阅读说明：本技术 一种甲壳素-壳聚糖纳米复合纤维及其制备方法和应用 (Chitin-chitosan nano composite fiber and preparation method and application thereof ) 是由 张宝德 吴高宇 王也 刘姝 于 2020-08-20 设计创作，主要内容包括：本发明适用于纤维材料技术领域,提供了一种甲壳素-壳聚糖纳米复合纤维及其制备方法和应用,该制备方法包括以下步骤：将甲壳素纳米纤丝置于水中进行均化处理,得到甲壳素水悬浮液；将壳聚糖粉末添加到甲壳素水悬浮液中进行混匀,得到混合液；往混合液中添加乙酸水溶液进行混匀,得到纺丝原液；将纺丝原液进行过滤和脱气处理后,再置于沉淀剂中进行凝固浴和拉伸处理,得到所述甲壳素-壳聚糖纳米复合纤维；所述沉淀剂包括乙醇和NaOH溶液。本发明通过以甲壳素纳米纤丝作为增强材料,以其衍生物壳聚糖作为基体材料,并通过湿法纺织工艺进行制备,可以得到高强度、高刚度、可生物降解、无细胞毒性、生态友好的有序取向结构的纳米复合纤维。(The invention is suitable for the technical field of fiber materials, and provides a chitin-chitosan nano composite fiber and a preparation method and application thereof, wherein the preparation method comprises the following steps: placing the chitin nanofibrils in water for homogenization treatment to obtain chitin aqueous suspension; adding chitosan powder into the chitin aqueous suspension, and uniformly mixing to obtain a mixed solution; adding an acetic acid aqueous solution into the mixed solution, and uniformly mixing to obtain a spinning solution; filtering and degassing the spinning stock solution, and then placing the spinning stock solution in a precipitator for coagulating bath and stretching treatment to obtain the chitin-chitosan nano composite fiber; the precipitant includes ethanol and NaOH solution. The invention uses chitin nanofibrils as a reinforcing material, uses chitosan which is a derivative of the chitin nanofibrils as a matrix material, and prepares the nano composite fiber by a wet spinning process, thereby obtaining the nano composite fiber with ordered orientation structure which has high strength, high rigidity, biodegradability, no cytotoxicity and eco-friendliness.)

1. A preparation method of chitin-chitosan nano composite fiber is characterized by comprising the following steps:

placing the chitin nanofibrils in water for homogenization treatment to obtain chitin aqueous suspension;

adding chitosan powder into the chitin aqueous suspension, and uniformly mixing to obtain a mixed solution;

adding an acetic acid aqueous solution into the mixed solution, and uniformly mixing to obtain a spinning solution;

filtering and degassing the spinning stock solution, and then placing the spinning stock solution in a precipitator for coagulating bath and stretching treatment to obtain the chitin-chitosan nano composite fiber; the precipitant includes ethanol and NaOH solution.

2. The method for preparing the chitin-chitosan nanocomposite fiber according to claim 1, wherein the mass of the chitin nanofibrils is 0.05% to 20% of the mass of the chitosan powder.

3. The method of claim 2, wherein the mass of the chitosan nanofibrils is 0.1-0.3% of the mass of the chitosan powder.

4. The method for preparing chitin-chitosan nano-composite fiber according to claim 1, wherein the total mass concentration of chitosan powder and chitin nanofibrils in the mixed solution is 2% -6%.

5. The method for preparing the chitin-chitosan nano composite fiber according to claim 1, wherein the mass concentration of acetic acid in the acetic acid aqueous solution is 1-3%.

6. The method for preparing the chitin-chitosan nano composite fiber according to claim 1, wherein the volume ratio of ethanol to NaOH solution in the precipitant is 1 (0.8-1.2).

7. The method for preparing the chitin-chitosan nano composite fiber according to claim 1 or 6, wherein the mass concentration of NaOH in the NaOH solution is 8-12%.

8. The chitin-chitosan nanocomposite fiber prepared by the preparation method according to any one of claims 1 to 7.

9. The chitin-chitosan nanocomposite fiber according to claim 8, wherein the tensile strength of the chitin-chitosan nanocomposite fiber is not less than 250MPa, and the Young's modulus is not less than 1.2 GPa.

10. Use of the chitin-chitosan nanocomposite fiber according to claim 8 or 9 as a textile material and/or a biomedical material and/or an aerospace manned closed cabin material.

Technical Field

The invention belongs to the technical field of fiber materials, and particularly relates to a chitin-chitosan nano composite fiber as well as a preparation method and application thereof.

Background

Chitosan is an N-deacetylated product of chitin, and is an ideal polymer with the characteristics of bioabsorbability, no cytotoxicity, and small environmental impact of the processing process. Since the properties of chitosan-based materials are unstable and their strength and rigidity are reduced in a wet environment, chitin nanoparticles or inorganic chrysotile nanotubes may be added to the chitosan matrix in order to optimize the mechanical properties of the chitosan-based materials. Through the property research of the composite material, the 1% -3% chrysotile nanotube is added to induce the preferred orientation of the chitosan matrix, and the strength and the Young modulus of the chitosan matrix can be increased to different degrees. However, since the chrysotile nanotubes have biodegradability and remain in the tissue body for a long time, it is necessary to develop a material having absorbability and no cytotoxicity for both the matrix and the filling material.

In addition, in the prior art, the process for preparing chitosan fiber is usually dry spinning, and the process comprises the steps of dissolving chitosan by using a solvent with a lower melting point and easy volatilization to prepare a spinning stock solution, then spraying the spinning stock solution from a spinning nozzle into a spinning channel under the action of pressure, introducing hot air flow into the spinning channel, and under the action of the hot air flow in the spinning channel, quickly volatilizing the low-boiling-point volatile solvent in the stock solution trickle, taking volatilized solvent steam away by the hot air flow, gradually solidifying the chitosan in the spinning stock solution along with the continuous volatilization of the solvent, and finally forming the chitosan fiber by lengthening and thinning under the action of winding tension. This method has the following disadvantages: in the dry spinning process, due to the problems of high viscosity, more impurities and the like of the chitosan spinning solution, spinneret orifices and filters are often blocked; and the fibers are easy to be adhered, and sectional washing, drying and the like are needed to be adopted in the subsequent spinning process, so that the difficulty of wet spinning is increased. Meanwhile, the dry spinning process is not favorable for orientation of chitosan to form high-strength fibers.

Disclosure of Invention

The embodiment of the invention aims to provide a preparation method of chitin-chitosan nano composite fiber, aiming at solving the problems in the background technology.

The embodiment of the invention is realized in such a way that the preparation method of the chitin-chitosan nano composite fiber comprises the following steps:

placing the chitin nanofibrils in water for homogenization treatment to obtain chitin aqueous suspension;

adding chitosan powder into the chitin aqueous suspension, and uniformly mixing to obtain a mixed solution;

adding an acetic acid aqueous solution into the mixed solution, and uniformly mixing to obtain a spinning solution;

filtering and degassing the spinning stock solution, and then placing the spinning stock solution in a precipitator for coagulating bath and stretching treatment to obtain the chitin-chitosan nano composite fiber; the precipitant includes ethanol and NaOH solution.

As a preferable scheme of the embodiment of the present invention, the mass of the chitin nanofibrils is 0.05% to 20% of the mass of the chitosan powder.

As another preferable scheme of the embodiment of the present invention, the mass of the chitin nanofibrils is 0.1% to 0.3% of the mass of the chitosan powder.

As another preferable scheme of the embodiment of the present invention, in the mixed solution, the total mass concentration of the chitosan powder and the chitosan nanofibrils is 2% to 6%.

In another preferable embodiment of the present invention, the mass concentration of acetic acid in the aqueous acetic acid solution is 1% to 3%.

As another preferable scheme of the embodiment of the invention, in the precipitator, the volume ratio of ethanol to NaOH solution is 1 (0.8-1.2).

In another preferable embodiment of the present invention, the mass concentration of NaOH in the NaOH solution is 8% to 12%.

The other purpose of the embodiment of the invention is to provide the chitin-chitosan nano composite fiber prepared by the preparation method.

As another preferred scheme of the embodiment of the invention, the tensile strength of the chitin-chitosan nano composite fiber is not lower than 250MPa, and the Young modulus is not lower than 1.2 GPa.

Another object of the embodiments of the present invention is to provide an application of the chitosan-chitosan nanocomposite fiber in textile materials and/or biomedical materials and/or aerospace manned closed cabin materials.

The biomedical materials include, but are not limited to, hemostatic tapes, surgical sutures, and the like.

According to the preparation method of the chitin-chitosan nano composite fiber provided by the embodiment of the invention, the chitin nano fibrils are used as a reinforcing material, the chitosan derivative thereof is used as a matrix material, and the chitin/chitosan nano composite fiber is prepared by a wet textile process, so that the chitin/chitosan nano composite fiber with an ordered structure, which has the advantages of high strength, high rigidity, biodegradability, no cytotoxicity and eco-friendliness, can be obtained. The preparation method adopts the technical principle that the orientation of the nano-fibers is realized by utilizing the rheology theory so as to obtain the nano-composite fibers with ordered structures, the ordered structures can endow the nano-composite fibers with enough strength and rigidity modulus, and the nano-composite fibers have excellent biomedical functions and excellent moisture absorption and heat preservation functions, so that the chitin-chitosan nano-composite fibers can be applied to the fields of biology and medicine (wound healing and repair of aorta), the textile and clothing industry and aerospace manned closed cabins.

Drawings

Fig. 1 is a process flow diagram of a preparation method of a chitin-chitosan nanocomposite fiber provided by an embodiment of the present invention.

In fig. 1: 1-dissolving tank, 2-first filter, 3-screw pump, 4-defoaming tank, 5-vacuum pump, 6-air compressor, 7-second filter, 8-metering pump, 9-third filter, 10-spinning nozzle, 11-solidifying bath, 12-first water-washing bath, 13-second water-washing bath and 14-winding roller.

Fig. 2 is an electron microscope image of the chitin-chitosan nanocomposite fiber prepared in example 1 of the present invention.

Fig. 3 is a scanning electron microscope image of an oriented structure of the chitin-chitosan nanocomposite fiber prepared in example 1 of the present invention.

Fig. 4 is an electron microscope image of the aortic part material being the chitin-chitosan nanocomposite fiber prepared in example 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.