CN-121991342-A - Self-supporting polypyrrole nano array and preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer preparation, and particularly relates to a 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 on the surface of ice, then adding pyrrole monomer, standing to form dispersion liquid, and (2) dripping acid solution containing oxidant into the dispersion liquid, reacting, washing and drying to obtain the self-supporting polypyrrole nano array. The array structure is a pre-constructed continuous conductive path relative to the zero-dimensional polypyrrole nanoparticles or polypyrrole nanoplates. In addition, the network structure of the polypyrrole nano sheet array with the self-supporting structure can interpenetrate with the resin matrix, uniformly transfer stress, inhibit crack growth, easily form a continuous conductive path, realize high conductivity with low addition, can be used as conductive filler of polyurethane in the technical field of 3D printing, and improve 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

20260508

Application Date

20260409

Claims (10)

1. 1. The preparation method of the self-supporting polypyrrole nano array is characterized by comprising the following steps of: (1) Firstly, dispersing an aqueous solution of hydroxypropyl-beta-cyclodextrin on the surface of ice, then adding pyrrole monomer, and standing for a period of time to form a dispersion liquid, wherein the mass ratio of the hydroxypropyl-beta-cyclodextrin to the pyrrole monomer 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 self-supporting polypyrrole nano array.
2. 2. The method for preparing a self-supporting polypyrrole nano array according to claim 1, wherein the standing time in the step (1) is 5-10min.
3. 3. The method for preparing a self-supporting polypyrrole nano array as set forth in claim 1, wherein the oxidant in the step (2) is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, ferric chloride and hydrogen peroxide.
4. 4. The method for preparing the self-supporting polypyrrole nano array as set forth in claim 1, wherein the mass ratio of the oxidant in the step (2) to the pyrrole monomer in the step (1) is (1-5): 1.
5. 5. The method for preparing self-supporting polypyrrole nano-arrays according to claim 1, wherein the acid in the step (2) is one or more of organic acid or inorganic acid.
6. 6. The method for preparing a self-supporting polypyrrole nano array according to claim 1, wherein the reaction temperature in the step (2) is below 0 ℃.
7. 7. The method of claim 1, wherein the washing in step (2) is performed with deionized water.
8. 8. A self-supporting polypyrrole nanoarray, characterized in that it is produced by a method for producing a self-supporting polypyrrole nanoarray as claimed in any one of claims 1 to 7.
9. 9. The use of the self-supporting polypyrrole nanoarray of claim 8, wherein the self-supporting polypyrrole nanoarray is used in a photo-curing molding technique, a selective laser sintering technique, a fused deposition technique, or a layered solid fabrication technique in a 3D printing technique.
10. 10. A3D printing polyurethane material is characterized by comprising a polyurethane resin material, a self-supporting polypyrrole nano array and an inorganic reinforcing filler, wherein the self-supporting polypyrrole nano array is the self-supporting polypyrrole nano array in claim 8.

Description

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 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 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 molecule hydroxypropyl-beta-cyclodextrin with hydrophilic and hydrophobic dual functions is introduced as an array growth auxiliary agent, so that the polypyrrole nano sheet array with a self-supporting structure is prepared by a one-step polymerization method, the self-supporting polypyrrole nano array is simple and efficient, can be used as a conductive filler of polyurethane in the technical field of 3D printing, and the mechanical pr