Preparation method and application of organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent

Abstract

The invention discloses a preparation method and application of an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent. The preparation method comprises the following steps: mixing and stirring nano-graphite powder and an inorganic acid solution, drying, dissolving in a coupling agent and dehydrated ions to obtain a modified graphene oxide dispersion liquid, adding quaternary ammonium salt and an amine catalyst into the dispersion liquid, adjusting the pH value, and stirring until full hydrolysis to obtain an organic / inorganic hybrid graphene-quaternary ammonium salt mixed solution; the preparation method comprises the following steps: adding keratin powder, carrying out magnetic stirring and ultrasonic oscillation treatment to obtain an organic / inorganic hybridized graphene-quaternary ammonium salt-keratin hybrid solution, and carrying out dipping and drying treatment on cashmere fibers to obtain the functional cashmere fibers with antibacterial, deodorizing, far-infrared, moisture-absorbing, heating and other properties. The preparation method is simple, low in cost and good in washability, and can be applied to cashmere products for outdoor sports, accessory protection, home life and the like.

Description

Technical Field

[0001] The invention relates to a preparation method and application of an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution finishing agent, belonging to the technical field of textile materials. Background Art

[0002] Organic quaternary ammonium salts are a new type of cationic antibacterial finishing agent. They use organic anions as a medium to strongly adsorb ammonium cation groups with bactericidal properties on the surface of bacteria, change the permeability of bacterial cell walls, and cause enzymes, coenzymes and metabolic intermediates in the bacteria to overflow, causing the microorganisms to stop breathing and die, thereby achieving bactericidal and antibacterial effects.

[0003] Graphene oxide is a graphene derivative with abundant oxygen-containing functional groups on its surface, and has a two-dimensional honeycomb lattice structure similar to graphene. Modified graphene oxide forms hydrogen bonds with sugars or proteins that make up the cell wall through a large number of oxygen-containing groups on its surface, wrapping the bacteria to hinder the exchange of substances inside and outside the cell, thereby achieving an antibacterial effect.

[0004] At present, keratin, as a natural high molecular weight protein, is one of the valuable resources that has not been fully utilized. It has good antibacterial properties, biocompatibility and degradability, and is often used in the field of textile finishing. However, due to the structural complexity of keratin, in practical applications, it is not used directly, but needs to undergo specific modification treatment to improve the stability and versatility of keratin.

[0005] In summary, organic quaternary ammonium salt type, inorganic graphene type and keratin type antibacterial finishing agents are currently the more commonly used cashmere antibacterial finishing agents. The former is more resistant to high temperatures and more stable, but has the defects of poor washability, easy shedding and poor compatibility, while the latter is non-toxic and has excellent antibacterial properties, but still has certain defects in washability and anti-shedding properties. Therefore, a preparation method is needed to composite organic and inorganic materials to give full play to their respective advantages to improve the performance of cashmere fibers and products; at the same time, through an efficient and simple preparation method, the preparation process of the finishing agent meets environmental protection requirements, meets the sustainable development of cashmere products and the pursuit of antibacterial and mildew resistance. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a method for preparing an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution functional finishing agent, which improves the deficiencies of traditional cashmere fibers in terms of antibacterial properties while maintaining the softness and air permeability of the cashmere fibers themselves.

[0007] In order to solve the above problems, the present invention provides an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent, a preparation method and application thereof, which mainly comprises mixing nano graphite powder with inorganic acid and coupling agent to obtain a modified graphene oxide dispersion, adding quaternary ammonium salt and amine catalyst to the dispersion, and adding keratin powder to obtain an organic / inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid antibacterial functional finishing agent.

[0008] The first aspect of the present invention provides a method for preparing an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent, comprising the following steps:

[0009] Step 1): mixing nanographene powder with an inorganic acid solution, subjecting the mixture to magnetic stirring, ultrasonic dispersion treatment, suction filtration and drying to obtain graphene oxide powder; weighing the graphene oxide powder, adding it to a coupling agent and deionized water, and subjecting it to ultrasonic oscillation treatment to obtain a modified graphene oxide dispersion;

[0010] Step 2): adding a quaternary ammonium salt and an amine catalyst to the modified graphene oxide dispersion obtained in step 1, adjusting the pH to 8-11, stirring at a low speed for 2 hours in a magnetically stirred constant temperature water bath at 25-35° C. to fully hydrolyze, and heating to 65-75° C. to generate an organic / inorganic hybrid graphene-quaternary ammonium salt mixed solution;

[0011] Step 3): adding keratin powder to the organic / inorganic hybrid graphene-quaternary ammonium salt solution obtained in step 2, and obtaining an organic / inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution through magnetic stirring and ultrasonic treatment.

[0012] Preferably, the mass ratio of the nanographite powder to the inorganic acid solution is 1:5; the mass ratio of the coupling agent to the graphene oxide powder to the dehydrated ion is 1:10:60; the mass ratio of the quaternary ammonium salt to the graphene oxide dispersion is 1:40; the mass ratio of the keratin powder to the organic-inorganic hybrid graphene-quaternary ammonium salt solution is 1:10; the mass ratio of the cashmere fiber to the organic-inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution is 1:20;

[0013] Preferably, the nanographene powder has a size of 10-50 nm;

[0014] Preferably, the inorganic acid solution includes one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, perchloric acid, boric acid, and carbonic acid;

[0015] Preferably, the coupling agent includes at least one of a silane coupling agent, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy)silane, a phosphate coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent;

[0016] Preferably, the quaternary ammonium salt is a C8-C 16 At least one of the long carbon chain quaternary ammonium salts;

[0017] Preferably, the magnetic stirring and ultrasonic treatment conditions are: stirring speed is 5000-10000r / min, stirring time is 100-150h, stirring temperature is 50-80°C; ultrasonic treatment conditions are: ultrasonic time is 1-2h, ultrasonic treatment power is 500-1000W;

[0018] Preferably, the amine catalyst comprises one of di-n-butylamine, triethylamine, n-butylamine, n-hexylamine or di-n-propylamine;

[0019] Preferably, the finishing agent prepared from the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution has antibacterial and deodorizing, mildew-proof, far-infrared-proof, heat-generating, wrinkle-resistant, and moisture-absorbing and perspiration-wicking functions;

[0020] Preferably, in the method for impregnating cashmere fibers, the cashmere fibers are evenly spread in a cylindrical container with a circular bottom, a functional finishing agent is poured into an inlet of the container until the surface of the cashmere fibers is completely immersed, and after the impregnation is completed, excess functional finishing agent is discharged from a discharge outlet.

[0021] More preferably, the impregnation area and the filtrate collecting area in the impregnation container can be separated to achieve repeated recycling of the functional finishing agent in the filtrate collecting area.

[0022] Preferably, the immersion temperature is 40-60°C, and the immersion time is 8-12h.

[0023] Preferably, the cashmere fiber is dried at a temperature of 55-85°C.

[0024] Preferably, the preparation and processing methods of the functional cashmere fiber product include knitting, weaving, non-woven and braiding weaving processes.

[0025] The second aspect of the present invention provides an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent prepared by the above method.

[0026] The third aspect of the present invention provides an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent prepared by the above method, which is used in daily outdoor sportswear, such as sweaters, cardigans, coats, underwear, pants and socks, etc., accessories and protective products, such as scarves, shawls, gloves, hats and eye masks, etc., and household products, such as bed sheets, quilt covers, pillowcases, etc. through knitting, weaving, non-woven and braiding processes.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution functional finishing agent of the present invention can have a synergistic effect between the quaternary ammonium salt cation and the modified graphene oxide, which can give full play to the functionality of inorganic and organic materials, and enhance the effect after synergistic enhancement. The modified graphene oxide dispersion and the quaternary ammonium salt are combined through chemical bonds to enhance the binding force between the two, which can not only give the cashmere fiber and its products good functionality, but also avoid shedding, separation and the like, so as to ensure the washability and durability of the subsequent cashmere products.

[0029] (2) The preparation method of the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent of the present invention has the advantages of simple operation method and low production cost, and can effectively improve the added value and market competitiveness of cashmere textiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a schematic diagram of the preparation method of the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent of the present invention;

[0031] Figure 2 This is a schematic diagram of the cross section of the functional cashmere fiber obtained by the present invention;

[0032] Figure 3 This is a schematic diagram of a container for impregnating cashmere fibers with the functional finishing agent obtained by the present invention. DETAILED DESCRIPTION

[0033] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0034] like Figure 1As shown, the preparation method of the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent provided by the present invention comprises the following steps: step 1): mixing a certain mass ratio of nanographite powder and an inorganic acid solution, and subjecting the mixture to magnetic stirring, ultrasonic dispersion treatment, suction filtration and drying to obtain graphene oxide powder; weighing the graphene oxide powder, adding it to a coupling agent and dehydrating ions, and subjecting the mixture to ultrasonic oscillation treatment to obtain a modified graphene oxide dispersion; step 2): adding a quaternary ammonium salt and an amine catalyst to the modified graphene oxide dispersion, and adjusting the pH to 8; -11, stirring at a low speed for 2 hours in a magnetically stirred constant temperature water bath at 25 to 35°C for full hydrolysis, heating to 65 to 75°C to generate an organic / inorganic hybrid graphene-quaternary ammonium salt mixed solution; step 3): adding keratin powder to the organic / inorganic hybrid graphene-quaternary ammonium salt solution, and obtaining an organic / inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution through magnetic stirring and ultrasonic treatment; step 4): fully immersing the cashmere fiber in the organic / inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution for 2-6 hours, and then drying and finishing to obtain functional cashmere fiber.

[0035] The mass ratio of the nanographite powder to the inorganic acid solution is 1:5; the mass ratio of the coupling agent to the graphene oxide powder to the dehydrated ion is 1:10:60; the mass ratio of the quaternary ammonium salt to the graphene oxide dispersion is 1:40; the mass ratio of the keratin powder to the organic-inorganic hybrid graphene-quaternary ammonium salt solution is 1:10; the mass ratio of the cashmere fiber to the organic-inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution is 1:20;

[0036] The nanographene powder has a scale of 10-50 nm;

[0037] The inorganic acid solution includes one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, perchloric acid, boric acid, and carbonic acid;

[0038] The coupling agent includes at least one of a silane coupling agent, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy)silane, a phosphate coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent;

[0039] The quaternary ammonium salt is at least one of a C8-C16 long carbon chain quaternary ammonium salt having a hydroxyl group, an amino group, a carboxyl group, an aldehyde group, or an epoxy group;

[0040] The magnetic stirring treatment conditions are: stirring speed of 5000-15000 r / min, stirring time of 72-120 h, stirring temperature of 50-85° C.;

[0041] The ultrasonic treatment conditions are: ultrasonic time is 2-8h, and ultrasonic treatment power is 1000-2000W;

[0042] The amine catalyst includes one of di-n-butylamine, triethylamine, n-butylamine, n-hexylamine or di-n-propylamine;

[0043] The finishing agent prepared from the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution has antibacterial and deodorizing, mildew-proof, far-infrared-proof, heat-generating, wrinkle-resistant, and moisture-absorbing and perspiration-wicking functions;

[0044] The method for impregnating cashmere fibers comprises: evenly spreading the cashmere fibers in a cylindrical container with a circular bottom, pouring a functional finishing agent into a pouring port of the container until the surface of the cashmere fibers is completely immersed, and discharging excess functional finishing agent from a discharge port after the impregnation is completed.

[0045] The impregnation area and the filtrate collecting area in the impregnation container can be separated, so that the functional finishing agent in the filtrate collecting area can be repeatedly recycled.

[0046] The immersion temperature is 40-60° C., and the immersion time is 8-12 hours.

[0047] The cashmere fiber drying temperature is 55-85°C.

[0048] The preparation and processing method of the functional cashmere fiber product includes knitting, weaving, non-woven and braiding weaving processes.

[0049] By using Figure 1 The preparation method described herein prepares 5 products to further illustrate the present invention:

[0050] Embodiment 1: socks; Embodiment 2: children's bath towel; Embodiment 3: insoles; Embodiment 4: underwear; Embodiment 5: quilt cover, pillowcase and bed sheet.

[0051] The setting parameters of the five embodiments are shown in Table 1.

[0052] Table 1

[0053]

Claims

1. A method for preparing an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent, characterized in that: The following steps are involved: Step 1: mixing nanographene powder with an inorganic acid solution, subjecting the mixture to magnetic stirring, ultrasonic dispersion treatment, suction filtration and drying to obtain graphene oxide powder; weighing the graphene oxide powder, adding it to a coupling agent and deionized water, and subjecting it to ultrasonic oscillation treatment to obtain a modified graphene oxide dispersion; Step 2: Add quaternary ammonium salt and amine catalyst to the modified graphene oxide dispersion obtained in step 1, adjust the pH to 8-11, stir at low speed for 2 hours in a magnetically stirred constant temperature water bath at 25-35° C. to fully hydrolyze, and heat to 65-75° C. to generate an organic / inorganic hybrid graphene-quaternary ammonium salt mixed solution; Step 3: adding keratin powder to the organic / inorganic hybrid graphene-quaternary ammonium salt solution obtained in step 2, and obtaining an organic / inorganic hybrid graphene-quaternary ammonium salt-keratin hybrid solution through magnetic stirring and ultrasonic treatment.

2. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 1, the mass ratio of nanographite powder to inorganic acid solution is 1:5; the mass ratio of coupling agent, graphene oxide powder to dehydrated ions is 1:10:

60.

3. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 1, the scale of the nanographene powder is 10-50nm.

4. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In step 1, the inorganic acid solution includes one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, perchloric acid, boric acid and carbonic acid.

5. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 1, the coupling agent includes at least one of a silane coupling agent, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy)silane, a phosphate coupling agent, a titanate coupling agent, an aluminate coupling agent and a zirconate coupling agent.

6. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 2, the quaternary ammonium salt is a C8-C 16 Long carbon chain quaternary ammonium salt; amine catalysts include di-n-butylamine, triethylamine, n-butylamine or n-hexylamine or di-n-propylamine.

7. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 2, the mass ratio of the quaternary ammonium salt to the modified graphene oxide dispersion is 1:

40.

8. The method for preparing the organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 1, characterized in that: In the step 3, the mass ratio of the keratin powder to the organic-inorganic hybrid graphene-quaternary ammonium salt solution is 1:10; the magnetic stirring treatment conditions are: the stirring speed is 5000-10000 r / min, the stirring time is 100-150h, and the stirring temperature is 50-80°C; the ultrasonic treatment conditions are: the ultrasonic time is 1-2h, and the ultrasonic treatment power is 500-1000W.

9. An organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent obtained by the preparation method according to any one of claims 1 to 8, characterized in that: It has the functions of antibacterial and deodorizing, anti-mildew, anti-far infrared, heat generation, anti-wrinkle, and moisture absorption and perspiration.

10. An application of an organic / inorganic hybrid graphene-quaternary ammonium salt / keratin hybrid solution multifunctional finishing agent according to claim 9, characterized in that: Used for daily wear clothing, accessories, cleaning products and protective products obtained through knitting, weaving, non-woven and braiding processes.

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