Preparation method and application of organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent

Abstract

The invention discloses an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing a keratin solution from waste wool and a deep eutectic solvent, adding organosilicon quaternary ammonium salt and an amine catalyst, dialyzing, and freeze-drying to obtain grafted organosilicon quaternary ammonium salt keratin powder with a semi-interpenetrating network structure; the functional cashmere fibers with antibacterial, deodorant, mildew-proof, mothproof and moisture-proof properties can be obtained after the cashmere fibers are fully impregnated, dried and finished; 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 an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent, a preparation method and application thereof, and belongs to the technical field of textile materials. Background Art

[0002] In recent years, with the development of society, people are paying more and more attention to the recycling of resources and the sustainable development of society. The resource energy utilization of waste / abandoned wool scraps has significant environmental and economic benefits, and promotes the recycling of waste resources.

[0003] 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.

[0004] As a new type of green solvent, low eutectic solvents have the advantages of good biocompatibility, low vapor pressure, simple preparation process, adjustable properties and easy recycling. Compared with ionic liquids, which are also environmentally friendly solvents, low eutectic solvents have the advantages of non-toxic synthetic raw materials, few by-products and good biocompatibility, and exhibit excellent physical and chemical properties.

[0005] Compared with the traditional single network structure, the semi-IPN uses keratin as a cross-linked polymer, which provides the skeleton structure and basic physical and chemical properties of the material; while the linear polymer exists in a non-cross-linked form, filling the gaps in the keratin network, which can play a role in strengthening and toughening. Therefore, the keratin semi-IPN structure has sufficient strength while maintaining a certain degree of flexibility and plasticity.

[0006] In summary, the traditional method of extracting wool keratin has the defects of high energy consumption and low yield. As a new type of environmentally friendly low eutectic solvent, it can improve the solubility of wool and achieve efficient output of keratin. Therefore, the study of keratin extracted by low eutectic solvent and organic modified quaternary ammonium salt to form a semi-interpenetrating network structure to prepare antibacterial and mildew-proof finishing agents is not only conducive to exerting the natural antibacterial advantages of keratin, but also can further improve its antibacterial stability and durability through the semi-interpenetrating network structure; the preparation process of the finishing agent meets environmental protection requirements and meets the sustainable development of cashmere products and the pursuit of antibacterial and mildew-proof properties. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent, a preparation method and application thereof, which solves the deficiencies of traditional cashmere fibers and their products in terms of antibacterial and mildew resistance while maintaining the softness and air permeability of the cashmere fibers and their products.

[0008] The first aspect of the present invention provides a method for preparing an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent, which mainly comprises using a low eutectic solvent to dissolve waste wool scraps to prepare keratin, and preparing an antibacterial, deodorizing and mildew-proof functional finishing agent with a semi-interpenetrating network structure with a modified organosilicon quaternary ammonium salt. The present invention comprises the following steps:

[0009] Step 1: Wash the waste wool scraps with a detergent, dry them, cut them into pieces, add them into a low eutectic solvent, heat and stir them to dissolve them to obtain a pretreatment solution, adjust the pH of the pretreatment solution with NaOH, add it into a reducing agent, and then filter, dialyze and freeze-dry them in sequence to obtain keratin powder;

[0010] Step 2: dissolving keratin powder in deionized water by stirring to obtain a keratin solution, adding organosilicon quaternary ammonium salt and amine catalyst, adjusting the pH to 8-11, stirring at room temperature for 2-5 hours, dialyzing, and freeze-drying to obtain grafted organosilicon quaternary ammonium salt keratin powder with a semi-interpenetrating network structure;

[0011] Step 3: Stir and dissolve the grafted silicone quaternary ammonium salt keratin powder in deionized water to obtain an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent.

[0012] Preferably, the method for processing the waste sheep scraps includes fully soaking them in a neutral detergent and repeatedly washing them twice to remove grease, drying them at a temperature of 45° C., and cutting them into short fibers with a length of 6 mm.

[0013] Preferably, the low eutectic solvent comprises a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond acceptor comprises at least one of choline chloride and betaine; and the hydrogen bond donor comprises at least one of urea, thiourea, phenylacetic acid, malic acid, citric acid, succinic acid, ethylene glycol, glycerol, butanediol, xylitol, amino acids, glucose, fructose and trifluoroacetamide.

[0014] Preferably, the mass ratio of the waste wool scraps / low eutectic solvent is 1:(10-30); the mass ratio of the keratin powder / ionic liquid is 1:(15-30); and the mass ratio of the grafted silicone quaternary ammonium salt keratin powder / deionized water is 1:500.

[0015] Preferably, in the method for extracting keratin with a low eutectic solvent, the pretreatment liquid in step 1 can be recovered to obtain a recyclable and reusable low eutectic solvent.

[0016] More preferably, the low eutectic solvent in the filtrate is recovered by rotary evaporation, freeze drying, electrodialysis ultrafiltration, or membrane separation.

[0017] Preferably, the pretreatment liquid is adjusted to a pH of 9-10 with NaOH and then added to a reducing agent with a concentration of 0.5-2.0 mol / L, the temperature condition is set to 40-65° C., and the reaction time is set to 4-12 h.

[0018] More preferably, the reducing agent comprises an aqueous solution of one or more of L-cysteine, urea, sodium sulfide, mercaptoethanol and sodium bisulfite.

[0019] Preferably, the dialysis solution is at least one of deionized water and ultrapure water, the molecular weight cutoff of the dialysis device is 2000-5000Da, the dialysis time is set to 72-108h, and the water is changed every 3h; the freezing temperature is set to -40 to -80°C, and the freezing time is set to 6-10h.

[0020] Preferably, the modified organosilicon quaternary ammonium salt is a fluoride salt 、 At least one of chloride salt, bromide salt and iodide salt;

[0021] Preferably, the amine catalyst includes one of di-n-butylamine, triethylamine, n-butylamine, n-hexylamine or di-n-propylamine.

[0022] The second aspect of the present invention provides an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent prepared by the above method, which has antibacterial and deodorizing, mildew and moth-proofing, and moisture-proofing functions.

[0023] The third aspect of the present invention provides an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent for use in cashmere products such as outdoor sports, accessory protection and home life through knitting, weaving, non-woven and braiding processes.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent of the present invention uses a green and environmentally friendly low eutectic solvent to dissolve waste wool scraps to prepare keratin, and forms a semi-interpenetrating network structure with the organic modified quaternary ammonium salt, which can provide more stable antibacterial, deodorizing and mildew-proof properties.

[0026] (2) The preparation method of the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent described in the present invention has the advantages of stable and durable performance, green and environmentally friendly preparation method, simple operation, low production cost, etc., which can effectively improve the added value and market competitiveness of cashmere textiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of the preparation method of the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent of the present invention;

[0028] Figure 2 This is a schematic diagram of the cross section of the functional cashmere fiber obtained by the present invention;

[0029] Figure 3 This is a schematic diagram of the organic modified quaternary ammonium salt / keratin semi-interpenetrating grid structure obtained by the present invention; DETAILED DESCRIPTION

[0030] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0031] like Figure 1 As shown, the present invention provides a method for preparing an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent, comprising the following steps: step 1): washing discarded wool scraps with a detergent, drying, chopping, adding them into a low eutectic solvent, heating and stirring to dissolve to obtain a pretreatment liquid, filtering, dialysis and freeze-drying the pretreatment liquid in sequence to obtain a keratin powder; step 2): stirring and dissolving the keratin powder in deionized water to obtain a keratin solution, adding an organosilicon quaternary ammonium salt and an amine catalyst, adjusting the pH to 8-11, stirring at room temperature for 2-5 hours, dialysis, freeze-drying to obtain a grafted organosilicon quaternary ammonium salt keratin powder with a semi-interpenetrating network structure; step 3): stirring and dissolving the grafted organosilicon quaternary ammonium salt keratin powder in deionized water, fully impregnating cashmere, and drying and finishing to obtain functional cashmere fiber.

[0032] The method for processing the waste sheep scraps includes fully soaking them in a neutral detergent and repeatedly washing them twice to remove grease, drying them at a temperature of 45° C., and cutting them into short fibers with a length of 6 mm.

[0033] The low eutectic solvent includes a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond acceptor includes at least one of choline chloride and betaine; the hydrogen bond donor includes at least one of urea, thiourea, phenylacetic acid, malic acid, citric acid, succinic acid, ethylene glycol, glycerol, butanediol, xylitol, amino acids, glucose, fructose and trifluoroacetamide.

[0034] The mass ratio of wool to low eutectic solvent is 1:10-1:30; the mass ratio of keratin powder to ionic liquid is 1:15-1:30; the mass ratio of organosilicon quaternary ammonium salt keratin powder to deionized water is 1:500; and the ratio of cashmere fiber to grafted organosilicon quaternary ammonium salt keratin functional finishing agent is 1:20-3:20.

[0035] In the method for extracting keratin with a low eutectic solvent, the filtrate in step 1) can be recovered to obtain a recyclable low eutectic solvent.

[0036] The low eutectic solvent in the filtrate is recovered by rotary evaporation, freeze drying, electrodialysis ultrafiltration, or membrane separation.

[0037] The pretreatment liquid needs to be further treated. The pH of the pretreatment liquid is adjusted to 9-10 with NaOH and then added to a reducing agent with a concentration of 0.5-2.0 mol / L. The temperature condition is set to 40-65° C. and the reaction time is set to 4-12 h.

[0038] The reducing agent includes one or more aqueous solutions of L-cysteine, urea, sodium sulfide, mercaptoethanol and sodium bisulfite.

[0039] The dialysis solution is at least one of deionized water and ultrapure water, the molecular weight cutoff of the dialysis device is 2000-5000Da, the dialysis time is set to 72-108h, and the water is changed every 3h; the freezing temperature is set to -40--80℃, and the freezing time is set to 6-10h.

[0040] The anion of the modified organosilicon quaternary ammonium salt is at least one of F-, Cl-, Br-, and I-.

[0041] The amine catalyst includes one of di-n-butylamine, triethylamine, n-butylamine, n-hexylamine or di-n-propylamine.

[0042] The preparation method and application of the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent are characterized in that the prepared finishing agent has antibacterial and deodorizing, mildew and moth-proofing, and moisture-proofing functions.

[0043] The preparation and processing method of the functional cashmere fiber product includes knitting, weaving, non-woven and braiding weaving processes.

[0044] By using Figure 1 The preparation method described herein prepares 5 products to further illustrate the present invention:

[0045] Example 1: socks; Example 2: insoles; Example 3: T-shirts; Example 4: towels; Example 5: pillowcases.

[0046] The setting parameters of the five embodiments are shown in Table 1.

[0047] Table 1

[0048]

[0049]

Claims

1. A method for preparing an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent, characterized in that: The following steps are involved: Step 1: Wash the waste wool scraps with a detergent, dry them, cut them into pieces, add them into a low eutectic solvent, heat and stir them to dissolve them to obtain a pretreatment solution, adjust the pH of the pretreatment solution with NaOH, add it into a reducing agent, and then filter, dialyze and freeze-dry them in sequence to obtain keratin powder; Step 2: stirring and dissolving keratin powder in deionized water to obtain a keratin solution, adding organosilicon quaternary ammonium salt and amine catalyst, adjusting the pH to 8-11, stirring at room temperature, dialyzing, and freeze-drying to obtain grafted organosilicon quaternary ammonium salt keratin powder with a semi-interpenetrating network structure; Step 3: Stir and dissolve the grafted silicone quaternary ammonium salt keratin powder in deionized water to obtain an organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent.

2. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 1, characterized in that: In the step 1, the low eutectic solvent includes a hydrogen bond donor and a hydrogen bond acceptor; the pH of the pretreatment solution is 9-10, the reducing agent concentration is 0.5-2.0 mol / L, the adjustment temperature condition is set to 40-65°C, and the adjustment time is 4-12h; the dialysis solution is at least one of deionized water and ultrapure water, the molecular weight cutoff of the dialysis device is 2000-5000Da, the dialysis time is set to 72-108h, and the water is changed every 3h; the freezing temperature is set to -40 to -80°C, and the freezing time is set to 6-10h; the mass ratio of waste wool scraps to the low eutectic solvent is 1:(10 to 30).

3. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 2, characterized in that: The hydrogen bond acceptor includes at least one of choline chloride and betaine; the hydrogen bond donor includes at least one of urea, thiourea, phenylacetic acid, malic acid, citric acid, succinic acid, ethylene glycol, glycerol, butanediol, xylitol, amino acids, glucose, fructose and trifluoroacetamide.

4. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 2, characterized in that: The reducing agent comprises one or more aqueous solutions of L-cysteine, urea, sodium sulfide, mercaptoethanol and sodium bisulfite.

5. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 1, characterized in that: The pretreatment liquid in step 1 is filtered and then recovered to obtain a recyclable low eutectic solvent; the recovery method is at least one of rotary evaporation, freeze drying, electrodialysis ultrafiltration, and membrane separation.

6. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 1, characterized in that: In the step 2, the mass ratio of keratin powder to deionized water is 1:(15-30); the modified organosilicon quaternary ammonium salt is a fluoride salt 、 At least one of chloride salt, bromide salt and iodide salt; the amine catalyst includes one of di-n-butylamine, triethylamine, n-butylamine, n-hexylamine or di-n-propylamine.

7. The method for preparing the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 1, characterized in that: In the step 3, the mass ratio of the grafted silicone quaternary ammonium salt keratin powder to deionized water is 1:

500.

8. An organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent obtained by the preparation method according to any one of claims 1 to 7, characterized in that: It has antibacterial, deodorizing, mildew-proof, moth-proof and moisture-proof properties.

9. An application of the organic modified quaternary ammonium salt / keratin semi-interpenetrating network antibacterial finishing agent according to claim 8, characterized in that: It is used in cashmere products for outdoor sports, protective accessories and home life prepared through knitting, weaving, non-woven and braiding processes.

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