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CN-122013451-A - Photodynamic heterogeneous composite spiral fiber antibacterial composite membrane, preparation method and application

CN122013451ACN 122013451 ACN122013451 ACN 122013451ACN-122013451-A

Abstract

The invention discloses a photodynamic heterogeneous composite spiral fiber antibacterial composite membrane and a preparation method and application thereof, wherein the preparation method comprises the steps of uniformly mixing dried polymer raw materials with titanium dioxide, and carrying out melt extrusion granulation to obtain PPLA/TiO 2 master batch; the method comprises the steps of adding dried PPLA/TiO 2 master batch into melt-blowing equipment, carrying out melt-spinning at 180-190 ℃ to obtain PPLA@TiO 2 melt-blown non-woven fabric, adopting a three-channel coaxial electrostatic spinning technology to spin and spray an inner channel spinning solution, a middle channel spinning solution and an outer channel spinning solution on the PPLA@TiO 2 melt-blown non-woven fabric, and finishing spinning to obtain the photodynamic heterogeneous composite spiral fiber antibacterial composite film.

Inventors

  • LI TINGTING
  • ZHOU JINLONG
  • WANG XIAOMENG
  • LI LETIAN
  • HU XIANJIN
  • REN HAITAO
  • LOU JINGWEN

Assignees

  • 天津工业大学

Dates

Publication Date
20260512
Application Date
20260407

Claims (10)

  1. 1. The preparation method of the photodynamic heterogeneous composite spiral fiber antibacterial composite membrane is characterized by comprising the following steps of: Step 1), uniformly mixing a dried polymer raw material with titanium dioxide, and carrying out melt extrusion granulation to obtain PPLA/TiO 2 master batch, wherein the polymer raw material comprises polypropylene and polylactic acid, and the ratio of the polypropylene to the polylactic acid to the titanium dioxide is (89-90) (8-9) (0.1-0.2) in parts by weight; Step 2), adding the dried PPLA/TiO 2 master batch into a melt-blowing device, and carrying out melt spinning at 180-190 ℃ to obtain PPLA@Ti 2 melt-blown non-woven fabric; Step 3), adopting a three-channel coaxial electrostatic spinning technology, spinning and spraying an inner channel spinning solution, a middle channel spinning solution and an outer channel spinning solution on the PPLA@TiO 2 melt-blown non-woven fabric, and finishing spinning to obtain a photodynamic heterogeneous composite spiral fiber antibacterial composite film, wherein the ratio of the inner channel spinning solution to the middle channel spinning solution to the outer channel spinning solution is 1 (1-2) (1-3) in parts by volume; the inner channel spinning solution comprises 4,4' -terephthaloyl diphthalic anhydride, caffeic acid, zeolite imidazole ester skeleton-8 and polycaprolactone; the medium channel spinning solution comprises cellulose acetate, lithium chloride, N-dimethylacetamide and acetone; the outer channel spinning solution comprises thermoplastic polyurethane and N, N-dimethylformamide.
  2. 2. The method according to claim 1, wherein in the step 1), the drying comprises standing at 45 to 60 ℃ for 8 to 14 hours; In the step 2), the drying temperature is 75-85 ℃ and the drying time is 8-12 h.
  3. 3. The method according to claim 1, wherein in the step 1), the melting temperature in the melt extrusion granulation is 190 to 200 ℃.
  4. 4. The method according to claim 1, wherein in the step 2), the diameter of the die orifice of the melt blowing apparatus is 0.8 to 0.9 mm.
  5. 5. The preparation method according to claim 1, wherein in the step 3), the method for obtaining the inner channel spinning solution comprises the steps of mixing polycaprolactone with N, N-dimethylformamide, stirring for 20-24 hours at 60-70 ℃ to obtain a PCL solution, wherein the concentration of the polycaprolactone in the PCL solution is 18-28 wt%, adding 4,4' -terephthaloyl diphthalic anhydride, caffeic acid and zeolite imidazole ester skeleton-8 into the PCL solution under the conditions of light shielding and stirring, and keeping at 50-60 ℃ for 4-8 hours to obtain the inner channel spinning solution, wherein the ratio of the 4,4' -terephthaloyl diphthalic anhydride, caffeic acid and ZIF-8 is 1 (1.5-2) in parts by weight, and the concentration of the 4,4' -terephthaloyl diphthalic anhydride in the inner channel spinning solution is 0.1-0.5 wt%.
  6. 6. The preparation method of the medium channel spinning solution according to claim 1, wherein in the step 3), the method for obtaining the medium channel spinning solution comprises the steps of uniformly dispersing cellulose acetate and lithium chloride in an N, N-dimethylacetamide/acetone mixed solution, heating and stirring for 6-8 hours at 60-70 ℃ to obtain the medium channel spinning solution, wherein the ratio of the cellulose acetate to the lithium chloride is (13-14): 1-2 by mass, the concentration of the cellulose acetate in the medium channel spinning solution is 13-14 wt%, the N, N-dimethylacetamide/acetone mixed solution comprises N, N-dimethylacetamide and acetone, and the ratio of the N, N-dimethylacetamide and the acetone in the N, N-dimethylacetamide/acetone mixed solution is (0.14-0.16): 1 by mass.
  7. 7. The method according to claim 1, wherein in the step 3), the method for obtaining the outer channel dope comprises dispersing thermoplastic polyurethane in N, N-dimethylformamide, and stirring at 60-70 ℃ for 6-8 hours to obtain the outer channel dope, wherein the concentration of the thermoplastic polyurethane in the outer channel dope is 15-25 wt%.
  8. 8. The photodynamic heterogeneous composite spiral fiber antibacterial composite membrane obtained by the preparation method according to any one of claims 1 to 7.
  9. 9. The photodynamic heterogeneous composite spiral fiber antibacterial composite membrane according to claim 8 has a thickness of 0.9-1 mm.
  10. 10. The use of the photodynamic heterogeneous composite spiral fiber antibacterial composite membrane as claimed in claim 8 in antibacterial materials.

Description

Photodynamic heterogeneous composite spiral fiber antibacterial composite membrane, preparation method and application Technical Field The invention belongs to the technical field of photodynamic type antibacterial films, and particularly relates to a photodynamic type heterogeneous composite spiral fiber antibacterial composite film, and a preparation method and application thereof. Background In recent years, public health events caused by pathogenic microorganisms such as bacteria and viruses are frequent, and particularly in crowded places such as hospitals, schools and markets, the risk of cross infection is remarkably increased. Taking respiratory diseases as an example, the relevant data show that more than about 60% of cases are caused by cross-infection. Although widespread vaccination and the use of modern protective equipment can reduce the speed of transmission of infectious diseases to some extent, it is difficult to completely block the pathogen's path of transmission. Under the background, the photodynamic antibacterial material has wide application prospect in reducing the cross-transmission risk of pathogenic microorganisms by virtue of the advantages of high-efficiency sterilization, low drug resistance, low biotoxicity and the like, and gradually becomes a research hot spot in the field of protective materials. The traditional photodynamic antibacterial material has extremely strong light dependence, and the antibacterial rate of the traditional photodynamic antibacterial material under the illumination condition can reach more than 99 percent. However, the antibacterial rate in dark conditions drops below 10% and even fails completely. The photosensitizer is extremely easy to generate rapid attenuation and quenching phenomena under the dark condition, and finally, the release efficiency of Reactive Oxygen Species (ROS) is low, so that the antibacterial effect is poor. And the traditional photodynamic antibacterial material is difficult to meet the comfort requirement in the sunshine environment, and has poor recycling performance, so that the actual application and popularization of the photodynamic antibacterial material in the personal protection field are severely limited. Therefore, the preparation of the photodynamic antibacterial material which can work under the conditions of illumination and darkness, can be repeatedly used and has comfort is important to solve the current health problem. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a preparation method of a photodynamic heterogeneous composite spiral fiber antibacterial composite membrane. The invention also aims to provide the photodynamic heterogeneous composite spiral fiber antibacterial composite membrane obtained by the preparation method. The invention also aims to provide the application of the photodynamic heterogeneous composite spiral fiber antibacterial composite membrane in antibacterial materials. The aim of the invention is achieved by the following technical scheme. A preparation method of a photodynamic heterogeneous composite spiral fiber antibacterial composite membrane comprises the following steps: Step 1), uniformly mixing a dried polymer raw material with titanium dioxide (TiO 2), and carrying out melt extrusion granulation to obtain PPLA/TiO 2 master batch, wherein the polymer raw material comprises polypropylene (PP) and polylactic acid (PLA), and the ratio of the polypropylene to the polylactic acid to the titanium dioxide is (89-90): (8-9): (0.1-0.2) in parts by weight; In the step 1), the drying comprises the steps of placing at 45-60 ℃ for 8-14 hours. In the step 1), the melting temperature in the melt extrusion granulation is 190-200 ℃. Step 2), adding the dried PPLA/TiO 2 master batch into a melt-blowing device, and carrying out melt spinning at 180-190 ℃ to obtain PPLA@Ti 2 melt-blown non-woven fabric; In the step 2), the drying temperature is 75-85 ℃ and the drying time is 8-12 h. In the step 2), the diameter of a die head spinneret orifice of the melt-blowing equipment is 0.8-0.9 mm. Step 3), adopting a three-channel coaxial electrostatic spinning technology, spinning and spraying an inner channel spinning solution, a middle channel spinning solution and an outer channel spinning solution on the PPLA@TiO 2 melt-blown non-woven fabric, and finishing spinning to obtain a photodynamic heterogeneous composite spiral fiber antibacterial composite film, wherein the ratio of the inner channel spinning solution to the middle channel spinning solution to the outer channel spinning solution is 1 (1-2) (1-3) in parts by volume; the inner channel spinning solution comprises 4,4' -terephthaloyl diphthalic anhydride (TDPA), caffeic acid (CFA), zeolite imidazole ester skeleton-8 (ZIF-8) and Polycaprolactone (PCL); the medium channel spinning solution comprises Cellulose Acetate (CA), lithium chloride (LiCl), N-dimethylacetamide (DMAc) and Acetone (ACE); The outer