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CN-122011381-A - High-strength self-supporting polypyrrole nano array and preparation method and application thereof

CN122011381ACN 122011381 ACN122011381 ACN 122011381ACN-122011381-A

Abstract

The invention belongs to the technical field of polymer preparation, and particularly relates to a high-strength self-supporting polypyrrole nano array, and a preparation method and application thereof. The preparation method comprises the steps of (1) dispersing aqueous solution of hydroxypropyl-beta-cyclodextrin and polyethylene glycol on the surface of ice, then adding pyrrole monomer to form dispersion liquid, and (2) dripping acid solution containing oxidant into the dispersion liquid, and reacting to obtain the high-strength self-supporting polypyrrole nano array. The invention directly adopts macroscopic ice cubes as a hard template for preparing polypyrrole, and prepares the high-strength polypyrrole nano sheet array with a self-supporting structure by a one-step polymerization method by introducing annular molecular hydroxypropyl-beta-cyclodextrin with hydrophilic and hydrophobic dual functions and polyethylene glycol with a linear high molecular chain as an array growth auxiliary agent, thus being capable of being used as a conductive filler of polyurethane in the technical field of 3D printing, and greatly improving the mechanical property and antistatic capability of the product.

Inventors

  • YAN XILI
  • LIU XIAOFEI
  • JIANG WEIJUAN
  • ZHANG CHENGLIANG
  • LI HERAN

Assignees

  • 苏州港睿通纳米材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260413

Claims (10)

  1. 1. The preparation method of the high-strength self-supporting polypyrrole nano array is characterized by comprising the following steps of: (1) Firstly, dispersing an aqueous solution of hydroxypropyl-beta-cyclodextrin and polyethylene glycol on the surface of ice, then adding pyrrole monomers, and standing to form a dispersion liquid, wherein the mass ratio of the hydroxypropyl-beta-cyclodextrin to the pyrrole monomers is (1-3): 1; (2) And (3) dripping an acid solution containing an oxidant into the dispersion liquid, reacting, washing, and drying to obtain the high-strength self-supporting polypyrrole nano array.
  2. 2. The method for preparing a high-strength self-supporting polypyrrole nano array according to claim 1, wherein the mass ratio of polyethylene glycol to hydroxypropyl-beta-cyclodextrin in the step (1) is (0.1-0.4): 1.
  3. 3. The method for preparing a high-strength self-supporting polypyrrole nano array as claimed in claim 1, wherein the polyethylene glycol in the step (1) has a number average molecular weight of 1000 to 10000.
  4. 4. The method for preparing a high-strength self-supporting polypyrrole nano array according to claim 1, wherein the acid in the step (2) is one or more of organic acid or inorganic acid.
  5. 5. The method for preparing a high-strength self-supporting polypyrrole nano array as set forth in claim 4, wherein the organic acid is one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sodium dodecylsulfonate, camphorsulfonic acid, sulfosalicylic acid and oxalic acid.
  6. 6. The method for preparing a high-strength self-supporting polypyrrole nano array as set forth in claim 4, wherein the inorganic acid is one or more of sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid.
  7. 7. The method for preparing the high-strength self-supporting polypyrrole nano array as set forth in claim 1, the method is characterized in that the step (2) is carried out in a vacuum drying oven.
  8. 8. A high-strength self-supporting polypyrrole nanoarray, characterized in that it is produced by a method for producing a high-strength self-supporting polypyrrole nanoarray as claimed in any one of claims 1 to 7.
  9. 9. The use of the high-strength self-supporting polypyrrole nanoarray as claimed in claim 8, wherein the high-strength self-supporting polypyrrole nanoarray is used in a photo-curing molding technique, a selective laser sintering technique, a fused deposition technique or a layered entity manufacturing technique in a 3D printing technique.
  10. 10. The 3D printing polyurethane material is characterized by comprising a polyurethane resin material, a high-strength self-supporting polypyrrole nano array and an inorganic reinforcing filler, wherein the high-strength self-supporting polypyrrole nano array is the high-strength self-supporting polypyrrole nano array in claim 8.

Description

High-strength self-supporting polypyrrole nano array and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer preparation, and particularly relates to a high-strength self-supporting polypyrrole nano array, and a preparation method and application thereof. Background As an innovative manufacturing approach, 3D printing technology presents a number of significant advantages over traditional manufacturing techniques. The traditional manufacturing technology is often limited by the preparation and processing technology of the mould, so that the manufacturing cost is high, the production period is long, and the degree of freedom design of the product structure is difficult to realize. The 3D printing technology can realize the controlled arrangement of materials in the printing process by virtue of the unique manufacturing mode of accumulating the materials layer by layer, so that the bottleneck problems are effectively solved. In the aspect of practical application, the 3D printing technology can solve the problem of overhigh cost of the traditional process through small-batch custom production, and the constraint of structural design is eliminated. In 3D printing, the most important is the preparation of the printed material. The thermoplastic engineering plastic does not generate chemical bonding in the 3D printing process, can be recycled, melted and reused, and is the most common material in the 3D printing technology. Polyurethane is a high molecular material prepared from raw materials such as isocyanate, polyol, chain extender and the like through chemical reaction, and the unique molecular structure and the controllable chemical composition of the polyurethane endow the material with extremely wide performance range. Since the realization of industrial production of polyurethane, the elastomer form thereof has established an important position by virtue of unique performance advantages. The material has the characteristics of high elasticity of rubber and high strength of plastic, can meet the requirements of different application scenes through flexible molecular design, and is widely applied to the key fields of automobile manufacture, medical equipment, sports equipment, aerospace, aviation and the like. The polyurethane is characterized by a microphase separation structure, and the interpenetrating network structure ensures the high bearing capacity of the material and gives the material excellent deformation recovery characteristics. The precise regulation and control of the special form ensures that the polyurethane keeps stable mechanical properties in a wide temperature range, and becomes a high polymer system with great application value in the field of engineering materials. The hard segment of polyurethane is composed of urethane rigid units formed by gradual polymerization of isocyanate and chain extender, and forms a physical cross-linked network through multiple hydrogen bonding, while the soft segment is composed of long chain polyol with conformational freedom, and gives the elastic response characteristic to the material through chain segment movement. The combined structure features of hardness and softness make the material not only able to disperse stress effectively, but also able to resist permanent deformation. By adjusting the ratio of hard to soft segments, selecting different types of polyols (e.g., polyester, polyether, polycarbonate) and controlling the synthesis process, precise tailoring of the crystallinity, crosslink density, and microscopic phase of the material can be achieved, thereby achieving a continuous performance spectrum from the ultra-soft elastomer to the rigid structure. At present, the development direction of the 3D printing polyurethane material mainly focuses on optimizing the mechanical properties of the material, but the antistatic property of the 3D printing polyurethane material is not studied to a certain extent. In the prior art, various conductive polymer fillers are added to solve the technical problem of poor antistatic property of polyurethane. But the bonding force between the conductive polymer filler and the polyurethane interface is low, and the conductive polymer filler is difficult to directly print and form through blending. Disclosure of Invention The invention aims to provide a high-strength self-supporting polypyrrole nano array, a preparation method and application thereof, wherein macroscopic ice cubes are directly adopted as a hard template for preparing polypyrrole, and annular molecular hydroxypropyl-beta-cyclodextrin with hydrophilic and hydrophobic dual functions and polyethylene glycol with a linear high polymer chain are introduced as an array growth auxiliary agent, so that the high-strength polypyrrole nano array with a self-supporting structure is prepared by a one-step polymerization method, and the method is a simple and efficient method for preparing the high