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CN-122011753-A - High molecular polymer with antibacterial slow-release function and preparation method thereof

CN122011753ACN 122011753 ACN122011753 ACN 122011753ACN-122011753-A

Abstract

The application relates to the technical field of functional high polymer materials, and particularly discloses a high polymer with an antibacterial slow-release function and a preparation method thereof. A preparation method of a high polymer with an antibacterial slow-release function comprises the following steps of S1, adding amino-terminated hyperbranched polyamide, p-aldehyde benzoic acid and a dehydrating agent into a reactor under an inert atmosphere, heating to 60-80 ℃, reacting for 45-60 min, adding a carboxyl-containing heterocyclic compound, a catalyst and N, N-dimethylformamide, heating to 80-100 ℃, reacting for 2-6 h, adding a metal salt, reacting for 1-2 h, cooling to obtain an antibacterial intermediate, and S2, uniformly mixing the antibacterial intermediate, the bio-based polyamide and an antioxidant in proportion under the inert atmosphere, extruding by an extruder, cooling and granulating to obtain the high polymer. The high molecular polymer prepared by the application has excellent antibacterial property and long-acting slow release property.

Inventors

  • JIANG YIJUN
  • LIU QINGYANG
  • YI GEER

Assignees

  • 青岛纽贝尔新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260311

Claims (10)

  1. 1. The preparation method of the high molecular polymer with the antibacterial slow-release function is characterized by comprising the following steps: S1, adding amino-terminated hyperbranched polyamide, p-aldehyde benzoic acid and a dehydrating agent into a reactor in an inert atmosphere, heating to 60-80 ℃, reacting for 45-60 min, adding a carboxyl-containing heterocyclic compound, a catalyst and N, N-dimethylformamide, heating to 80-100 ℃, reacting for 2-6 h, adding metal salt, reacting for 1-2 h, and cooling to obtain an antibacterial intermediate; s2, uniformly mixing the antibacterial intermediate, the bio-based polyamide and the antioxidant in proportion under inert atmosphere, extruding by an extruder, and cooling and granulating to obtain the high-molecular polymer.
  2. 2. The method for preparing a polymer with an antibacterial slow release function according to claim 1, wherein the bio-based polyamide is one or more of PA11, PA510 ‌ and PA610, ‌.
  3. 3. The method for preparing the high molecular polymer with the antibacterial slow-release function according to claim 2, wherein the molar ratio of the amino-terminated hyperbranched polyamide (calculated by amino-terminated), the p-aldehyde benzoic acid, the carboxyl-containing heterocyclic compound and the metal salt is 1 (0.2-0.3): (0.15-0.25): (0.08-0.15).
  4. 4. The preparation method of the high molecular polymer with the antibacterial slow-release function according to claim 2, wherein the mass ratio of the antibacterial intermediate to the bio-based polyamide to the antioxidant is (5-25): 75-95): 0.2-0.5.
  5. 5. The method for preparing a polymer with an antibacterial sustained-release function according to claim 1, wherein the carboxyl-containing heterocyclic compound is one or more of 3-hydroxy-2-picolinic acid and 4-picolinic acid.
  6. 6. The method for preparing a polymer with an antibacterial slow-release function according to claim 1, wherein the metal salt is one or more of silver acetate, zinc acetate and copper acetate.
  7. 7. The method for preparing a polymer with an antibacterial slow release function according to claim 1, wherein in the step S2, after the bio-based polyamide, the method further comprises the step of adding toluene diisocyanate accounting for 1% -5% of the mass of the antibacterial intermediate.
  8. 8. The method for producing a polymer having an antibacterial sustained-release function according to claim 1, wherein in step S1, after the addition of the carboxyl group-containing heterocyclic compound, a step of adding quercetin or/and gallic acid is further included.
  9. 9. The method for producing a polymer having an antibacterial sustained-release function according to claim 8, wherein the molar ratio of quercetin or gallic acid to the amino-terminated hyperbranched polyamide (based on amino-terminated) is (0.03 to 0.07): 1.
  10. 10. A polymer having an antibacterial sustained-release function produced by the production method according to any one of claims 1 to 9.

Description

High molecular polymer with antibacterial slow-release function and preparation method thereof Technical Field The application relates to the technical field of functional high polymer materials, in particular to a high polymer with an antibacterial slow-release function and a preparation method thereof. Background The polyamide material has excellent mechanical strength, wear resistance, processability and chemical resistance, is popularized and applied in the fields of antibacterial fabrics, functional coatings, medical sanitation, household products and the like, and has no active antibacterial property, so that the use requirements of sanitary protection and high-end products are difficult to meet, and the antibacterial modification of the polyamide material becomes the core direction of industrial research and industrialization. The existing polyamide antibacterial modification technology mostly adopts an organic antibacterial agent or a simple inorganic antibacterial agent compounding scheme, has obvious defects, cannot take into account long-acting antibacterial property, processing stability and use safety, firstly, the organic antibacterial agents such as chitosan, chitosan oligosaccharide and the like have certain biocompatibility, but are only physically blended and combined with a polyamide matrix, migration, dissolution and loss are extremely easy to occur in the processes of repeatedly washing fabrics, long-term soaking of coatings and long-term use of products, the antibacterial property is fast attenuated, the long-acting antibacterial property is not guaranteed, the heat resistance of the organic antibacterial agents is poor, the thermal degradation and carbonization are easy to occur in the high-temperature melt processing (more than 180 ℃) process of the polyamide, and the antibacterial activity is lost. The patent application document with the publication number of CN102241887A discloses an antibacterial polyamide material which consists of polyamide resin, an antibacterial agent, a compatilizer and an antioxidant, wherein the antibacterial agent is one or more of chitosan, chitosan oligosaccharide and derivatives thereof. According to the technical scheme, the chitosan organic antibacterial agent and the polyamide matrix are combined mainly through physical blending, the binding force is weak, the antibacterial agent is easy to run off, the heat-resistant short plates of the chitosan antibacterial agent protrude, the main flow processing technologies such as high-temperature melt extrusion, spinning and injection molding of polyamide cannot be adapted, the antibacterial durability and the processing stability of the material are both lost, and the application scene is severely limited. Disclosure of Invention Aiming at the defects of easy loss and poor heat resistance of an organic antibacterial agent in the prior art, the application provides a high molecular polymer with an antibacterial slow-release function and a preparation method thereof. In a first aspect, the application provides a preparation method of a high molecular polymer with an antibacterial slow-release function, which adopts the following technical scheme: a preparation method of a high molecular polymer with an antibacterial slow-release function comprises the following steps: S1, adding amino-terminated hyperbranched polyamide, p-aldehyde benzoic acid and a dehydrating agent into a reactor in an inert atmosphere, heating to 60-80 ℃, reacting for 45-60 min, adding a carboxyl-containing heterocyclic compound, a catalyst and N, N-dimethylformamide, heating to 80-100 ℃, reacting for 2-6 h, adding metal salt, reacting for 1-2 h, and cooling to obtain an antibacterial intermediate; s2, uniformly mixing the antibacterial intermediate, the bio-based polyamide and the antioxidant in proportion under inert atmosphere, extruding by an extruder, and cooling and granulating to obtain the high-molecular polymer. According to the technical scheme, the p-aldehyde benzoic acid and the amino-terminated hyperbranched polyamide form partial imine bond to construct a reversible network, then the carboxyl-containing heterocyclic compound is connected into the hyperbranched network through amidation reaction, metal coordination sites are introduced, and finally metal ions are introduced to realize anchoring through coordination. And then the obtained antibacterial intermediate, the bio-based polyamide and the antioxidant are subjected to melt blending, extrusion and granulation under inert atmosphere, so that the antibacterial component is uniformly dispersed in the polyamide matrix, and finally the high polymer with long-acting antibacterial performance, slow release characteristic and excellent processing stability is prepared. Preferably, the bio-based polyamide is one or more of PA11, PA510 ‌, PA610, ‌. Preferably, the extruder is a twin-screw extruder, and the temperature ranges of each section of the twin-screw extruder are 200-210 ℃