A multi-network bio-matrix hydrogel conductive coating and a preparation method and application thereof

Abstract

The present application belongs to the field of functional materials and textile technology, and particularly relates to a multi-network biological matrix hydrogel conductive coating as well as a preparation method and application thereof. Compared with the prior art, the multi-network biological matrix hydrogel conductive coating provided by the present application takes natural polymers and biological-based ionic liquids as core raw materials, and has the characteristics of biodegradability; through the compounding of a CNTs / ionic liquid conductive network and a natural polymer ternary network, both light absorption and heating and antistatic functions are simultaneously realized in one-step coating process; through the heat crosslinking and Ca 2+ ion crosslinking to form a double crosslinking network, the mechanical strength of the coating and the interfacial bonding force between the coating and the synthetic fiber fabric are greatly enhanced, so that the functional coating has excellent wash resistance, abrasion resistance and long-term use stability.

Description

Technical Field

[0001] This invention belongs to the field of functional materials and textile technology, and particularly relates to a multi-network biomatrix hydrogel conductive coating, its preparation method and application. Background Technology

[0002] As materials that come into direct contact with the human body, textiles have always been a key focus of industrial upgrading due to their skin-friendly comfort, environmental friendliness, and added functions. Especially in cold environments, developing technologies that combine durable antistatic properties, light absorption and heat generation without compromising the original comfort of the fabric is of great significance.

[0003] Currently, there are significant shortcomings in the relevant technologies in the market:

[0004] Regarding antistatic properties: mainstream technologies use antistatic agents (mostly surfactants) to finish fabrics. This method has significant drawbacks: antistatic agents have extremely poor water resistance, and their effectiveness rapidly diminishes after multiple washes; some chemical antistatic agents may cause skin allergies and impair skin-friendliness; furthermore, their antistatic effect is greatly affected by environmental humidity, and their effectiveness drops sharply in dry environments.

[0005] In terms of heat retention through photothermal conversion, the traditional method involves incorporating far-infrared radiating materials (such as ceramic powder and zirconium oxide). These materials are typically inorganic powders with weak bonding to organic fibers, making them prone to detachment during use and washing, resulting in insufficient functional durability. Furthermore, adding large amounts of powder can cause fabrics to feel stiff and rigid, severely sacrificing their flexibility and breathability, which contradicts the initial goal of achieving skin-friendly comfort.

[0006] In terms of environmental friendliness: Most of the aforementioned functional finishing agents are derived from petroleum-based chemicals or non-renewable mineral resources, and their production and disposal processes are environmentally unfriendly. Furthermore, their non-biodegradable nature increases the environmental burden and fails to meet the growing demand for green consumption.

[0007] In terms of functional integration: existing technologies mostly use "layering processes" to achieve antistatic and heat preservation functions separately. The process is complex, and the use of multiple chemical reagents may interfere with each other or even produce side effects, making it difficult to achieve efficient and stable integration of multiple functions.

[0008] Therefore, there is an urgent need in this field for a new technology that can fundamentally solve the above problems and develop an environmentally friendly textile coating that is derived from nature, comfortable against the skin, long-lasting, and integrates antistatic and light-absorbing heat generation. Summary of the Invention

[0009] In view of this, the technical problem to be solved by the present invention is to provide a multi-network bio-matrix hydrogel conductive coating with skin-friendly, light-absorbing and heat-generating and antistatic functions, as well as its preparation method and application.

[0010] This invention provides a multi-network bio-based hydrogel conductive coating, formed by cross-linking a coating slurry; the coating slurry includes: carbon nanotubes, bio-based ionic liquids, polymers, cross-linking agents, leveling agents, and adhesives; the polymers include chitosan-like substances, alginate, and thickeners; the cross-linking agents are selected from polycarboxylic acid compounds.

[0011] The mass ratio of the carbon nanotubes to the bio-based ionic liquid is 1:(5~15).

[0012] The mass of the carbon nanotubes is 5% to 20% of the mass of the polymer material;

[0013] The mass ratio of chitosan, alginate and thickener is (2~4):(1~3):(1~3).

[0014] Preferably, the mass of the crosslinking agent is 5% to 25% of the mass of the polymer.

[0015] Preferably, the mass of the polymeric substance is 2% to 10% of the mass of the coating slurry;

[0016] The leveling agent is present in an amount of 0.1% to 0.5% of the coating slurry mass.

[0017] The adhesive accounts for 5% to 15% of the mass of the coating slurry.

[0018] Preferably, the bio-based ionic liquid is selected from one or more of choline amino acid ionic liquids, benzyl-functionalized imidazolium salts, benzimidazole systems, and urea-functionalized ionic liquids;

[0019] The chitosan-like substance is selected from chitosan and / or carboxymethyl chitosan;

[0020] The alginate is selected from sodium alginate;

[0021] The thickener is selected from gelatin.

[0022] Preferably, the choline amino acid ionic liquid is selected from choline glycinate ionic liquid;

[0023] The crosslinking agent is selected from citric acid;

[0024] The leveling agent is selected from silicone leveling agents;

[0025] The adhesive is selected from waterborne polyurethane.

[0026] Preferably, the crosslinking includes covalent crosslinking and ionic crosslinking.

[0027] This invention also provides a method for preparing the above-mentioned multi-network bio-matrix hydrogel conductive coating, comprising the following steps:

[0028] S1) Carbon nanotubes, bio-based ionic liquids and water are mixed to obtain a carbon nanotube ionic liquid dispersion;

[0029] A polymer solution is obtained by mixing a polymer with water.

[0030] S2) The carbon nanotube ionic liquid dispersion, polymer solution, crosslinking agent, leveling agent and adhesive are mixed to obtain a coating slurry;

[0031] S3) The coating slurry is transferred to the substrate surface, heated and cross-linked, and then immersed in a solution containing calcium salt for ionic cross-linking to obtain a multi-network biomatrix hydrogel conductive coating.

[0032] Preferably, the concentration of carbon nanotube ionic liquid in the carbon nanotube ionic liquid dispersion is 2~10 mg / mL;

[0033] The mass concentration of the polymer in the polymer solution is 3% to 8%.

[0034] Preferably, in step S2), the mixing speed is 100~1000 rpm; the mixing time is 0.5~2 h;

[0035] The heating temperature in step S3) is 110℃~130℃; the heating time is 5~20 min.

[0036] In step S3), the concentration of calcium salt in the solution containing calcium salt is 1% to 5%; the soaking time is 5 to 20 minutes.

[0037] After the ion crosslinking in step S3) is completed, post-processing is performed to obtain a multi-network biomatrix hydrogel conductive coating.

[0038] The post-processing steps include soaking in water and drying at room temperature in the dark.

[0039] The present invention also provides a functional textile, comprising a textile substrate and the aforementioned multi-network biomatrix hydrogel conductive coating disposed on at least one surface of the textile substrate.

[0040] Compared with existing technologies, the multi-network bio-matrix hydrogel conductive coating provided by this invention has the following advantages:

[0041] 1) Bio-based environmental protection core: Using natural polymers and bio-based ionic liquids as core raw materials, it replaces traditional petroleum-based chemical finishing agents and inorganic powders from the source and has the characteristics of being biodegradable;

[0042] 2) Superior performance: By introducing carbon nanotubes (CNTs) and using ionic liquids to efficiently disperse them, a stable and highly conductive network is constructed, which endows the fabric with efficient and long-lasting photothermal conversion performance and antistatic properties. Its performance far exceeds that of traditional inorganic powders that are easy to fall off or antistatic agents that are not washable.

[0043] 3) Integrated and multifunctional: By combining "CNTs / ionic liquid conductive network" with "natural polymer ternary network", both light absorption and heat generation and antistatic functions are achieved in a one-step coating process, avoiding the complex process of traditional "layering process" and the mutual interference between different chemicals.

[0044] 4) Ultimate durability: achieved through thermal cross-linking (first stage) and Ca 2+ The "double cross-linking network" formed by ionic cross-linking (second stage) greatly enhances the mechanical strength inside the coating and its interfacial bonding with synthetic fiber fabrics (nylon, polyester), giving the functional coating excellent water resistance, abrasion resistance and long-term stability. Attached Figure Description

[0045] Figure 1 A schematic diagram illustrating the preparation process of the multi-network biomatrix hydrogel conductive coating provided by this invention;

[0046] Figure 2 A schematic diagram of the structure of the functional textile provided by the present invention. Detailed Implementation

[0047] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] This invention provides a multi-network bio-based hydrogel conductive coating, formed by cross-linking a coating slurry; the coating slurry includes: carbon nanotubes, bio-based ionic liquid, polymer, cross-linking agent, leveling agent, and adhesive; the cross-linking agent is selected from polycarboxylic acid compounds; the polymer includes chitosan, alginate, and thickener; the mass ratio of carbon nanotubes to bio-based ionic liquid is 1:(5~15); the mass of carbon nanotubes is 5%~20% of the mass of polymer; the mass ratio of chitosan, alginate, and thickener is (2~4):(1~3):(1~3).

[0049] This invention innovatively constructs a natural polymer ternary blend system, reinforced with carbon nanotubes, and utilizes a double cross-linked network technology to develop a new one-step coating technology for composite functional coatings on textile substrates. The aim is to overcome the aforementioned technical bottlenecks and provide a multifunctional textile solution that combines efficient photothermal heating, long-lasting antistatic properties, excellent durability, and fully biodegradable characteristics. This technology is simple to implement, low in cost, and simultaneously meets consumers' comprehensive needs for technological functionality, wearing comfort, and environmental friendliness.

[0050] In one specific embodiment of the present invention, optionally, the mass ratio of the carbon nanotubes to the bio-based ionic liquid is 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15 or any two of the above values.

[0051] In one specific embodiment of the present invention, the carbon nanotube can be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture of the two; the average diameter of the carbon nanotube is preferably less than or equal to 2 nm; and the length of the carbon nanotube is preferably 0.5 to 30 μm.

[0052] In one specific embodiment of the present invention, the bio-based ionic liquid is preferably one or more of choline amino acid ionic liquids, benzyl-functionalized imidazolium salts, benzimidazole systems, and urea-functionalized ionic liquids. The cation-π interaction between the bio-based ionic liquid and carbon nanotubes, as well as the possible steric hindrance, enables the carbon nanotubes to be uniformly dispersed, reducing the formation of agglomerates. The special structure of the carbon nanotubes also allows them to crosslink and entangle with polymers, making them easier to fix. At the same time, the ionic solution acts as both a dispersant and a crosslinking agent, forming ionic crosslinks with polymers (especially sodium alginate). The synchronous and uniform dispersion of the ionic solution and carbon nanotubes gives the material antistatic and light-absorbing and heat-generating functions.

[0053] In one specific embodiment of the present invention, the bio-based ionic liquid is preferably a choline amino acid ionic liquid, and more preferably a choline glycinate ionic liquid.

[0054] In one specific embodiment of the present invention, the mass of the carbon nanotube is preferably 5% to 20% of the mass of the polymer material; optionally, the mass of the carbon nanotube is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% of the mass of the polymer material or any two of the above values.

[0055] In this invention, the polymeric substance includes chitosan, alginate, and a thickener; the mass ratio of the chitosan, alginate, and thickener is (2~4):(1~3):(1~3); optionally, the mass ratio of the chitosan, alginate, and thickener is 2:1:1, 2:2:1, 2:3:1, 2:1:2, 2:2:2, 2:3:2, 2:1:3, 2:2:3, 2:3:3, 3:1:1, 3:2:1, 3:3:1, 3:1:2, 3:2:2, 3:3:2, 3:1:3, 3:2:3, 4:1:1, 4:2:1, 4:3:1, 4:1:2, 4:3:2, 4:1:3, 4:2:3, 4:3:3, or any range between any two of the above ratios. Through the synergistic effect of chitosan, alginate, and thickener, the polymer triple cross-linking forms a special three-dimensional network structure. The long chains of chitosan are rich in carboxyl and amino groups, which can form hydrogen bonds with thickener and alginate, becoming a flexible network, i.e., a fluid state, which facilitates uniform coating in the future.

[0056] In a specific embodiment of the present invention, the chitosan-like substance is preferably chitosan and / or carboxymethyl chitosan, more preferably carboxymethyl chitosan; the molecular weight of the carboxymethyl chitosan is preferably 100,000 to 400,000 Da; optionally, the molecular weight of the carboxymethyl chitosan is 100,000 Da, 200,000 Da, 300,000 Da, 400,000 Da or any two of the above values; the degree of substitution of the carboxymethyl chitosan is preferably greater than or equal to 80%, more preferably greater than or equal to 90%.

[0057] In one specific embodiment of the present invention, the alginate is preferably sodium alginate; the viscosity of the sodium alginate is preferably 100~500 mPa·s; optionally, the viscosity of the sodium alginate is 100 mPa·s, 150 mPa·s, 200 mPa·s, 250 mPa·s, 300 mPa·s, 350 mPa·s, 400 mPa·s, 450 mPa·s, 500 mPa·s or any two of the above values.

[0058] In one specific embodiment of the present invention, the thickener is preferably gelatin.

[0059] In one specific embodiment of the present invention, the coating slurry further includes water to make it fluid enough for coating; the mass of the polymer is preferably 2% to 10% of the mass of the coating slurry; optionally, the mass of the polymer is 2%, 4%, 6%, 8%, 10% of the mass of the coating slurry or a range between any two of the above values.

[0060] In one specific embodiment of the present invention, the mass of the crosslinking agent is preferably 5% to 25% of the mass of the polymer; optionally, the mass of the crosslinking agent is 5%, 10%, 15%, 20%, 25% of the mass of the polymer or any two of the above values.

[0061] The crosslinking agent can chemically crosslink with the functional groups of polymeric substances to form a stable covalent network, thereby improving the coating's properties and stability. In this invention, the crosslinking agent is preferably a polycarboxylic acid compound that can react with hydroxyl or amino groups to form covalent bonds under heating conditions, while ensuring a fully bio-based material; citric acid is preferred.

[0062] In one specific embodiment of the present invention, the mass of the leveling agent is preferably 0.1% to 0.5% of the mass of the coating slurry; optionally, the mass of the leveling agent is 0.1%, 0.2%, 0.3%, 0.4%, 0.5% of the mass of the coating slurry or a range between any two of the above values.

[0063] The coating performance of the slurry can be improved by using a leveling agent; the leveling agent can be any leveling agent known to those skilled in the art, and there are no special restrictions. In this invention, an organosilicon leveling agent is preferred, and a polyether-modified siloxane leveling agent is more preferred.

[0064] In one specific embodiment of the present invention, the mass of the adhesive is preferably 5% to 15% of the mass of the coating slurry; optionally, the mass of the adhesive is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% of the mass of the coating slurry or a range between any two of the above values.

[0065] Adding an adhesive can improve the adhesion between the coating and the fabric; the adhesive can be any adhesive known to those skilled in the art and there are no special restrictions, but waterborne polyurethane is preferred in this invention.

[0066] In this invention, the multi-network biomatrix hydrogel conductive coating is formed by cross-linking of the coating slurry; the cross-linking includes covalent cross-linking and ionic cross-linking.

[0067] This invention also provides a method for preparing the above-mentioned multi-network bio-based hydrogel conductive coating, comprising the following steps: S1) mixing carbon nanotubes, bio-based ionic liquids and water to obtain a carbon nanotube ionic liquid dispersion; mixing a polymer with water to obtain a polymer solution; S2) mixing the carbon nanotube ionic liquid dispersion, the polymer solution, a crosslinking agent, a leveling agent and an adhesive to obtain a coating slurry; S3) transferring the coating slurry to the surface of a substrate, crosslinking it by heating, and then immersing it in a solution containing calcium salts for ionic crosslinking to obtain a multi-network bio-based hydrogel conductive coating.

[0068] In this invention, there are no special restrictions on the source of any raw materials; they can be commercially available. The carbon nanotubes, bio-based ionic liquids, polymers, crosslinking agents, leveling agents, and adhesives are all as described above and will not be repeated here.

[0069] Carbon nanotubes, bio-based ionic liquids, and water are mixed to obtain a carbon nanotube ionic liquid dispersion; the water is preferably deionized water; the mixing method can be any method well known to those skilled in the art, and in this invention, ultrasonic mixing is preferred; the ultrasonic power is preferably 200~800 W; optionally, the ultrasonic power is 200 W, 300 W, 400 W, 500 W, or any two of the above values; the mixing time is preferably 10~60 min; optionally, the mixing time is 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, or any two of the above values; the concentration of carbon nanotube ionic liquid in the carbon nanotube ionic liquid dispersion is preferably 2~10 mg / mL; optionally, the concentration of carbon nanotube ionic liquid in the carbon nanotube ionic liquid dispersion is 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL, 10 mg / mL, or any two of the above values.

[0070] A polymer is mixed with water to obtain a polymer solution; the water is preferably deionized water; the mixing method is preferably stirring; the mass concentration of the polymer in the polymer solution is preferably 3% to 8%; optionally, the mass concentration of the polymer in the polymer solution is 3%, 4%, 5%, 6%, 7%, 8% or any two of the above values.

[0071] The carbon nanotube ionic liquid dispersion, polymer solution, crosslinking agent, leveling agent, and adhesive are mixed to obtain a coating slurry. The mixing speed is preferably 100~1000 rpm; optionally, the mixing speed is 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm, or any two of the above values. The mixing time is preferably 0.5~2 h; optionally, the mixing time is 0.5 h, 1 h, 1.5 h, 2 h, or any two of the above values.

[0072] The coating slurry is transferred to the substrate surface, crosslinked by heating, and then immersed in a solution containing calcium salt for ionic crosslinking. The transfer method is preferably coating. The thickness of the coating slurry transferred to the substrate surface is preferably 0.1~2 mm, more preferably 0.5~1 mm. The substrate can be any substrate known to those skilled in the art and is not particularly limited; in this invention, a textile substrate is preferred. The heating temperature is preferably 110℃~130℃; optionally, the heating temperature is 110℃, 115℃, 120℃, 125℃, 130℃, or any two of the above values. The heating time is preferably 5~25 min; optionally, the heating time is 5 min, 10 min, 15 min, 20 min, 25 min, or any two of the above values. The calcium salt is preferably calcium chloride. The concentration of calcium salt in the solution containing calcium salt is preferably 1%~5%; optionally, the concentration of calcium salt in the solution containing calcium salt is 1%, 2%, 3%, 4%, 5%, or any two of the above values. The immersion time is preferably 5~20 min. The soaking time can be 5 min, 10 min, 15 min, 20 min, or any two of the above values. Soaking in a solution containing calcium salts can replenish ions in the already formed three-dimensional network, improving antistatic properties. Furthermore, due to the ionic cross-linking properties of alginate and calcium ions, alginate not only provides carboxyl groups in the chemical cross-linking process but also fixes calcium ions, enhancing coating toughness and improving antistatic properties.

[0073] After ionic crosslinking, post-treatment is preferably performed to obtain a multi-network bio-matrix hydrogel conductive coating. The post-treatment preferably includes immersion in water and drying at room temperature in the dark, more preferably immersion in deionized water and drying at room temperature in the dark. Furthermore, gentle stirring is preferably performed during immersion to remove residual ions. The immersion time is preferably 10-30 min; optionally, the immersion time is 10 min, 15 min, 20 min, 25 min, 30 min or any two of the above values. The drying time is preferably 10-30 h; optionally, the drying time is 10 h, 15 h, 20 h, 24 h, 28 h, 30 h or any two of the above values.

[0074] In a specific embodiment provided by the present invention, the preparation process of the multi-network biomatrix hydrogel conductive coating is as follows: Figure 1 As shown.

[0075] This invention achieves a dual integration of light absorption and heat generation in a coating and long-lasting antistatic function by constructing a synergistic system of ionic liquid dispersed carbon nanotube conductive network and natural polymer triple cross-linked stable framework, while maintaining excellent biocompatibility and environmental friendliness.

[0076] The present invention also provides a functional textile, comprising a textile substrate and the aforementioned multi-network biomatrix hydrogel conductive coating disposed on at least one surface of the textile substrate.

[0077] See Figure 2 , Figure 2 A schematic diagram of the structure of the functional textile provided by the present invention.

[0078] In one specific embodiment of the present invention, the thickness of the multi-network biomatrix hydrogel conductive coating is preferably 0.1~2 mm, more preferably 0.5~1 mm.

[0079] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a multi-network bio-matrix hydrogel conductive coating, its preparation method, and its application.

[0080] All reagents used in the following examples are commercially available; raw materials used in the examples and comparative examples: raw materials: carbon nanotubes, 96%, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; choline glycinate ionic liquid ([Ch][Gly]), 99%, manufacturer: Xi'an Qiyue Biotechnology Co., Ltd.; carboxymethyl chitosan, degree of substitution 90%, molecular weight 100,000 - 400,000 Da, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; sodium alginate, viscosity: 200-250 mPa·S, AR, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; gelatin, CP, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; citric acid, AR, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; waterborne polyurethane, industrial grade, manufacturer: Anhui Luyang New Material Technology Co., Ltd.; polyether modified siloxanes, industrial grade, manufacturer: Guangdong Sandingjia New Material Technology Co., Ltd.; calcium chloride (CaCl2) solution, CP, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.

[0081] Examples 1-9 and Comparative Examples 1-4

[0082] A1) Preparation of CNTs / ionic liquid dispersions

[0083] Carbon nanotubes (CNTs) and choline glycinate ionic liquid ([Ch][Gly]) were mixed with deionized water (the water volume was included in the total water volume of subsequent steps) at a mass ratio of 1:5~15 (specific ratios are shown in Table 1). The mixture was placed in an ultrasonic disruptor and ultrasonically treated at 500 W for 30 minutes to obtain a uniform and stable 6 mg / mL CNTs / IL dispersion.

[0084] A2) Preparation of hydrogel precursor coating solution

[0085] Preparation of polymer solution: Carboxymethyl chitosan (CMCS), sodium alginate (SA), and gelatin are dissolved in deionized water at a mass ratio of 2~4:1~3:1~3 (specific ratios are shown in Table 1), stirred until completely dissolved, and a solution with a total concentration of 6wt% is prepared to obtain the polymer solution.

[0086] Add the following to the above polymer solution in sequence:

[0087] The CNTs / IL dispersion obtained in A1) is added in such a way that the CNTs account for 5% to 20% of the total mass of CMCS / SA / gelatin (the specific dosage is shown in Table 1).

[0088] The cross-linking agent citric acid is used at a rate of 5% to 25% of the total mass of carboxymethyl chitosan (CMCS), sodium alginate (SA), and gelatin (specific amounts are shown in Table 1).

[0089] Leveling agents (such as polyether-modified siloxanes) are used at a rate of 0.3% of the total slurry mass.

[0090] The amount of adhesive (such as water-based polyurethane) used is 10% of the total slurry mass;

[0091] Homogenization: Stir the mixture at 500 rpm for 1 hour on a mechanical stirrer to ensure that all components are mixed evenly, and obtain the hydrogel precursor coating solution.

[0092] A3) Coating and Double Crosslinking Curing

[0093] Coating: The hydrogel precursor coating solution prepared in A2) is uniformly coated onto the surface of the pretreated fabric using a doctor blade coater (0.5 mm gap between the blades).

[0094] Thermal crosslinking: The coated fabric is placed in a 120°C oven and heated for 15 minutes. Citric acid reacts with the hydroxyl / amino groups of CMCS, gelatin, etc., to undergo thermally induced esterification / amidation reactions, forming the first covalent crosslinking network.

[0095] Ionic crosslinking: The above fabric is immersed in a 3 wt% calcium chloride (CaCl2) solution for 10 minutes to carry out ionic crosslinking and form a second sodium alginate network.

[0096] A4) Post-processing

[0097] Washing: Soak the cross-linked fabric in deionized water and gently agitate for 15 minutes to remove residual Ca. 2+ and Cl - ion.

[0098] Drying: Place the washed fabric at room temperature away from light and dry slowly for 24 hours to eventually form a firmly adhered conductive hydrogel coating on the fabric surface.

[0099] Experimental Test

[0100] Light absorption and heat storage performance test: Refer to GB / T 18319-2019 "Test Method for Light and Heat Storage Performance of Textiles";

[0101] Antistatic property test: Refer to GB / T 12703.1-2021 Electrostatic performance evaluation - Static voltage half-life;

[0102] Flexibility test: GB / T 18318-2009 Inclined plane method;

[0103] Washing method: GB / T8629-2017 Type A washing machine 4N program, detergent "Standard Detergent 3" should be selected;

[0104] The performance test results are shown in Table 1.

[0105] Table 1 Performance Test Results

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] As shown in Table 1, compared with Example 1, Example 2 had a lower amount of ionic liquid in the coating, resulting in uneven CNT dispersion and fine spots on the coating; Example 3 had uniform carbon nanotube dispersion in the coating, but the excessive ionic liquid made the network slightly softer; Example 4 had a lower amount of carbon nanotubes in the coating, resulting in slightly poorer light absorption and heat generation, antistatic properties, and durability; Example 5 had excessive carbon nanotubes causing agglomeration; Example 6 was dominated by chitosan, resulting in a hard and brittle feel; Example 7 had a high content of sodium alginate and gelatin, making it too hard and easy to fall off; Example 8 had low crosslinking, resulting in partial detachment; Example 9 had strong crosslinking, making it hard; Comparative Example 1 did not add bio-based ionic liquid, resulting in severely deteriorated functionality and durability; Comparative Example 2 lacked chitosan, resulting in fewer crosslinking sites; Comparative Example 3 did not add the crosslinking agent citric acid, resulting in no covalent crosslinking and poor water resistance; Comparative Example 4 used graphene to replace carbon nanotubes, which easily agglomerated, resulting in brittle mechanical properties, a stiff feel, weakened electrical conductivity and photothermal properties, and was also expensive and environmentally unfriendly.

[0113] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multi-network bio-matrix hydrogel conductive coating, characterized in that, The coating is formed by cross-linking a coating slurry; the coating slurry includes: carbon nanotubes, bio-based ionic liquid, polymer, cross-linking agent, leveling agent, and adhesive; the polymer includes chitosan-like substances, alginate, and thickener; the cross-linking agent is selected from polycarboxylic acid compounds; the bio-based ionic liquid is selected from choline amino acid ionic liquids; and the thickener is selected from gelatin. The mass ratio of the carbon nanotubes to the bio-based ionic liquid is 1:(5~15). The mass of the carbon nanotubes is 5% to 20% of the mass of the polymer material; The mass ratio of chitosan, alginate and thickener is (2~4):(1~3):(1~3).

2. The multi-network bio-matrix hydrogel conductive coating according to claim 1, characterized in that, The mass of the crosslinking agent is 5% to 25% of the mass of the polymer.

3. The multi-network bio-matrix hydrogel conductive coating according to claim 1, characterized in that, The mass of the polymeric substance is 2% to 10% of the mass of the coating slurry; The leveling agent is present in an amount of 0.1% to 0.5% of the coating slurry mass. The adhesive accounts for 5% to 15% of the mass of the coating slurry.

4. The multi-network bio-matrix hydrogel conductive coating according to claim 1, characterized in that, The chitosan-like substance is selected from chitosan and / or carboxymethyl chitosan; The alginate is selected from sodium alginate.

5. The multi-network bio-matrix hydrogel conductive coating according to claim 4, characterized in that, The choline amino acid ionic liquid is selected from choline glycinate salt ionic liquid. The crosslinking agent is selected from citric acid; The leveling agent is selected from silicone leveling agents; The adhesive is selected from waterborne polyurethane.

6. The multi-network bio-matrix hydrogel conductive coating according to claim 1, characterized in that, The crosslinking includes covalent crosslinking and ionic crosslinking.

7. A method for preparing the multi-network bio-matrix hydrogel conductive coating according to claim 1, characterized in that, Includes the following steps: S1) Carbon nanotubes, bio-based ionic liquids and water are mixed to obtain a carbon nanotube ionic liquid dispersion; A polymer solution is obtained by mixing a polymer with water. S2) The carbon nanotube ionic liquid dispersion, polymer solution, crosslinking agent, leveling agent and adhesive are mixed to obtain a coating slurry; S3) The coating slurry is transferred to the substrate surface, heated and cross-linked, and then immersed in a solution containing calcium salt for ionic cross-linking to obtain a multi-network biomatrix hydrogel conductive coating.

8. The preparation method according to claim 7, characterized in that, The concentration of carbon nanotube ionic liquid in the carbon nanotube ionic liquid dispersion is 2~10 mg / mL; The mass concentration of the polymer in the polymer solution is 3% to 8%.

9. The preparation method according to claim 7, characterized in that, In step S2), the mixing speed is 100~1000 rpm; the mixing time is 0.5~2 h. The heating temperature in step S3) is 110℃~130℃; the heating time is 5~20 min. In step S3), the concentration of calcium salt in the solution containing calcium salt is 1% to 5%; the soaking time is 5 to 20 minutes. After the ion crosslinking in step S3) is completed, post-processing is performed to obtain a multi-network biomatrix hydrogel conductive coating. The post-processing steps include soaking in water and drying at room temperature in the dark.

10. A functional textile, characterized in that, The invention includes a textile substrate and a multi-network biomatrix hydrogel conductive coating disposed on at least one surface of the textile substrate, as described in any one of claims 1 to 6.

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