阅读说明：本技术 具有反应活性羊毛角蛋白微球抗折皱整理剂的制备方法 (Preparation method of wool keratin microsphere anti-wrinkle finishing agent with reaction activity ) 是由 彭雄义 刘仰硕 娄看看 粟斯伟 蔡映杰 王强 于 2019-10-06 设计创作，主要内容包括：本发明属于纺织化学技术领域,具体涉及具有反应活性羊毛角蛋白微球抗折皱整理剂的制备方法。本发明以废旧羊毛为主要原料,通过乳化-固化法将其制备为羊毛角蛋白纤维微球,然后对此微球进行表面功能化改性,接枝二氯均三嗪基团,得到抗折皱整理剂。本发明的抗折皱整理剂具有反应活性,其反应活性表现在与含纤维素织物可发生化学反应。棉织物经过羊毛角蛋白微球抗折皱整理剂整理后,其折皱回复角明显提高,说明羊毛角蛋白微球抗折皱整理剂对棉织物具有很好的抗折皱整理性能。棉织物经过多次水洗,其抗折皱性能仍能保持。本发明制备的羊毛角蛋白微球抗折皱整理剂使用方便,可以像活性染料一样使用,对环境无污染,具有良好的市场前景。(The invention belongs to the technical field of textile chemistry, and particularly relates to a preparation method of a wool keratin microsphere anti-wrinkle finishing agent with reaction activity. The invention takes waste wool as a main raw material, prepares the waste wool into wool keratin fiber microspheres by an emulsification-solidification method, then carries out surface functional modification on the microspheres, grafts the dichloro-s-triazine group and obtains the anti-wrinkle finishing agent. The anti-crease finishing agent of the invention is reactive in that it reacts chemically with the cellulose-containing fabric. After the cotton fabric is finished by the wool keratin microsphere anti-wrinkle finishing agent, the wrinkle recovery angle of the cotton fabric is obviously improved, which shows that the wool keratin microsphere anti-wrinkle finishing agent has good anti-wrinkle finishing performance on the cotton fabric. The anti-crease performance of the cotton fabric can be still maintained after the cotton fabric is washed by water for many times. The wool keratin microsphere anti-wrinkle finishing agent prepared by the invention is convenient to use, can be used like reactive dye, has no pollution to the environment, and has good market prospect.)

1. The preparation method of the wool keratin microsphere anti-wrinkle finishing agent with reactivity is characterized by comprising the following steps: the method comprises the following steps:

(1) preparation of wool keratin: cleaning and airing waste wool, soaking 5-10 g of wool into 100ml of deionized water, and adding NaOH and H₂O₂And ethylenediamine, and placing the mixture in a constant-temperature oscillator at 40-50 ℃ to oscillate for 60min to obtain a keratin solution; filtering, dialyzing and concentrating the crude solution to obtain a keratin solution; centrifuging the keratin solution by using a centrifugal machine, removing supernatant, and drying the lower solution at low temperature to obtain keratin solid;

(2) preparation of O/W emulsion: putting 2-5 g of wool keratin solid into a round-bottom flask, adding 20-50 ml of N-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding the mixed solution into a round-bottom flask containing a proper amount of span 80, and stirring to uniformly mix the mixed solution; adding the mixed solution into a sodium dodecyl sulfate aqueous solution saturated by N-methylmorpholine, and uniformly stirring by using a magnetic rotor to obtain O/W type emulsion;

(3) and (3) curing the microspheres: adding the emulsion into deionized water, adjusting the water temperature and the stirring speed, continuously diffusing the N-methylmorpholine into the water, reducing the solubility of the wool protein, forming microspheres and separating out to obtain a microsphere precipitation solution; carrying out centrifugal separation, multiple washing and vacuum drying on the microsphere precipitation solution to obtain wool keratin fiber microspheres;

(4) surface functional modification of the microspheres: under the ice bath condition, 1.0-2.0 g of wool keratin microspheres obtained in the step (3) are placed in a three-neck flask filled with 100-200 mL of tetrahydrofuran, a proper amount of cyanuric chloride and 1.0-2.0 g of potassium carbonate are dissolved in 30mL of tetrahydrofuran to obtain a mixed solution, then the mixed solution is dripped into the three-neck flask filled with the wool keratin microsphere anti-wrinkle finishing agent, stirring and reacting are continued for 2 hours after dripping is finished, and finally, filtering, washing and drying are carried out to obtain the wool keratin microsphere anti-wrinkle finishing agent with reaction activity.

2. The process for the preparation of reactive wool keratin microsphere anti-wrinkle finishing agents as claimed in claim 1, characterized in that: in the step (1), the concentration of NaOH in deionized water is 1-5 g/l, and H₂O₂The deionized water accounts for 5-10% of the volume content of the deionized water, and the ethylenediamine accounts for 1-3% of the volume content of the deionized water.

3. The process for the preparation of reactive wool keratin microsphere anti-wrinkle finishing agents as claimed in claim 1, characterized in that: in the step (2), the span 80 accounts for 5-10% of the volume content of the N-methylmorpholine, and the concentration of the sodium dodecyl sulfate aqueous solution is 10-15%.

4. The process for the preparation of reactive wool keratin microsphere anti-wrinkle finishing agents as claimed in claim 1, characterized in that: the ratio of the emulsion to the deionized water in the step (3) is 1: 5-15.

5. The process for the preparation of reactive wool keratin microsphere anti-wrinkle finishing agents as claimed in claim 1, characterized in that: the mass ratio of the cyanuric chloride in the step (4) to the wool keratin microspheres obtained in the step (3) is 1: 0.2-1.

Technical Field

The invention belongs to the technical field of textile chemistry, and particularly relates to a preparation method of a wool keratin microsphere anti-wrinkle finishing agent with reaction activity.

Background

Wool, an important natural fiber material, plays an important role in the development of the human civilization history, and is an important raw material since the development of the textile industry. During the processing and use of textile and leather industries, a great deal of waste wool is produced, such as: how to more efficiently utilize the waste wool becomes a problem to be solved urgently, such as short wool, old wool, flawed wool and the like. The main component of wool is keratin which is rich in various amino acids and has good health care performance. The waste wool is used as raw material, dissolved to prepare wool keratin solution which is used as textile finishing agent to improve the application performance of the fabric. In recent years, the research on the wool keratin solution has attracted much attention, and many researchers use the wool keratin solution to finish bamboo fabrics, cotton fabrics, wool fabrics and polyester fabrics, and as a result, the following findings are obtained: the wool keratin solution can obviously improve and enhance the performance of textile fabrics, such as: crease resistance, setting finishing, moisture absorption and quick drying of fabrics and the like. However, the application of the wool keratin solution is not sufficient, the wool keratin has no functional group with high reactivity and low chemical reactivity, and the wool keratin and the fabric are mainly combined by non-covalent bonds such as hydrogen bonds, van der waals force and the like in finishing, so that the wool keratin can gradually fall off after the fabric is washed by water for many times, and the efficacy of the wool keratin is weakened. In order to overcome the defect of application of the wool keratin, the invention aims to prepare the wool keratin microsphere anti-wrinkle finishing agent with reaction activity.

In recent years, many studies have been reported on the modification of wool keratin, such as: the patent application with the application number of 201210088783.4 discloses a preparation method of a wool keratin finishing liquid, which can enable the product yield to be close to 100% and has good antibacterial property; the patent application with the application number of 201610020624.9 discloses a wool protein modified pure cotton fabric softening process, and the wool keratin modified pure cotton fabric prepared by the process is soft and does not reduce softness after long-term use. Therefore, the wool keratin has a plurality of good effects on the modification of the fabric, and in addition, the wool keratin solution also has certain effects on the anti-crease finishing of the fabric, such as: the storage singapore and the like find that the crease resistance of the raw bamboo fiber is obviously improved after the raw bamboo fiber is treated by the wool keratin solution (the research on improving the crease resistance of the bamboo raw fabric by the wool keratin solution, Shanghai textile science, 2009, 37, 12: 31-36). The fabrics treated by the wool keratin are washed with water for many times, the wool keratin can be gradually lost, the application process is complex, and the cost of the fabrics treated by the wool keratin is higher. The wool keratin microspheres with reactivity prepared by the invention can chemically react with fabrics, and can be washed for many times without loss. The research of the literature finds that the preparation of the wool keratin into microspheres with reactivity is not reported.

Disclosure of Invention

The invention aims to provide a preparation method of a wool keratin microsphere anti-wrinkle finishing agent with reaction activity. The process for treating the fabric with the wool keratin solution is complex, the wool keratin can be gradually lost along with multiple times of water washing of the fabric treated with the wool keratin solution, and the cost for treating the fabric with the wool keratin solution is higher. Aiming at the defects and shortcomings of the wool keratin solution, the wool keratin is prepared into the microspheres with reaction activity and is successfully applied to the aspect of improving the anti-wrinkle performance of the fabric.

In order to achieve the above object, the present invention provides a method for preparing an anti-wrinkle finishing agent of wool keratin microspheres with reactivity, comprising the steps of:

(1) preparation of wool keratin: cleaning and airing a proper amount of waste wool, soaking 5-10 g of wool into 100ml of deionized water, and adding a proper amount of woolNaOH、H₂O₂And placing the mixture and ethylenediamine in a constant-temperature oscillator at 40-50 ℃ to oscillate for 60min to obtain the keratin solution. The crude solution is filtered, dialyzed and concentrated to obtain a keratin solution. Centrifuging the keratin solution by a centrifugal machine, removing supernatant, and drying the lower solution at low temperature to obtain keratin solid.

(2) Preparation of O/W emulsion: 2-5 g of wool keratin solid is taken to be put into a round-bottom flask, 20-50 ml of N-methylmorpholine is added, and the mixture is continuously stirred and completely dissolved at 40 ℃ on a constant-temperature electromagnetic stirrer. When the wool keratin is completely dissolved, the mixed solution is added into a round-bottom flask containing a proper amount of span 80, and the mixture is stirred to be uniformly mixed. Adding the mixed solution into a sodium dodecyl sulfate aqueous solution saturated by N-methylmorpholine, and uniformly stirring by using a magnetic rotor to obtain O/W type emulsion.

(3) And (3) curing the microspheres: and adding excessive deionized water into the emulsion, adjusting the water temperature and the stirring speed, continuously diffusing the N-methylmorpholine into the water, reducing the solubility of the wool protein, forming microspheres and separating out to obtain a microsphere precipitation solution. And carrying out centrifugal separation, multiple washing and vacuum drying on the microsphere precipitation solution to obtain the wool keratin fiber microspheres.

(4) Surface functional modification of the microspheres: under the ice bath condition, placing 1.0-2.0 g of wool keratin microspheres obtained in the step (3) into a three-neck flask filled with 100-200 mL of tetrahydrofuran, dissolving a proper amount of cyanuric chloride and 1.0-2.0 g of potassium carbonate into 30mL of tetrahydrofuran to obtain a mixed solution, then dropwise adding the mixed solution into the three-neck flask filled with the wool keratin microsphere anti-wrinkle finishing agent, continuously stirring for reacting for 2h after dropwise adding is finished, and finally filtering, washing and drying to obtain the wool keratin microsphere anti-wrinkle finishing agent with reaction activity.

Further, in the technical scheme, the concentration of NaOH in deionized water in the step (1) is 1-5 g/l, and H₂O₂The deionized water accounts for 5-10% of the volume content of the deionized water, and the ethylenediamine accounts for 1-3% of the volume content of the deionized water.

Further, in the technical scheme, the span 80 in the step (2) accounts for 5-10% of the volume content of the N-methylmorpholine, and the concentration of the sodium dodecyl sulfate aqueous solution is 10-15%.

Further, the ratio of the emulsion in the step (3) to the deionized water in the technical scheme is 1: 5-15.

Further, in the technical scheme, the mass ratio of the cyanuric chloride in the step (4) to the wool keratin microspheres obtained in the step (3) is 1: 0.2-1.

The invention has the positive effects that:

(1) the wool keratin microsphere anti-wrinkle finishing agent prepared by the invention has reactivity and can chemically react with fabric, so that the wool keratin microsphere anti-wrinkle finishing agent can be well combined with the fabric after being washed for many times.

(2) The wool keratin microsphere anti-wrinkle finishing agent prepared by the invention is convenient to use, can be used like reactive dye, and has no pollution to the environment.

(3) The wool keratin microsphere anti-wrinkle finishing agent prepared by the invention has obvious anti-wrinkle effect on cotton fabrics, and the anti-wrinkle effect of the cotton fabrics can still be kept stable after multiple times of washing.

Detailed Description

The present invention will be described in detail with reference to specific embodiments in order to make those skilled in the art better understand the technical solutions of the present invention.