阅读说明：本技术 自清洁羊毛角蛋白纤维膜材及其制备方法 (Self-cleaning wool keratin fiber membrane material and preparation method thereof ) 是由 彭雄义 邓健 刘仰硕 粟斯伟 蔡映杰 于 2019-10-06 设计创作，主要内容包括：本发明涉及自清洁羊毛角蛋白纤维膜材及其制备方法。该膜材可由下述制备方法制得：先将废旧羊毛清洗,然后将废旧羊毛溶解并提取其中的羊毛角蛋白,将羊毛角蛋白溶液进行冷冻干燥,研磨成粉；将粉体羊毛角蛋白溶于有机溶剂制得成膜乳液；将成膜乳液经过浸渍、提拉和溶剂蒸发工艺流程制得自清洁羊毛角蛋白纤维膜材。本发明制备的自清洁羊毛角蛋白纤维膜材的制备工艺简单,该膜材的耐沾污性强,其自清洁性能好；该膜材在纺织领域具有很好的应用前景。(The invention relates to a self-cleaning wool keratin fiber membrane material and a preparation method thereof. The membrane material can be prepared by the following preparation method: cleaning waste wool, dissolving the waste wool, extracting wool keratin in the waste wool, freeze-drying the wool keratin solution, and grinding the wool keratin solution into powder; dissolving the powdery wool keratin in an organic solvent to prepare a film-forming emulsion; the self-cleaning wool keratin fiber membrane material is prepared by the film-forming emulsion through the process flows of dipping, lifting and solvent evaporation. The self-cleaning wool keratin fiber membrane material prepared by the invention has simple preparation process, strong stain resistance and good self-cleaning performance; the membrane material has good application prospect in the textile field.)

1. Self-cleaning wool keratin fiber membrane material, characterized in that the membrane material can be prepared by the following method: cleaning waste wool, dissolving the waste wool, extracting wool keratin in the waste wool, freeze-drying the wool keratin solution, and grinding the wool keratin solution into powder; dissolving the powdery wool keratin in an organic solvent to prepare a film-forming emulsion; the self-cleaning wool keratin fiber membrane material is prepared by the film-forming emulsion through the process flows of dipping, lifting and solvent evaporation.

2. The method for preparing a self-cleaning wool keratin fiber membrane material of claim 1, comprising the steps of:

(1) selecting waste wool: selecting waste wool discarded in a factory, cleaning the waste wool with a clothing cleaning agent, cleaning the waste wool with a large amount of water, and drying the waste wool;

(2) extraction of wool keratin: weighing a certain mass of waste wool, adding dissolved NaHSO₃Dissolving the mixed water solution of/LiBr/sodium dodecyl sulfate, adjusting the pH value to 8-10, setting the temperature to 60-80 ℃, reacting for 4-6 h under the condition of nitrogen to obtain a wool keratin solution, dialyzing for 24-48 h by using flowing water in a dialysis bag, and dialyzing for 12-24 h by using deionized water to prepare the wool keratin solutionObtaining a purified wool keratin solution;

(3) preparation of powder wool keratin: freeze-drying the wool keratin solution prepared in the step (2), wherein the set temperature is as follows: -50 to-60 ℃, and the drying time is as follows: 8-10 h; grinding and sieving the dried wool keratin with a sieve of 50-150 meshes to prepare powdery wool keratin;

(4) preparation of film-forming emulsion: dissolving the powder wool keratin in N, N-dimethylformamide; after the wool keratin is completely dissolved, adding the mixed solution into Ningru 110, and stirring to uniformly mix the mixed solution; dropwise adding the mixed solution into a saturated sodium dodecyl sulfate aqueous solution for 1-3 h; uniformly stirring by using a magnetic rotor to obtain O/W type emulsion; adding a film forming promoter polyvinyl alcohol to prepare film forming emulsion;

(5) dipping and pulling: and (3) immersing the clean substrate into the film-forming emulsion prepared in the step (4) for the following time: 3-10 min; slowly lifting the substrate from the film-forming emulsion at a speed of: 1-10 cm/min;

(6) solvent evaporation: placing the substrate in air, and naturally cooling at the following cooling temperature: and (3) cooling at 20-25 ℃ for the following time: and (5) preparing the self-cleaning wool keratin fiber membrane material after 12-24 hours.

3. The method for preparing a self-cleaning wool keratin fiber membrane material of claim 2, wherein: the intercepted molecular mass of the dialysis bag in the step (2) is 10000-16000; NaHSO in mixed aqueous solution₃The mass fractions of LiBr and sodium dodecyl sulfate are respectively as follows: 2-4%, 4-6% and 3-5%; the mass volume ratio of the waste wool to the mixed aqueous solution is as follows: 1: 100 to 200.

4. The method for preparing a self-cleaning wool keratin fiber membrane material of claim 2, wherein: the dosage ratio of the powder wool keratin to the N, N-dimethylformamide in the step (4) is as follows: 1g to (10-20) mL; the dosage ratio of Ningru 110 to N, N-dimethylformamide is as follows: 1g to (20-40) mL; the proportion of the mixed solution to the saturated sodium dodecyl sulfate aqueous solution is as follows: 1: 3-5; the molecular weight of the polyvinyl alcohol is 400, and the dosage ratio of the polyvinyl alcohol to the powder wool keratin is as follows: 1g to (3-5).

Technical Field

The invention belongs to the technical field of membrane materials, and particularly relates to a self-cleaning wool keratin fiber membrane material and a preparation method thereof.

Background

The application of textile membrane materials in textile garment materials is receiving more and more attention, and at present, the textile membrane materials mainly comprise polyethylene glycol ether (PEO), Polyethylene (PCL), Polytetrafluoroethylene (PTFE), Polyurethane (PU) and the like. Textile films are used in the textile sector mainly in the following areas: firstly, raw materials for preparing a film laminated fabric; secondly, the membrane is bonded and laminated with knitted fabric, plain woven fabric, thin film and non-woven fabric through an ultra-thin film special adhesive, so that the fabric obtains special performance; and thirdly, the fabric is used for the fabric, so that the fabric has the performances of moisture permeability, water resistance and the like. With the increasing demand of people for the quality of textile clothes, the development and utilization of new textile film materials are hot spots of current research.

In recent years, textile films have received much attention. Chinese invention patent application No. 201780075988.X discloses stretched silicone films that produce porous films from crosslinkable silicone compositions, which films can be used in textile films; the disadvantage of its use in textile films is its poor comfort. Great changes in the spring and wisdom et al reported the performance of urea modified wool keratin composite membranes (Chinese leather 2015,44 (18): 11-16,23), which were prepared from wool keratin, sodium carboxymethylcellulose, urea, etc.; due to its complex composition, its application durability is under further investigation. Wool keratin is a natural biological high molecular polymer, has the advantages similar to wool fiber, and can be widely applied to the fields of artificial fiber, membrane material, fabric finishing agent and the like. The waste wool in China has huge yield, and the preparation of wool keratin in the waste wool into a membrane material with stable structure and excellent performance is an urgent problem to be solved.

Disclosure of Invention

The invention aims to provide a self-cleaning wool keratin fiber membrane material, which aims to overcome the defects in the prior art, has strong stain resistance and shows good self-cleaning performance; the membrane material has good potential in the field of membranes for spinning, and the high-efficiency utilization of waste wool is realized.

The invention aims to provide a self-cleaning wool keratin fiber membrane material, which can be prepared by the following preparation method: cleaning waste wool, dissolving the waste wool, extracting wool keratin in the waste wool, freeze-drying the wool keratin solution, and grinding the wool keratin solution into powder; dissolving the powdery wool keratin in an organic solvent to prepare a film-forming emulsion; the self-cleaning wool keratin fiber membrane material is prepared by the film-forming emulsion through the process flows of dipping, lifting and solvent evaporation.

The invention also aims to provide a preparation method of the self-cleaning wool keratin fiber membrane material, which comprises the following specific steps:

(1) selecting waste wool: waste wool discarded in factories is selected, washed by a clothes washing agent, then washed by a large amount of water and dried.

(2) Extraction of wool keratin: weighing a certain mass of waste wool, adding dissolved NaHSO₃Dissolving the mixed water solution of/LiBr/sodium dodecyl sulfate, adjusting the pH value to 8-10, setting the temperature to 60-80 ℃, reacting for 4-6 h under the condition of nitrogen to obtain a wool keratin solution, dialyzing for 24-48 h by using flowing water of a dialysis bag, and dialyzing for 12-24 h by using deionized water to obtain the purified wool keratin solution.

Preferably, the intercepted molecular mass of the dialysis bag is 10000-16000; NaHSO in mixed aqueous solution₃(g) The mass fractions of LiBr (g) and sodium dodecyl sulfate (g) are respectively as follows: 2-4%, 4-6% and 3-5%; the mass volume ratio of the waste wool to the mixed aqueous solution is as follows: 1: 100-200.

(3) Preparation of powder wool keratin: freeze-drying the wool keratin solution prepared in the step (2), wherein the set temperature is as follows: -50 to-60 ℃, and the drying time is as follows: 8-10 h; and grinding and sieving the dried wool keratin, wherein the size of a screen is 50-150 meshes, so as to prepare the powdery wool keratin.

(4) Preparation of film-forming emulsion: dissolving the powder wool keratin in N, N-dimethylformamide; after the wool keratin is completely dissolved, adding the mixed solution into Ningru 110, and stirring to uniformly mix the mixed solution; dropwise adding the mixed solution into a saturated sodium dodecyl sulfate aqueous solution for 1-3 h; uniformly stirring by using a magnetic rotor to obtain O/W type emulsion; adding film forming promoter polyvinyl alcohol to prepare film forming emulsion.

Preferably, the dosage ratio of the powder wool keratin (g) to the N, N-dimethylformamide (mL) is as follows: 1: 10-20; the dosage ratio of Ningru 110(g) to N, N-dimethylformamide (mL) is as follows: 1: 20-40; the proportion of the mixed solution to the saturated sodium dodecyl sulfate aqueous solution is as follows: 1: 3-5; the molecular weight of the polyvinyl alcohol is 400, and the dosage ratio of the polyvinyl alcohol (g) to the powder wool keratin (g) is as follows: 1: 3-5.

(5) Dipping and pulling: and (3) immersing the clean substrate into the film-forming emulsion prepared in the step (4) for the following time: 3-10 min; slowly lifting the substrate from the film-forming emulsion at a speed of: 1-10 cm/min.

(6) Solvent evaporation: placing the substrate in air, and naturally cooling at the following cooling temperature: and (3) cooling at 20-25 ℃ for the following time: and (5) preparing the self-cleaning wool keratin fiber membrane material after 12-24 hours.

The invention has the following remarkable characteristics:

(1) the self-cleaning wool keratin fiber membrane material prepared by the invention takes waste wool as a raw material, and realizes the efficient utilization of the waste wool.

(2) The self-cleaning wool keratin fiber membrane material prepared by the method has the characteristics of simple preparation process, high membrane forming efficiency and the like; in addition, the film material has strong stain resistance, which shows that the self-cleaning performance is good; the membrane material has good application prospect in the textile field.

(3) The self-cleaning wool keratin fiber membrane material is prepared by adopting an emulsion film forming method, and the prepared membrane material is uniform in thickness.

Detailed Description

The examples described below illustrate the invention in detail.