Graphene-containing waterproof, windproof and cold-proof cloth and preparation method thereof

Abstract

The invention discloses waterproof, windproof and cold-proof cloth containing graphene and a preparation method of the waterproof, windproof and cold-proof cloth. The preparation method comprises the following steps: firstly, carrying out surface activation treatment on graphene oxide, preparing a stable-dispersion modified graphene dispersion system through coordinated grafting modification of a silane coupling agent and a flexible macromolecular chain segment, then adding the modified graphene dispersion system into water-based waterproof finishing resin to prepare a functional finishing liquid, and carrying out water-based waterproof finishing on the functional finishing liquid. And through padding, drying and curing treatment, the composite material is firmly combined on the surface of the cloth. By constructing a chemical-physical double anchoring structure between the graphene and a fiber film forming system, the dispersion stability of the graphene in a water-based finishing system and the binding strength of the graphene in a fabric are remarkably improved, so that the waterproof, windproof and cold-proof functions have good durability and use stability; the method is suitable for preparing functional protective textiles.

Description

Technical Field

[0001] This invention relates to the field of functional textile technology, and in particular to a graphene-containing waterproof, windproof, and cold-proof fabric and its preparation method. Background Technology

[0002] With the development of outdoor protective clothing and functional textiles, waterproof, windproof, and cold-proof integrated fabrics are widely used in clothing, protective equipment, and other fields. Traditional waterproof, windproof, and cold-proof fabrics often achieve their function by coating with waterproof resin or using composite film structures. However, these fabrics often suffer from insufficient breathability, a stiff feel, and reduced comfort, making it difficult to balance functionality and wearing experience. In recent years, graphene, due to its excellent barrier and thermal regulation properties, has been gradually applied to functional textiles. Existing technologies typically involve directly adding graphene or graphene oxide to the fabric finishing solution, or attaching it to the fiber surface through impregnation or spraying, to improve the windproof or heat-retaining properties of the fabric. These methods are simple and can impart certain functions to the fabric in the initial stage.

[0003] However, in existing technologies, graphene tends to aggregate in aqueous finishing systems, exhibiting poor compatibility with textile fibers and finishing resin systems, resulting in uneven distribution on the fabric surface. Furthermore, graphene primarily exists through physical adsorption, lacking a stable interfacial bonding structure, making it prone to migration and detachment during washing or use, significantly reducing its waterproof, windproof, and cold-resistant properties, and compromising durability. Treatment with surfactants or dispersants to improve dispersibility only provides short-term improvements and cannot fundamentally solve the problem of poor bonding strength between graphene and fabric.

[0004] Therefore, obtaining functional fabrics that combine waterproof, windproof, and cold-proof properties with good wash fastness remains a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the above problems, this invention proposes a graphene-containing waterproof, windproof, and cold-proof fabric and its preparation method. This invention solves the problems of easy agglomeration, easy migration, and poor wash fastness of graphene in existing graphene functional fabrics.

[0006] This invention can be achieved through the following technical solutions:

[0007] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0008] Step 1: Graphene oxide is dispersed in an aqueous medium and mechanically stirred and ultrasonically dispersed. Then, silane coupling agent and flexible polymer grafting component are added to carry out grafting reaction to obtain a surface-grafted modified graphene dispersion system.

[0009] Step 2: Add the water-based waterproof finishing resin system to the modified graphene dispersion system obtained in Step 1, mix evenly, and obtain the functional finishing liquid containing modified graphene.

[0010] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric, and then dry and cure it to obtain a graphene-containing waterproof, windproof and cold-proof fabric.

[0011] Preferably, the graphene oxide sheet diameter in step 1 is 0.5-5 μm.

[0012] Preferably, in step 1, mechanical stirring is performed for 1-3 hours, and ultrasonic dispersion is performed for 30-60 minutes.

[0013] Preferably, the aqueous medium in step 1 is deionized water, a mixture of deionized water and alcohol solvent, or an aqueous system containing an aqueous polymer dispersion.

[0014] Preferably, the silane coupling agent in step 1 is a silane coupling agent containing amino, epoxy, or isocyanate.

[0015] Preferably, the flexible polymer grafting component in step 1 is a waterborne polyurethane segment or an acrylate polymer segment.

[0016] Preferably, the grafting reaction in step 1 is carried out under aqueous conditions, with a reaction temperature of 40-80℃ and a reaction time of 2-8h.

[0017] Preferably, the water-based waterproof finishing resin system in step 2 is a water-based polyurethane resin or an acrylic resin.

[0018] Preferably, the rolling residue in step 3 is 60-90%.

[0019] Preferably, in step 3, the drying temperature is 80-120℃ and the drying time is 2-10 min; the curing temperature is 130-170℃ and the curing time is 2-6 min.

[0020] The beneficial effects of this invention are:

[0021] This invention modifies graphene oxide under aqueous conditions by synergistic grafting of silane coupling agents and flexible polymer segments. This simultaneously introduces a chemically anchored structure that can form covalent bonds with textile fibers and a flexible interface structure that can form molecular entanglements with waterproof finishing resin systems onto the graphene sheet surface, thus constructing a stable chemical-physical dual anchoring interface. This structural modification enables graphene to form a long-term stable and non-migrating functional structure on the fabric surface and in the waterproof film-forming system, significantly improving the dispersion stability of graphene in aqueous finishing systems and its binding strength in fabrics. The synergistic grafting method effectively avoids graphene aggregation in the finishing solution and interface detachment during film formation and use, allowing graphene sheets to exhibit a uniform and parallel dense spread on the fabric surface and within the resin film, thereby constructing a continuous barrier network structure at the microscopic level. This network structure effectively extends and blocks the transfer paths of water molecules, air, and heat, enabling waterproof, windproof, and cold-proof functions to work synergistically and be maintained for a long time.

[0022] This invention is not a simple superposition or replacement of existing graphene finishing technologies, but rather achieves the stabilization and durability of graphene functions on textile substrates through the systematic design of interface structures, which has outstanding substantive features and significant technological progress. Attached Figure Description

[0023] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0024] Figure 1 To improve the waterproof and windproof properties of the fabric;

[0025] Figure 2 For the cold-proof properties of the fabric. Detailed Implementation

[0026] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0027] Example 1:

[0028] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0029] Step 1: 1.0g of graphene oxide with a sheet diameter of 0.5μm was dispersed in 1L of deionized water and mechanically stirred for 1h, followed by ultrasonic dispersion for 30min. Then, 2.0g of amino-containing silane coupling agent and 10.0g of waterborne polyurethane segments were added. Under aqueous conditions, the grafting reaction was carried out at 40℃ for 8h to obtain a surface-grafted modified graphene dispersion system.

[0030] Step 2: Add 500g of aqueous polyurethane resin to the 500mL modified graphene dispersion system obtained in Step 1, mix evenly, and obtain a functional finishing liquid containing modified graphene.

[0031] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric once, with a roll-off rate of 60%. Then, dry the fabric at 80°C for 10 minutes and cure it at 130°C for 6 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0032] Example 2:

[0033] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0034] Step 1: 1.0 g of graphene oxide with a sheet diameter of 2.5 μm was dispersed in 1 L of deionized water / ethanol (volume ratio 8:2) mixed solvent and mechanically stirred for 2 h, followed by ultrasonic dispersion for 45 min. Then, 2.0 g of epoxy-containing silane coupling agent and 10.0 g of acrylate polymer segments were added. Under aqueous conditions, the grafting reaction was carried out at 60 °C for 5 h to obtain a surface-grafted modified graphene dispersion system.

[0035] Step 2: Add 500g of acrylate resin to the 500mL modified graphene dispersion system obtained in Step 1, mix evenly, and obtain a functional finishing liquid containing modified graphene.

[0036] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric, apply it once, with a roll-off rate of 75%, then dry the fabric at 100℃ for 6 minutes and cure it at 150℃ for 4 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0037] Example 3:

[0038] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0039] Step 1: 1.0g of graphene oxide with a sheet diameter of 5μm was dispersed in 1L of deionized water and mechanically stirred for 3h, followed by ultrasonic dispersion for 60min. Then, 2.0g of isocyanate-containing silane coupling agent and 10.0g of acrylate polymer segments were added. Under aqueous conditions, the grafting reaction was carried out at 80℃ for 2h to obtain a surface-grafted modified graphene dispersion system.

[0040] Step 2: Add 500g of acrylate resin to the 500mL modified graphene dispersion system obtained in Step 1, mix evenly, and obtain a functional finishing liquid containing modified graphene.

[0041] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric, apply it once, with a roll-off rate of 90%, then dry the fabric at 120℃ for 2 minutes and cure it at 170℃ for 2 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0042] Comparative Example 1: The difference between this comparative example and Example 1 is that no silane coupling agent and waterborne polyurethane segments are added for graphene grafting modification.

[0043] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0044] Step 1: Disperse 1.0g of graphene oxide with a sheet diameter of 0.5μm in 1L of deionized water, mechanically stir for 1h, and then ultrasonically disperse for 30min. Then add 500g of waterborne polyurethane resin and mix evenly to obtain a graphene-containing functional finishing solution.

[0045] Step 2: Apply the functional finishing liquid to the surface of the polyester fiber fabric once, with a roll-off rate of 60%. Then, dry the fabric at 80°C for 10 minutes and cure it at 130°C for 6 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0046] Comparative Example 2: The difference between this comparative example and Example 1 is that no waterborne polyurethane segments are added for synergistic grafting modification.

[0047] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0048] Step 1: Disperse 1.0g of graphene oxide with a sheet diameter of 0.5μm in 1L of deionized water, mechanically stir for 1h, and then ultrasonically disperse for 30min. Then add 2.0g of amino-containing silane coupling agent and carry out grafting reaction at 40℃ for 8h under aqueous conditions to obtain a surface-grafted modified graphene dispersion system.

[0049] Step 2: Add 500g of aqueous polyurethane resin to the 500mL modified graphene dispersion system obtained in Step 1, mix evenly, and obtain a functional finishing liquid containing modified graphene.

[0050] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric once, with a roll-off rate of 60%. Then, dry the fabric at 80°C for 10 minutes and cure it at 130°C for 6 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0051] Comparative Example 3: The difference between this comparative example and Example 1 is that no silane coupling agent is added for synergistic grafting modification.

[0052] A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric includes the following steps:

[0053] Step 1: Disperse 1.0g of graphene oxide with a sheet diameter of 0.5μm in 1L of deionized water, mechanically stir for 1h, and then ultrasonically disperse for 30min. Then add 10.0g of waterborne polyurethane segments and carry out grafting reaction at 40℃ for 8h under aqueous conditions to obtain a surface-grafted modified graphene dispersion system.

[0054] Step 2: Add 500g of aqueous polyurethane resin to the 500mL modified graphene dispersion system obtained in Step 1, mix evenly, and obtain a functional finishing liquid containing modified graphene.

[0055] Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric once, with a roll-off rate of 60%. Then, dry the fabric at 80°C for 10 minutes and cure it at 130°C for 6 minutes to obtain a waterproof, windproof and cold-proof fabric containing graphene.

[0056] Performance testing

[0057] 1 Waterproof performance test

[0058] Refer to GB / T 4744-2013 standard. Cut 5 samples with a diameter ≥100mm. Clamp the samples on the fixture of the hydrostatic pressure tester, ensuring that the functional side of the fabric faces the water. Start the tester and increase the water pressure at the bottom of the sample by 10±0.5cm H2O / min. Observe the back of the sample. When water droplets appear to penetrate at three different locations, record the water pressure value at this time. Calculate the average value of the hydrostatic pressure results for each group of samples as the waterproof performance data of the fabric.

[0059] Table 1 Waterproof performance test results

[0060] sample Hydrostatic pressure (kPa) Example 1 65.3 Example 2 68.5 Example 3 72.1 Comparative Example 1 28.7 Comparative Example 2 42.9 Comparative Example 3 39.6

[0061] As shown in Table 1, the hydrostatic pressure of Examples 1-3 is ≥65.3 kPa, reaching the level of high-performance professional waterproof fabrics. This is mainly because: on the one hand, the silane coupling agent is chemically anchored to the graphene sheet at one end and forms a covalent bond with the polyester fiber surface at the other end. At the same time, the flexible polymer chain segments are chemically similar to the main waterproof resin matrix, enabling the modified graphene to establish a strong physicochemical connection with both the fiber and the resin matrix. On the other hand, the modified graphene is uniformly dispersed and has strong interfacial bonding, allowing it to spread densely and parallelly on the fiber surface and inside the resin film during film formation, extending and hindering the penetration path of water molecules, thus significantly improving the hydrostatic pressure. In contrast, in Comparative Example 1, the graphene oxide was directly added to the resin, resulting in severe agglomeration and an inability to be uniformly impregnated onto the fabric. The graphene-resin bond was extremely weak, leading to poor waterproof performance. Comparative Example 2 only used silane coupling agent modification, lacking buffering and fusion. The graphene was connected to the resin matrix through short-chain silane molecules, which easily caused stress concentration, inducing microcracks and water molecule penetration. Comparative Example 3 uses only water-based polyurethane segments. The entire functional layer lacks chemical bonding with the polyester fiber substrate. Under water pressure impact or washing, the functional layer is prone to overall migration or detachment from the fiber surface, resulting in poor waterproof performance.

[0062] 2. Windproof and cold-proof performance test

[0063] Refer to GB / T 5453-1997 standard. Cut 5 samples and clamp them flat on the test head of the fabric air permeability meter, ensuring no air leakage. Start the equipment under a pressure difference of 100Pa, measure the air flow rate passing vertically through a unit area of ​​the sample per unit time, record the air permeability of each sample, and calculate the average value as the test result of the fabric's windproof performance (the lower the value, the better the windproof performance).

[0064] Referencing GB / T 11048-2018 standard, two complete samples were cut from the fabric to be tested. The cut samples were placed in a standard atmospheric environment at 20±2℃ and 65±4% relative humidity for 24 hours to acclimate the moisture content of the samples to the test environment. The evaporative hot plate apparatus was turned on and preheated to a stable state. Thermal resistance calibration was performed using a standard reference plate. The following parameters were set in the control software: test plate temperature 35.0±0.1℃ to simulate average human skin temperature, ambient chamber temperature 20.0±0.5℃ to simulate a typical cold environment, relative humidity 65±, and wind speed 1.0±0.1m / s to simulate the airflow velocity over a stationary human body. The acclimated samples were placed on the test plate, and the test program was started. After the system reached a steady state, the thermal resistance value (R) was automatically recorded and calculated. ct The higher the thermal resistance value, the better the cold-proof performance of the fabric.

[0065] Table 2. Test results of windproof and cold-proof performance

[0066] sample Air permeability (mm / s) <![CDATA[Thermal resistance (m 2 ·K / W)]]> Example 1 18.8 0.039 Example 2 22.3 0.041 Example 3 25.7 0.042 Comparative Example 1 85.4 0.030 Comparative Example 2 42.6 0.035 Comparative Example 3 48.1 0.034

[0067] As shown in Table 2, the air permeability of Examples 1-3 is ≤25.7mm / s, and the thermal resistance is ≥0.039m. 2 The K / W ratio is primarily due to the synergistic grafting modification of graphene with silane coupling agents and flexible polymer segments. This allows graphene to be stably dispersed in an aqueous system, forming a continuous, dense, and parallel-aligned nano-barrier structure on the fabric surface. This structure effectively blocks air penetration, significantly reducing air permeability and achieving excellent windproof performance. Furthermore, the low thermal conductivity of the graphene sheets and the continuous network they form greatly hinder heat transfer, improving the fabric's thermal resistance and warmth retention. In addition, the covalent bonds established between the silane coupling agent and the graphene / fiber / resin, synergistically with the physical entanglement of the flexible segments, constitute a robust chemical-physical dual-anchoring interface. This ensures the structural integrity and durability of the functional layer during washing and use, maintaining its windproof and cold-proof performance over time. In contrast, the unmodified graphene in Comparative Example 1 easily aggregates in water-based resins due to van der Waals forces, resulting in an uneven and discontinuous coating on the fabric surface. This coating contains numerous micropores and weak points, allowing air to easily penetrate (air permeability as high as 85.4 mm / s) and causing rapid heat loss (thermal resistance of only 0.030 m). 2 (K / W). Comparative Example 2 uses only silane coupling agent to modify graphene, lacking the buffering and toughening of flexible polymer chains, resulting in the aforementioned microcracks at the interface. The compatibility between the modified graphene and the resin matrix is ​​poor, and its windproof and warmth retention properties are lower than those of Example 1. Comparative Example 3 uses only waterborne polyurethane segment grafted graphene, lacking the strong covalent bond connection with the fiber surface provided by the silane coupling agent. The entire functional layer is only bonded to the fabric by physical adsorption and weak van der Waals forces, and its windproof and warmth retention properties are significantly lower than those of Example 1.

[0068] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a graphene-containing waterproof, windproof, and cold-proof fabric, characterized in that, Includes the following steps: Step 1: Graphene oxide is dispersed in an aqueous medium and mechanically stirred and ultrasonically dispersed. Then, silane coupling agent and flexible polymer grafting component are added to carry out grafting reaction to obtain a surface-grafted modified graphene dispersion system. Step 2: Add the water-based waterproof finishing resin system to the modified graphene dispersion system obtained in Step 1, mix evenly, and obtain the functional finishing liquid containing modified graphene. Step 3: Apply the functional finishing liquid to the surface of the polyester fiber fabric, and then dry and cure it to obtain a graphene-containing waterproof, windproof and cold-proof fabric.

2. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, The graphene oxide sheet diameter in step 1 is 0.5-5 μm.

3. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 1, mechanical stirring is performed for 1-3 hours, and ultrasonic dispersion is performed for 30-60 minutes.

4. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 1, the aqueous medium is deionized water, a mixture of deionized water and alcohol solvents, or an aqueous system containing an aqueous polymer dispersion.

5. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 1, the silane coupling agent is a silane coupling agent containing amino, epoxy, or isocyanate groups.

6. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 1, the flexible polymer grafting component is a waterborne polyurethane segment or an acrylate polymer segment.

7. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 1, the grafting reaction is carried out under aqueous conditions at a temperature of 40-80℃ for 2-8 hours.

8. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 2, the water-based waterproof finishing resin system is a water-based polyurethane resin or an acrylate resin.

9. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, The rolling allowance in step 3 is 60-90%.

10. The method for preparing the graphene-containing waterproof, windproof, and cold-proof fabric according to claim 1, characterized in that, In step 3, the drying temperature is 80-120℃ and the drying time is 2-10 min; the curing temperature is 130-170℃ and the curing time is 2-6 min.

Images