CN-119552354-B - Chitosan grafted modified bio-based nylon material and preparation method and application thereof

CN119552354BCN 119552354 BCN119552354 BCN 119552354BCN-119552354-B

Abstract

The invention belongs to the technical field of high polymer material modification, and provides a chitosan grafted modified bio-based nylon material, and a preparation method and application thereof. The preparation method comprises the following steps of mixing the bio-based nylon salt, water, the catalyst and the chitosan quaternary ammonium salt in a protective atmosphere, and sequentially carrying out a prepolymerization reaction and a final polymerization reaction to obtain the chitosan grafted modified bio-based nylon material. According to the invention, chitosan quaternary ammonium salt is selected to react with bio-based nylon salt, so that the number of positive charges on the surface of original polyamide is increased, a large number of positive charges can promote flocculation of polyamide and proteins, teichoic acids, lipopolysaccharides and the like with negative charges on the surface of cells of the bacteria, and further the permeation barrier effect of cytoplasmic membranes is destroyed, so that the integrity of the cells of the bacteria is destroyed, and nutrient substances are lost, thereby achieving the effect of intrinsic bacteriostasis. The chitosan grafted modified bio-based nylon material has excellent antibacterial performance, mechanical performance and high temperature resistance.

Inventors

HUANG YUHONG
MA ZHANLING
DONG SHANSHAN
CHU BING
LI ZHENZHU
QIN SHAOJIE
ZHANG SUOJIANG

Assignees

中国科学院过程工程研究所
郑州中科新兴产业技术研究院

Dates

Publication Date: 20260512
Application Date: 20241209

Claims (7)

1. The preparation method of the chitosan grafted modified bio-based nylon material is characterized by comprising the following steps of: Mixing a bio-based nylon salt, water, a catalyst and chitosan quaternary ammonium salt in a protective atmosphere, and sequentially performing a prepolymerization reaction and a final polymerization reaction to obtain the chitosan grafted modified bio-based nylon material; the chitosan quaternary ammonium salt is hydroxypropyl trimethyl ammonium chloride chitosan, and the deacetylation degree of the hydroxypropyl trimethyl ammonium chloride chitosan is 97-99%; The mass ratio of the nylon salt to the water to the catalyst to the chitosan quaternary ammonium salt is 80-100:50-70:0.3-0.5:2-8; The temperature of the prepolymerization reaction is 150-200 ℃, the pressure of the prepolymerization reaction is 5-9 kPa, and the time of the prepolymerization reaction is 1-8 hours.
2. The method for preparing a chitosan grafted modified bio-based nylon material according to claim 1, wherein the bio-based nylon salt comprises a nylon 56 salt, a nylon 54 salt, a nylon 510 salt, a nylon 512 salt, or a nylon 513 salt.
3. The method for preparing a chitosan grafted modified bio-based nylon material according to claim 2, wherein the catalyst comprises sodium hydroxide, toluene diisocyanate, titanium-based catalyst, phosphorus-containing compound or boric acid-based compound.
4. The method for preparing the chitosan grafted modified bio-based nylon material according to claim 1, wherein the mixing temperature is 45-55 ℃, the mixing pressure is 8-12 kpa, and the mixing time is 0.3-0.7 h.
5. The method for preparing the chitosan grafted modified bio-based nylon material according to claim 1, wherein the temperature of the final polymerization reaction is 210-280 ℃, the vacuum degree of the final polymerization reaction is 0.005-0.015 MPa, and the time of the final polymerization reaction is 1-8 h.
6. The chitosan grafted modified bio-based nylon material prepared by the preparation method of the chitosan grafted modified bio-based nylon material of any one of claims 1-5.
7. The use of the chitosan grafted modified bio-based nylon material of claim 6 in medical supplies packaging or food packaging.

Description

Chitosan grafted modified bio-based nylon material and preparation method and application thereof Technical Field The invention relates to the technical field of high polymer material modification, in particular to a chitosan grafted modified bio-based nylon material, and a preparation method and application thereof. Background The existing bio-based nylon material has the advantages of environmental protection, reproducibility and the like, but has insufficient antibacterial performance, so that the application of the bio-based nylon material in the fields of medical treatment, food packaging and the like is limited to a certain extent. The chitosan has excellent biocompatibility, blood compatibility, safety and microbial degradability, and has wide application in the fields of medicine, food, chemical industry, cosmetics, water treatment, metal extraction, recovery and the like. The chitosan is grafted to the bio-based nylon material, so that the antibacterial performance of the bio-based nylon material is expected to be improved. However, the preparation process is faced with the problems of compatibility of chitosan and bio-based nylon, controllability of graft polymerization reaction and stability and durability of antibacterial function. To overcome these problems, there is a need to enhance the study of the interaction mechanism of chitosan and bio-based nylon, optimize the conditions and parameters of the graft polymerization reaction, and explore a more stable and durable implementation of bacteriostatic function. On the other hand, nylon is often not the best choice in applications requiring high tensile bending or torsional stiffness compared to metals or other engineering plastics, and in addition, nylon is very prone to softening or melting at high temperatures, thereby losing its original mechanical properties and shape stability. Therefore, improving the mechanical property and the high temperature resistance of nylon is also a problem to be solved. In conclusion, the novel method for preparing the chitosan grafted modified bio-based nylon material is provided, so that the modified bio-based nylon material with excellent antibacterial performance, good mechanical performance and high temperature resistance is obtained, and the method has very important significance. Disclosure of Invention The invention aims to overcome the problems in the prior art and provides a chitosan grafted modified bio-based nylon material, and a preparation method and application thereof. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a preparation method of a chitosan grafted modified bio-based nylon material, which comprises the following steps: under the protective atmosphere, the bio-based nylon salt, water, the catalyst and the chitosan quaternary ammonium salt are mixed, and the pre-polymerization reaction and the final polymerization reaction are sequentially carried out, so that the chitosan grafted modified bio-based nylon material is obtained. Preferably, the biobased nylon salt comprises a nylon 56 salt, a nylon 54 salt, a nylon 510 salt, a nylon 512 salt, or a nylon 513 salt. Preferably, the catalyst includes sodium hydroxide, toluene diisocyanate, titanium-based catalyst, phosphorus-containing compound or boric acid-based compound. Preferably, the chitosan quaternary ammonium salt is hydroxypropyl trimethyl ammonium chloride chitosan, and the deacetylation degree of the hydroxypropyl trimethyl ammonium chloride chitosan is 97-99%. Preferably, the mass ratio of the nylon salt to the water to the catalyst to the chitosan quaternary ammonium salt is 80-100:50-70:0.3-0.5:2-8. Preferably, the mixing temperature is 45-55 ℃, the mixing pressure is 8-12 kPa, and the mixing time is 0.3-0.7 h. Preferably, the temperature of the prepolymerization reaction is 150-200 ℃, the pressure of the prepolymerization reaction is 5-9 kPa, and the time of the prepolymerization reaction is 1-8 hours. Preferably, the temperature of the final polymerization reaction is 210-280 ℃, the vacuum degree of the final polymerization reaction is 0.005-0.015 MPa, and the time of the final polymerization reaction is 1-8 h. The invention also provides the chitosan grafted modified bio-based nylon material prepared by the preparation method of the chitosan grafted modified bio-based nylon material. The invention also provides application of the chitosan grafted modified bio-based nylon material in medical product packaging or food packaging. The beneficial effects of the invention are as follows: The invention provides a preparation method of a chitosan grafted modified bio-based nylon material, which comprises the following steps of mixing bio-based nylon salt, water, a catalyst and chitosan quaternary ammonium salt under a protective atmosphere, and sequentially carrying out a prepolymerization reaction and a final polymerization reaction to obtain the chitosan g