, filter, the twin-screw extrusion pressure is 4-5 MPa, the winding rate is 700-900 m / min, then stretch with a stretching machine, the total stretching multiple is 4-5, and perform weaving with an air-jet loom. The weaving process is: the reed count is 100, the number of warp ends per reed is 2, the warp and weft density on the loom is 220 ends / 10 cm × 210 ends / 10 cm, the loom reed width is 210 cm, and the total number of warp ends is 7000 to obtain triazine-modified high-strength polyester fiber.

4. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 3, characterized in that, In step A1, the mass ratio of cyanuric chloride, 4-(oxiran-2-ylmethyl)benzene-1,2-diol, sodium hydroxide, and deionized water is 1:4-4.2:1.2-1.4:5.5-6. In step A2, the mass ratio of intermediate 1 to 6-amino-1-hexanol is 1.8-2:

1. In step A3, the mass ratio of intermediate 2 to terephthalic acid is 4-5:

1.

5. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 2, characterized in that, The carbon fiber modified polyurethane film is prepared as follows: Step B1: Add carbon fiber to acetone solvent, heat to 50-60°C, react for 10-14 hours, and after the reaction is complete, ultrasonically treat for 3-7 minutes and dry to obtain debonded carbon fiber; Step B2: adding the debonded carbon fiber to a 65% concentrated nitric acid solution, heating to 80-100° C., reacting for 110-130 min, adjusting the pH to 7, adding a cyclotriphosphazene-modified silane coupling agent, heating to 90-110° C., reacting for 1-3 h, and rinsing with boiling water to obtain a cyclotriphosphazene-modified silane coupling agent-modified carbon fiber; Step B3: Mix polyether polyol YD-4110, YD-889, YD-204, and YD-380 evenly, add foam stabilizer and antioxidant, and stir for 20-40 minutes to obtain component A; Step B4: Add polymethylene polyphenyl polyisocyanate into a beaker, raise the temperature to 50-70°C, and preheat for 50-70 minutes to obtain component B; Step B5: Add component A and component B to a beaker, heat to 30-50°C, react for 2-4 minutes, stir for 1-3 minutes, then add cyclotriphosphazene-modified silane coupling agent to modify the carbon fiber, heat to 50-60°C, cure for 50-70 minutes, cool to 20-30°C, and let stand for 22-26 hours to obtain a carbon fiber modified polyurethane film.

6. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 5, characterized in that, In step B2, the mass ratio of the debonded carbon fiber, concentrated nitric acid solution, and cyclotriphosphazene-modified silane coupling agent is 1:9-11:0.02-0.04; The mass ratio of the polyether polyol YD-4110, YD-889, YD-204, YD-380, foam stabilizer and antioxidant in step B3 is 5.8-6.2:2.8-3.2:1:1.4-1.6:0.35-0.45:0.023-0.27; In step B5, the mass ratio of component A, component B and cyclotriphosphazene-modified silane coupling agent-modified carbon fiber is 1:1.0-1.2:0.02-0.

04.

7. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 5, characterized in that, The preparation method of the cyclotriphosphazene modified silane coupling agent is as follows: Step C1: Under an argon atmosphere, hexachlorocyclotriphosphazene and hydroquinone are added to tetrahydrofuran solvent, stirred and mixed uniformly, triethylamine is added, the temperature is raised to 65-75°C, and the reaction is stirred for 45-50 hours. After the reaction is complete, the temperature is lowered, the mixture is cooled, filtered, distilled under reduced pressure, and recrystallized to obtain intermediate 3; Step C2: Add paraformaldehyde to tetrahydrofuran solvent, add CaH2, raise the temperature to 20-30°C, react for 20-40 minutes, then raise the temperature to 50-70°C, add N-[3-(trimethoxysilyl)propyl]ethylenediamine, raise the temperature to 75-85°C, add intermediate 3, react for 2-4 hours, filter, and distill under reduced pressure to obtain a cyclotriphosphazene-modified silane coupling agent.

8. The method for preparing the wear-resistant and tear-resistant foam flame composite fabric according to claim 7, characterized in that: The mass ratio of hexachlorocyclotriphosphazene, hydroquinone and triethylamine in step C1 is 1:0.33-0.37:0.80-0.83; The mass ratio of paraformaldehyde, CaH2, N-[3-(trimethoxysilyl)propyl]ethylenediamine and intermediate 3 in step C2 is 0.43-0.47:0.45-0.49:1.65-1.70:

1.

9. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 2, characterized in that, The modified polyurethane foam is prepared as follows: Step D1: Add tetrakis(hydroxymethyl)phosphonium sulfate to diethylene glycol dimethyl ether solvent, raise the temperature to 20-25°C, add n-octadecyltrichlorosilane, raise the temperature to 50-60°C, react for 50-70 minutes, raise the temperature to 120-140°C, react for 8-10 hours, cool, crystallize, and filter to obtain a caged quaternary phosphonium salt long-chain organosilicate; Step D2: Under a nitrogen atmosphere, hexamethylene diisocyanate and polyether polyol LY-4110 are heated to 70-80°C, reacted for 1-3 hours, cooled to 50-60°C, and a chain extender, diethylene glycol, and catalysts, stannous octoate and dibutyl dilaurate, are added and reacted for 3-5 hours. Isocyanate trimer, caged quaternary phosphonium salt long-chain organosilicate and chemical foaming microspheres are added and stirred evenly. The temperature is raised to 110-130°C and reacted for 1-3 hours to obtain silane long-chain modified polyurethane foam.

10. The preparation method of the wear-resistant and tear-resistant foam flame composite fabric according to claim 9, characterized in that, The mass ratio of tetrakis(hydroxymethyl)phosphonium sulfate to n-octadecyltrichlorosilane in step D1 is 1:0.50-0.53; The mass ratio of hexamethylene diisocyanate, polyether polyol LY-4110, diethylene glycol, stannous octoate, dibutyl dilaurate, isocyanate trimer, caged quaternary phosphonium salt long-chain organic silicate and chemical foaming microspheres in step D2 is 1:12-14:1.3-1.5:0.1-0.3:0.1-0.2:2-4:0.5-0.7:0.7-0.9.

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