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CN-121972028-A - Light double-response polybutadiene film and preparation method and application thereof

CN121972028ACN 121972028 ACN121972028 ACN 121972028ACN-121972028-A

Abstract

The application discloses a light-force double-response polybutadiene film, and a preparation method and application thereof, and belongs to the technical field of high-molecular functional materials and new energy sources. The method comprises the steps of firstly carrying out photosensitive functional modification on a polybutadiene main chain through molecular grafting, then constructing a soluble sacrificial layer on the surface of a substrate, spin-coating a photosensitive polybutadiene solution for film formation, annealing and crosslinking, and finally removing the sacrificial layer through selective solvent etching to obtain the independent optical power double-response polybutadiene film. The application makes the film material have the dual response functions of light and force by introducing photosensitive groups and utilizing the self mechanical response characteristic of polybutadiene. The dual response characteristics can synergistically regulate and control the ion selectivity and flux of the membrane, and effectively break the performance bottleneck of the traditional membrane, so that the energy density and the controllability of the salt-differential energy conversion are obviously improved, and the membrane is further used for developing high-performance salt-differential energy power generation membrane materials.

Inventors

  • WEN WEI
  • ZHOU YUE
  • YAN NING
  • YANG TAO
  • DENG QI
  • DING LIZHAO

Assignees

  • 成都飞机工业（集团）有限责任公司

Dates

Publication Date
20260505
Application Date
20260119

Claims (20)

  1. 1. A method for preparing a photo-responsive polybutadiene film, comprising the steps of: Carrying out photosensitive functional modification on a main chain of a polybutadiene material by a molecular grafting technology to obtain a photosensitive polydibutene solution; Constructing a soluble sacrificial layer on the surface of the substrate to obtain a pretreated substrate; Performing film forming treatment on the photosensitive polydibutene solution on the surface of the pretreated substrate to obtain a substrate material containing a polymer film; annealing and crosslinking the matrix material containing the polymer film to obtain a light double-response polybutadiene film composite material; and removing the soluble sacrificial layer of the optical power double-response polybutadiene film composite material by a selective solvent etching method to prepare the optical power double-response polybutadiene film.
  2. 2. The preparation method according to claim 1, wherein the molecular grafting technique is carried out by an esterification reaction or an amidation reaction, wherein, The amidation reaction comprises the following steps of carrying out an acyl chlorination reaction on a carboxylic acid group through an acyl chlorination reagent, wherein the obtained reaction product reacts with an amino group or a hydroxyl group, and the acyl chlorination reagent comprises thionyl chloride, oxalyl chloride, phosphorus trichloride or phosphorus pentachloride.
  3. 3. The method of claim 1 or 2, wherein the photoactive molecule in the photoactive polydibutene solution is 5- (4-hydroxyphenyl) -10,15,20- (triphenylporphyrin, 5, 15-bis (4-hydroxyphenyl) -10, 20-diphenylporphyrin, 4-hydroxyazobenzene, 5- (4-aminophenyl) -10,15,20- (triphenylporphyrin, 5, 15-bis (4-aminophenyl) -10, 20-diphenylporphyrin, 4-aminoazobenzene, 1- (4-aminophenyl) -1, 2-triphenylethylene, 5- (4-carboxyphenyl) -10,15,20- (triphenylporphyrin, 5, 15-bis (4-carboxyphenyl) -10, 20-diphenylporphyrin or azobenzene-4, 4-dicarboxylic acid, 1- (4-carboxybenzene) -1, 2-triphenylethylene.
  4. 4. The preparation method of claim 1, wherein the polydibutene material is carboxyl-terminated polybutadiene, amino-terminated polybutadiene or hydroxyl-terminated polybutadiene, and the molecular weight of the polydibutene material is 1000-15000.
  5. 5. The preparation method of claim 1, wherein the material of the soluble sacrificial layer is polyvinyl alcohol or cellulose acetate, and the thickness of the soluble sacrificial layer is 100 nm-500 nm.
  6. 6. The method of claim 1, wherein the substrate is mica or silicon flakes and the substrate has a surface contact angle of less than 90 °.
  7. 7. The method according to claim 1, wherein the solvent of the photosensitive polydibutene solution comprises at least one of chloroform, toluene, methylene chloride and tetrahydrofuran, and the concentration of the photosensitive polydibutene solution is 1wt% to 10wt%.
  8. 8. The method of claim 1, wherein the annealing process is thermal annealing, solvent annealing, or interfacial annealing.
  9. 9. The method according to claim 8, wherein the thermal annealing environment is vacuum, nitrogen or inert gas, the annealing temperature is 50 ℃ to 100 ℃, and the annealing time is 4h to 72h.
  10. 10. The method according to claim 8, wherein the solvent for solvent annealing comprises at least one of chloroform, toluene, methylene chloride, acetone, tetrahydrofuran, ethanol, methanol, and water, the annealing temperature is 0 ℃ to 50 ℃, and the annealing time is 1d to 7d.
  11. 11. The method according to claim 8, wherein the liquid phase material for interface annealing is at least one of deionized water, 0.1 mol/L-2 mol/L dilute hydrochloric acid, 0.1 mol/L-2 mol/L dilute sulfuric acid, acetonitrile and ethanol, the annealing temperature is 0 ℃ to 50 ℃, and the annealing time is 0.5h to 24h.
  12. 12. The method of claim 1, wherein the crosslinking treatment is chemical crosslinking, photo crosslinking, or thermal crosslinking.
  13. 13. The method according to claim 12, wherein the chemical crosslinking agent comprises at least one of 1, 12-amphiphobic dodecane, disulfide, sublimed sulfur, and iodine, the crosslinking temperature is 0 ℃ to 50 ℃, and the crosslinking time is 1min to 720min.
  14. 14. The method according to claim 12, wherein the photocrosslinking agent is at least one of 2, 2-dimethoxy-2-phenylacetophenone, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide, the photocrosslinking agent is irradiated by an ultraviolet lamp, the wavelength of the ultraviolet lamp is 254nm to 365nm, the ultraviolet intensity is 0.1mW/cm2 to 6mW/cm2, and the irradiation time is 5min to 60min.
  15. 15. The method according to claim 12, wherein the thermal crosslinking temperature is 10 ℃ to 50 ℃ and the crosslinking time is 4d to 12d.
  16. 16. The method according to claim 1, wherein the solvent used in the selective solvent etching method comprises at least one of water, ethanol and chloroform, and the etching temperature is 10 ℃ to 60 ℃.
  17. 17. The method according to claim 1, wherein the film forming process is spin coating, blade coating or drop coating, and the spin coating is performed at a rotation speed of 20rpm to 4000rpm.
  18. 18. A light-force double-responsive polybutadiene film, characterized in that it is obtained according to the preparation method of any one of claims 1 to 17.
  19. 19. Use of the dual-power responsive polybutadiene film of claim 18 for salt-differential power generation, comprising the steps of: the photodynamic double-response polybutadiene membrane is used as a selective ion transmission medium and used for separating chambers of electrolyte solutions, and the electrolyte solution concentrations of the two separated chambers are inconsistent; And (3) applying ultraviolet light illumination and/or pressure to the light double-response polybutadiene film to generate electricity.
  20. 20. The use of claim 19, wherein the method of applying pressure is to vary the level difference of the electrolyte solution.

Description

Light double-response polybutadiene film and preparation method and application thereof Technical Field The application belongs to the technical field of high molecular functional materials and new energy, and particularly relates to a light double-response polybutadiene film, and a preparation method and application thereof. Background The salt difference can be used as an energy source with rich reserves, cleanness and renewable energy sources, and the efficient development and utilization of the salt difference have important significance for relieving energy crisis. Currently, the technology of salt-tolerant energy conversion mainly relies on membrane materials to achieve energy capture, wherein the traditional commercial ion exchange membrane is restricted from large-scale application due to the problems of high preparation cost, difficulty in collaborative optimization of ion selectivity and flux, limited energy density and controllability and the like. In order to improve the energy density, the existing research prepares a membrane material with low internal resistance and high selectivity through molecular design and structure optimization, but the performance of the membrane material is still limited by the inherent ion selectivity and flux balance of the membrane, and the controllability is insufficient. Further, by introducing single external stimulus response characteristics such as light, heat, force and pH, the membrane performance can be dynamically adjusted to break through the limitations, however, single response membranes have limitations in response dimension and function integration, and it is difficult to meet the higher demands of complex application scenarios on energy density and controllability. Therefore, developing a membrane material with multiple response characteristics to cooperatively improve the energy density and the controllability of the salt-differential energy conversion system is a technical problem to be solved in the art. Disclosure of Invention The application aims to provide a light-force double-response polybutadiene membrane, a preparation method and application thereof, which have the double response characteristics of light and force, and can improve the energy density and the adjustability of an ion exchange membrane so as to promote the application of the ion channel membrane in salt difference power generation. In order to achieve the above object, the present application provides a method for preparing a light-force dual-response polybutadiene film, comprising the steps of: Carrying out photosensitive functional modification on a main chain of a polybutadiene material by a molecular grafting technology to obtain a photosensitive polydibutene solution; Constructing a soluble sacrificial layer on the surface of the substrate to obtain a pretreated substrate; performing film forming treatment on the photosensitive polydibutene solution on the surface of the pretreated substrate to obtain a substrate material containing a polymer film; annealing and crosslinking the base material containing the polymer film to obtain a light double-response polybutadiene film composite material; And removing the soluble sacrificial layer of the optical double-response polybutadiene film composite material by a selective solvent etching method to prepare the optical double-response polybutadiene film. Further, the molecular grafting technique is realized by an esterification reaction or an amidation reaction, wherein, The amidation reaction includes the step of subjecting a carboxylic acid group to an acid chlorination reaction by an acid chlorination reagent, and reacting the obtained reaction product with an amino group or a hydroxyl group, wherein the acid chlorination reagent includes thionyl chloride, oxalyl chloride, phosphorus trichloride or phosphorus pentachloride. Further, the photoactive molecule in the photoactive polydibutene solution is 5- (4-hydroxyphenyl) -10,15,20- (triphenyl) porphyrin, 5, 15-bis (4-hydroxyphenyl) -10, 20-diphenylporphyrin, 4-hydroxyazobenzene, 5- (4-aminophenyl) -10,15,20- (triphenyl) porphyrin, 5, 15-bis (4-aminophenyl) -10, 20-diphenylporphyrin, 4-aminoazobenzene, 1- (4-aminophenyl) -1, 2-triphenylethylene, 5- (4-carboxyphenyl) -10,15,20- (triphenyl) porphyrin, 5, 15-bis (4-carboxyphenyl) -10, 20-diphenylporphyrin or azobenzene-4, 4-dicarboxylic acid, 1- (4-carboxyphenyl) -1, 2-triphenylethylene. Further, the polydibutene material is carboxyl-terminated polybutadiene, amino-terminated polybutadiene or hydroxyl-terminated polybutadiene, and the molecular weight of the polydibutene material is 1000-15000. Further, the material of the soluble sacrificial layer is polyvinyl alcohol or cellulose acetate, and the thickness of the soluble sacrificial layer is 100 nm-500 nm. Further, the substrate is mica or silicon wafer, and the contact angle of the surface of the substrate is smaller than 90 degrees. Further, the solvent of the photosensitive p