阅读说明：本技术 导电复合纳米纤维膜的制备方法 (Preparation method of conductive composite nanofiber membrane ) 是由 冯章启 杜丽娟 吴方方 袁旭 严珂 金飞 李�瑞 于 2018-07-21 设计创作，主要内容包括：本发明公开了一种导电复合纳米纤维膜的制备方法。所述方法先采用静电纺丝技术,制备具有能与磺酸基形成氢键的基团的聚合物纳米纤维膜,然后将聚合物纳米纤维膜平整的置于铜网上,滴加PEDOT：PSS溶液,使之均匀铺展在纳米纤维膜上,静置,除去表面多余的溶液,在100～160℃退火,稀硫酸处理,得到PEDOT：PSS包覆的导电复合纳米纤维。本发明的制备工艺简单,充分利用了PEDOT：PSS电化学和氧化稳定性,制得的导电纳米纤维的导电率达到了3.28ⅹ10<Sup>-2</Sup>S cm<Sup>-1</Sup>。(The invention discloses a preparation method of conductive composite nanofiber membranes, which comprises the steps of firstly preparing a polymer nanofiber membrane with groups capable of forming hydrogen bonds with sulfonic acid groups by adopting an electrostatic spinning technology, then flatly placing the polymer nanofiber membrane on a copper net, dropwise adding PEDOT (Polytetrafluoroethylene-styrene) PSS solution to uniformly spread the polymer nanofiber membrane on a nanofiber membrane, standing, and removing redundant solution on the surfaceAnd (3) annealing the solution at 100-160 ℃, and treating with dilute sulfuric acid to obtain PEDOT: PSS coated conductive composite nanofibers. The preparation process is simple, and the method makes full use of the following steps: the PSS has electrochemical and oxidation stability, and the conductivity of the prepared conductive nano-fiber reaches 3.28 x 10 ‑2 S cm ‑1 。)

1. The preparation method of the conductive composite nanofiber membrane is characterized by comprising the following specific steps of:

step 1, preparing a polymer nanofiber membrane with a group capable of forming a hydrogen bond with a sulfonic group by adopting an electrostatic spinning technology;

step 2, flatly placing the polymer nanofiber membrane on a copper net, and dropwise adding PEDOT: and (3) uniformly spreading the PSS solution on the nanofiber membrane, standing, removing redundant solution on the surface, annealing at 100-160 ℃, and treating with dilute sulfuric acid to obtain PEDOT: PSS coated conductive composite nanofibers.

2. The method according to claim 1, wherein in step 1, the polymer having a group capable of forming a hydrogen bond with a sulfonic acid group is selected from polyacrylonitrile, polycaprolactone, polylactic acid-glycolic acid copolymer, or polyvinylpyrrolidone.

3. The method according to claim 1, wherein in step 2, the ratio of PEDOT: the mass fraction of the PSS solution is 0.2 wt% -1.4 wt%.

4. The method according to claim 1, wherein the standing time in step 2 is 2 to 5 min.

5. The method according to claim 1, wherein the annealing time in step 2 is 10 to 15 min.

6. The method according to claim 1, wherein the concentration of the dilute sulfuric acid in step 2 is 0.2-1.0 mol/L.

7. The method according to claim 1, wherein the time for the dilute sulfuric acid treatment in step 2 is 5 to 10 min.

Technical Field

The invention belongs to the technical field of electrostatic spinning, and relates to a preparation process of conductive composite nanofiber membranes.

Background

The conductive polymer has high conductivity, special optical performance and high mechanical flexibility, and has important application in the fields of biosensors, tissue engineering scaffolds, nerve probes, drug delivery devices, biological actuators and the like. Due to its high conductivity, it can promote the charge generated by biochemical reaction to transfer to electronic circuit, and can improve the response speed, sensitivity and versatility of biosensor.

Among the conducting polymers, poly (3,4-ethylenedioxythiophene) (PEDOT) is often used as an electrode or active substance in, for example, the nervous system, heart and skeletal muscle. The existing poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS) nano composite fiber membrane mostly adopts an in-situ polymerization method. However, the in-situ polymerization method requires control of a plurality of conditions, which is complicated. Wang et al (Wang S, et al. Chitosan/gelatin porous suspensions assembled with a reduced poly (3,4-ethylenedioxythiophene) nanoparticles for neural tissue engineering [ J]Journal of Materials Chemistry B,2017,5(24).) PEDOT/chitosan gelatin scaffolds obtained by in situ polymerization have a conductivity of only 4.95 × 10^-4S cm^-1。

Disclosure of Invention

The invention aims to provide a preparation method of conductive composite nanofiber membranes, which adopts a simple ex-situ permeation method to coat polymer electrostatic spinning nanofiber membranes with conductive high polymers PEDOT and PSS to prepare the conductive composite nanofiber membranes.

The technical scheme for realizing the purpose of the invention is as follows:

the preparation method of the conductive composite nanofiber membrane comprises the following specific steps:

step 1, preparing the polymer with the energy-compatible sulfonic acid group (— SO) by adopting an electrostatic spinning technology₃H) A polymer nanofiber membrane of hydrogen bond-forming groups;

step 2, flatly placing the polymer nanofiber membrane on a copper net, and dropwise adding PEDOT: and (3) uniformly spreading the PSS solution on the nanofiber membrane, standing, removing redundant solution on the surface, annealing at 100-160 ℃, and treating with dilute sulfuric acid to obtain PEDOT: PSS coated conductive composite nanofibers.

Preferably, in step 1, the compound having a functional group capable of reacting with a sulfonic acid group (— SO)₃H) The polymer of the group forming hydrogen bond is selected from polyacrylonitrile, polycaprolactone, polylactic acid-glycolic acid copolymer or polyvinylpyrrolidone.

Preferably, in step 2, the PEDOT: the mass fraction of the PSS solution is 0.2 wt% -1.4 wt%, the standing time is 2 min-5 min, and the annealing time is 10 min-15 min.

Preferably, in the step 2, the concentration of the dilute sulfuric acid is 0.2-1.0 mol/L.

Preferably, in the step 2, the treatment time of the dilute sulfuric acid is 5min to 10 min.

The invention successfully obtains the PEDOT: the PSS-coated conductive composite nanofiber membrane is treated by dilute sulfuric acid, so that the nanofiber membrane has high conductivity which reaches 3.28 x 10^-2S cm^-1。

Drawings

FIG. 1 is a scanning electron microscope image of conductive polyacrylonitrile composite nanofiber.

FIG. 2 is a scanning electron microscope image of the composite nanofiber prepared in comparative example 1 without removing surface surplus substances.

Fig. 3 is a cyclic voltammogram of the composite nanofibers prepared in example 1 and comparative example 2.

Detailed Description

The present invention will be described in further detail at with reference to specific examples.