Method for preparing carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material

Abstract

The application discloses a preparation method of a carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material, and specifically comprises the following steps: mixing carboxymethyl starch and deionized water to obtain a carboxymethyl starch dispersion; dispersing hydrochloric acid dopamine in deionized water, pouring into the carboxymethyl starch dispersion, adjusting pH to perform a polymerization reaction, and forming a polydopamine dispersion; adding pyrrole monomers dropwise into the polydopamine dispersion, adding an iron trioxide hexahydrate solution to perform an oxidation reaction, then adding glycerol to continuously perform a film forming reaction, and finally demolding. Since polypyrrole is a typical conductive polymer, it has the advantages of good conductivity and good biocompatibility; the addition of glycerol can improve the overall adhesion and flexibility; and finally prepared coating material has good moisture absorption and retention performance, conductivity and adhesion, and the preparation method is simple, low in cost and green and environment-friendly.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of coating material preparation, and particularly relates to a preparation method of a carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material. BACKGROUND

[0002] Smart fabric, also known as electronic fabric or smart clothing, is a product of the mutual fusion of electronics, communication, new materials and traditional textile technology. Smart fabric can be made of conductive fibers, conductive yarns, conductive coatings, conductive embroidery patterns, conductive laminates and various conductive materials. Among them, the conductive coating process is widely used in flexible sensors due to its simple operation, short process flow and low energy consumption, such as wearable flexible fiber-based sensing elements, which can realize the transmission of electricity and signals.

[0003] In the prior art, carbon nanotubes and water-based polyurethane are used as main components to synthesize conductive ink and prepare conductive coating cotton fabric. The influence of carbon nanotube mass fraction on the conductive performance of the ink is studied. The influence law of coating finishing times on the micro-morphology and macro-performance of the conductive coating cotton fabric is discussed. The water washing resistance, rubbing resistance and thermal stability of the conductive coating cotton fabric are tested. In addition, the improved in-situ solution polymerization method can be used to deposit pyrrole on the surface of the fabric, so that the conductive coating on the surface of the fabric has excellent mechanical stability and chemical reagent corrosion resistance. Compared with the conductive fibers made by the in-situ polymerization method, the coating coating is to coat the conductive material on the surface of the textile material, so that the surface of the finished product is conductive; it has the advantages of saving materials and less influence on the performance of the base material. SUMMARY

[0004] The purpose of the present application is to provide a preparation method of a carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material, which has excellent conductivity and adhesion.

[0005] The technical scheme adopted by the present application is a preparation method of a carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material, which is implemented according to the following steps:

[0006] Step 1, mix carboxymethyl starch and deionized water, gradually heat under stirring, continue to stir until the carboxymethyl starch is completely gelatinized and clarified, and obtain a carboxymethyl starch dispersion;

[0007] Step 2, disperse hydrochloric acid dopamine in deionized water, pour into the carboxymethyl starch dispersion under stirring, adjust the pH, and perform a polymerization reaction to form a polydopamine dispersion;

[0008] Step 3, the pyrrole monomer is slowly added into the stirring polydopamine dispersion liquid, the ferric oxide trihydrate solution is added, the oxidation reaction is carried out, the carboxymethyl starch / polydopamine / poly pyrrole dispersion liquid is prepared, then the glycerol is added, the film forming reaction is continuously carried out, the demolding is carried out, and the carboxymethyl starch / polydopamine / poly pyrrole composite conductive coating material is obtained.

[0009] The application also has the characteristics that,

[0010] In step 1, the mass ratio of carboxymethyl starch and deionized water is 1:40-90; the stirring speed is 300-500 r / min; the temperature is raised to 70-80 DEG C; and the continuous stirring time is 30-60 min.

[0011] In step 2, the mass ratio of dopamine hydrochloride and deionized water is 1:10-30; the pH is adjusted to 8-10 by using NaOH solution.

[0012] In step 2, the polymerization reaction time is 30-60 min; and the stirring speed is 300-500 r / min.

[0013] In step 3, the concentration of the ferric oxide trihydrate solution is 0.9-1 mol / L; and the mass ratio of pyrrole monomer, carboxymethyl starch / polydopamine dispersion liquid, ferric oxide trihydrate solution and glycerol is 0.5-1.5:120-150:17-20:2-4.

[0014] In step 3, the oxidation reaction time is 60-90 min, the film forming reaction time is 30-60 min; and the stirring speed is 300-500 r / min.

[0015] The application has the advantages that, the carboxymethyl starch which is a green, renewable and biodegradable natural polymer material is used as a base, dopamine hydrochloride and pyrrole monomer are used as basic raw materials; according to the self-polymerization reaction of dopamine in weak alkaline environment, the polydopamine with dark brown color is formed; the polydopamine has the advantages of easy preparation and modification, strong adhesion, biocompatibility, excellent light-heat conversion performance and the like, and can neutralize the rigidity of poly pyrrole; the pyrrole monomer is oxidized by using FeCl3 as an oxidant, and the poly pyrrole is synthesized by using a chemical oxidation method; the poly pyrrole is a typical conductive polymer, and has the advantages of good conductivity and good biocompatibility; then the glycerol is added to improve the adhesion and flexibility of the whole, and the composite coating material is prepared after drying at room temperature. The coating material has good moisture absorption and retention performance, conductivity and adhesion, and has the advantages of simple preparation method, low cost and green environmental protection. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is the light emitting diagram of a small bulb connected with the circuit of the composite conductive coating material prepared in example 1 of the application;

[0017] Figure 2 is a light emitting diagram of a small bulb connected with circuit after the composite conductive coating material prepared in embodiment 2 of the present application;

[0018] Figure 3 is a light emitting diagram of a small bulb connected with circuit after the composite conductive coating material prepared in embodiment 3 of the present application;

[0019] Figure 4 is a light emitting diagram of a small bulb connected with circuit after the composite conductive coating material prepared in embodiment 4 of the present application. DETAILED DESCRIPTION

[0020] The present application will be described in detail below with specific embodiments and drawings.

[0021] The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material is implemented according to the following steps:

[0022] Step 1, mix carboxymethyl starch and deionized water, gradually heat to 70-80℃ under constant stirring, stir for 30-60min, so that the carboxymethyl starch is completely gelatinized and clarified, and a carboxymethyl starch dispersion is obtained;

[0023] The mass ratio of carboxymethyl starch to deionized water is 1:40-90; the stirring speed is 300-500r / min;

[0024] Step 2, disperse dopamine hydrochloride in deionized water, pour into the carboxymethyl starch dispersion under stirring, use 0.1mol / L NaOH solution to adjust the pH to 8-10, so that the dopamine monomer undergoes polymerization reaction in the carboxymethyl starch dispersion, and self-polymerization forms a polydopamine dispersion;

[0025] The mass ratio of dopamine hydrochloride to deionized water is 1:10-30;

[0026] The polymerization reaction time is 30-60min; the stirring speed is 300-500r / min;

[0027] Step 3, slowly drop the pyrrole monomer into the polydopamine dispersion under stirring, add ferric oxide hexahydrate solution for oxidation of pyrrole, react for 60-90min, so that the pyrrole monomer self-polymerizes to form polypyrrole, and a carboxymethyl starch / polydopamine / polypyrrole dispersion is prepared, then add glycerol, continue the film forming reaction for 30-60min, and the film is dried and demolded, to obtain the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material.

[0028] The stirring speed is 300-500r / min;

[0029] The concentration of the ferric oxide hexahydrate solution is 0.9-1 mol / L;

[0030] The mass ratio of the pyrrole monomer, the carboxymethyl starch / polydopamine dispersion, the ferric oxide hexahydrate solution and the glycerol is 0.5-1.5:120-150:17-20:2-4.

[0031] Example 1

[0032] A preparation method of a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material, the coating material including the following components by mass fraction:

[0033] The carboxymethyl starch dispersion is 100 g, the carboxymethyl starch / polydopamine dispersion is 130 g, and the carboxymethyl starch / polydopamine / poly-pyrrole dispersion is 140 g;

[0034] The carboxymethyl starch and deionized water are added into a single-mouth bottle, and the temperature is gradually increased to 70°C under constant stirring for 30 min, so that the carboxymethyl starch is completely gelatinized and clarified to obtain a carboxymethyl starch dispersion.

[0035] The mass ratio of the carboxymethyl starch to deionized water is 1:50, and the stirring speed is 300 r / min.

[0036] The dopamine is dispersed in deionized water, and the prepared solution is poured into the carboxymethyl starch dispersion under stirring, the pH is adjusted to 8, and the reaction is performed for 30 min, so that the dopamine monomer is polymerized in the carboxymethyl starch dispersion to form polydopamine by self-polymerization.

[0037] The mass ratio of the dopamine hydrochloride to deionized water is 1:15, and the stirring speed is 300 r / min.

[0038] 1 g of pyrrole monomer is slowly added into the carboxymethyl starch / polydopamine dispersion under stirring at a stirring speed of 300 r / min, and the ferric oxide hexahydrate solution is added to oxidize the pyrrole for 65 min, so that the pyrrole monomer is self-polymerized to form poly-pyrrole, thereby preparing a carboxymethyl starch / polydopamine / poly-pyrrole dispersion, and then glycerol is added, and the reaction is continuously performed for 30 min, and the film is dried and demolded to obtain a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material.

[0039] Example 2

[0040] A preparation method of a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material, the coating material including the following components by mass fraction:

[0041] The carboxymethyl starch dispersion is 100 g, the carboxymethyl starch / polydopamine dispersion is 120 g, and the carboxymethyl starch / polydopamine / poly-pyrrole dispersion is 130 g;

[0042] Carboxymethyl starch and deionized water were added to a single-mouth bottle, and gradually heated to 75℃ under constant stirring for 40min to make the carboxymethyl starch completely gelatinized and clear, obtaining a carboxymethyl starch dispersion.

[0043] The mass ratio of carboxymethyl starch to water was 1:50; the stirring speed was 400r / min.

[0044] Dopamine was dispersed in deionized water, and the prepared solution was poured into the carboxymethyl starch dispersion under stirring, the pH was adjusted to 8.5, and the reaction was carried out for 45min to make the dopamine monomer in the carboxymethyl starch dispersion undergo polymerization reaction, and self-polymerization to form polydopamine.

[0045] The mass ratio of dopamine hydrochloride to water was 1:10; the stirring speed was 450r / min;

[0046] 2g of pyrrole monomer was slowly added to the carboxymethyl starch / polydopamine dispersion under stirring, the stirring speed was 450r / min; iron oxide solution was added to oxidize pyrrole, and the reaction was carried out for 65min to make the pyrrole monomer self-polymerize to form polypyrrole, and the carboxymethyl starch / polydopamine / polypyrrole dispersion was prepared, then glycerol was added and the reaction was continued for 45min, and after the film was dried, it was demolded to obtain the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material.

[0047] Example 3

[0048] The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material, the coating material, by mass fraction, includes the following components:

[0049] Carboxymethyl starch dispersion 120g, carboxymethyl starch / polydopamine dispersion 130g, carboxymethyl starch / polydopamine / polypyrrole dispersion 140g;

[0050] Carboxymethyl starch and deionized water were added to a single-mouth bottle, and gradually heated to 80℃ under constant stirring for 60min to make the carboxymethyl starch completely gelatinized and clear, obtaining a carboxymethyl starch dispersion.

[0051] The mass ratio of carboxymethyl starch to deionized water was 1:60; the stirring speed was 400r / min;

[0052] Dopamine was dispersed in deionized water, and the prepared solution was poured into the carboxymethyl starch dispersion under stirring, the pH was adjusted to 10, and the reaction was carried out for 60min to make the dopamine monomer in the carboxymethyl starch dispersion undergo polymerization reaction, and self-polymerization to form polydopamine.

[0053] The mass ratio of dopamine hydrochloride to deionized water is 1:10; the stirring speed is 500 r / min;

[0054] 2 g of pyrrole monomer is slowly added dropwise into the carboxymethyl starch / polydopamine dispersion liquid under stirring at a stirring speed of 500 r / min; iron trioxide hexahydrate solution is added to oxidize pyrrole, and the reaction is carried out for 90 min to make pyrrole monomers self-polymerize to form poly-pyrrole, thereby preparing a carboxymethyl starch / polydopamine / poly-pyrrole dispersion liquid; then glycerol is added, and the reaction is continuously carried out for 60 min; after the film is dried and demolded, a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material is obtained.

[0055] Example 4

[0056] A preparation method of a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material, which comprises the following components by mass fraction:

[0057] Carboxymethyl starch dispersion liquid 90 g, carboxymethyl starch / polydopamine dispersion liquid 110 g, and carboxymethyl starch / polydopamine / poly-pyrrole dispersion liquid 120 g;

[0058] Carboxymethyl starch and deionized water are added into a single-neck flask, and the temperature is gradually increased to 80°C under continuous stirring for 55 min to make the carboxymethyl starch completely gelatinize and clarify, thereby obtaining a carboxymethyl starch dispersion liquid.

[0059] The mass ratio of carboxymethyl starch to water is 1:90; the stirring speed is 430 r / min.

[0060] Dopamine is dispersed in deionized water, and the prepared solution is poured into the carboxymethyl starch dispersion liquid under stirring, the pH value is adjusted to 8, and the reaction is carried out for 30 min to make the dopamine monomers polymerize in the carboxymethyl starch dispersion liquid to form polydopamine through self-polymerization.

[0061] The mass ratio of dopamine hydrochloride to water is 1:10; the polymerization reaction is carried out for 30-60 min; the stirring speed is 325 r / min; and the pH value is adjusted to 8-10.

[0062] 2 g of pyrrole solution is slowly added dropwise into the carboxymethyl starch / polydopamine dispersion liquid under stirring, iron trioxide hexahydrate solution is added to oxidize pyrrole, and the reaction is carried out for 75 min to make pyrrole monomers self-polymerize to form poly-pyrrole, thereby preparing a carboxymethyl starch / polydopamine / poly-pyrrole dispersion liquid; then glycerol is added, and the reaction is continuously carried out for 45 min; after the film is dried and demolded, a carboxymethyl starch / polydopamine / poly-pyrrole composite conductive coating material is obtained.

[0063] The carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material prepared by the method of the present application is placed in air for 1-2 hours, and the surface thereof becomes wet, thus proving that it has moisture absorption and moisture retention properties;

[0064] The carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material prepared by the method of the present application is placed in air for 1-2 hours, and the surface thereof becomes wet, thus proving that it has moisture absorption and moisture retention properties; Figures 1-4 As shown in the circuit connection of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material prepared by the method of the present application,

[0065] In addition, the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material of the present application has good adhesion, can be smoothly coated on the surface of the fabric, and is uniform and complete; and has good mechanical properties and ductility.

Claims

1. A method for preparing a carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material, characterized in that, The specific steps are as follows: Step 1: Mix carboxymethyl starch and deionized water, gradually heat while stirring, and continue stirring until the carboxymethyl starch is completely gelatinized and clarified to obtain a carboxymethyl starch dispersion. Step 2: Disperse dopamine hydrochloride in deionized water, pour it into the carboxymethyl starch dispersion under stirring, adjust the pH, and carry out the polymerization reaction to form a carboxymethyl starch / polydopamine dispersion. Step 3: Pyrrole monomer is slowly added dropwise to the carboxymethyl starch / polydopamine dispersion under stirring. Ferric chloride hexahydrate solution is added to carry out the oxidation reaction to obtain carboxymethyl starch / polydopamine / polypyrrole dispersion. Then, glycerol is added to continue the film-forming reaction, thus obtaining the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material.

2. The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material as described in claim 1, characterized in that, In step 1, the mass ratio of carboxymethyl starch to deionized water is 1:40-90; the stirring speed is 300-500 r / min; the temperature is raised to 70-80℃; and the stirring time is continued for 30-60 min.

3. The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material as described in claim 1, characterized in that, In step 2, the mass ratio of dopamine hydrochloride to deionized water is 1:10-30; the pH is adjusted to 8-10 using NaOH solution.

4. The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material as described in claim 1, characterized in that, In step 2, the polymerization reaction time is 30-60 min; the stirring speed is 300-500 r / min.

5. The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material as described in claim 1, characterized in that, In step 3, the concentration of the ferric chloride hexahydrate solution is 0.9~1mol / L; the mass ratio of pyrrole monomer, carboxymethyl starch / polydopamine dispersion, ferric chloride hexahydrate solution and glycerol is 0.5-1.5:120-150:17-20:2-4.

6. The preparation method of the carboxymethyl starch / polydopamine / polypyrrole composite conductive coating material as described in claim 1, characterized in that, In step 3, the oxidation reaction time is 60-90 min, the film formation reaction time is 30-60 min, and the stirring speed is 300-500 r / min.

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