Inorganic oxide conductive powder/polyaniline conductive polymer composite material and its preparation method

[0022] Example 1:

[0023] 14g of aniline was weighed and dissolved in 140g of water, and 42.5g of dodecylbenzenesulfonic acid was dissolved in the mixed acid solution of 100ml [HCL]=2mol/L and added to the reactor together, and stirred on an electric mixer (the rotation speed interval was 1000~ 1500 rpm); after half an hour of emulsification, add 1.12 g of 300-1200 mesh inorganic oxide conductive powder ATO (antimony oxide doped tin oxide); after stirring for another half an hour, the mixed solution is milky white. Weigh 27.4 g Ammonium sulfate was dissolved in 274g of water, and then added dropwise to the reactor. The ice-water bath controlled the reaction temperature to 0-10°C, and the reaction occurred immediately. After 1 hour of dropwise addition, the reaction was stirred for 24 hours. Blue, blue, blue-green, green, the final solution is dark green latex, filter, separate, wash with distilled water until no sulfate radicals can be detected in the filtrate; vacuum dry at 75°C to constant weight to obtain conductive powder ATO/polyaniline conductive polymer composite material. The yield of the composite material was 86 wt %, and the conductivity was 21.0 S/cm measured by a four-probe digital conductivity tester from Suzhou Telecommunications Instrument Factory.

[0024] In the same way, the general chemical oxidation in-situ polymerization of polyaniline synthesized without adding ATO has an electrical conductivity of only 1-2 S/cm, and the yield of the obtained polyaniline is 74%.

[0025] In the same way, dissolve dodecylbenzenesulfonic acid in 100ml [H 2 SO 4 ]=1mol/L mixed acid solution instead of dodecylbenzenesulfonic acid dissolved in 100ml [HCL]=2mol/L mixed acid solution to carry out the above reaction, the synthesized conductive powder ATO/polyaniline conductive polymer composite material, its The yield was 88 wt %, and the conductivity was 15.0 S/cm measured by a four-probe digital conductivity tester from Suzhou Telecommunications Instrument Factory. It can be seen that using dodecylbenzenesulfonic acid-sulfuric acid mixed acid solution instead of dodecylbenzenesulfonic acid-hydrochloric acid mixed acid solution, the yield of the synthesized conductive powder ATO/polyaniline conductive polymer composite material is slightly increased, but the conductivity is much lower, so hydrochloric acid is the best inorganic acid in the inorganic acid/organic acid mixed acid-doped acid aqueous solution, followed by sulfuric acid, and other inorganic acids are either less effective or more expensive.

[0026] In the same way, the conductive powder ATO/polyaniline conductive polymer composites synthesized when the addition amount of inorganic oxide conductive powder ATO reaches 2.5, 5.0, 7.5, 10.0, 12.5, 15.0 and 17.5% of aniline, respectively, the conductivity The ratios are 2.4, 9.4, 18.6, 24.5, 9.6, 5.6, and 2.3 S/cm, respectively, which are higher than the conductivity of ordinary chemical oxidation in-situ polymerized polyaniline synthesized without adding ATO, and the obtained inorganic oxide The yield of conductive powder ATO/polyaniline conductive polymer composite material is 81-89%. The particle surface morphology of the obtained inorganic oxide conductive powder ATO/polyaniline conductive polymer composite material was analyzed by scanning electron microscopy, and it was found that when the content of the inorganic oxide conductive powder ATO was below about 10%, the inorganic oxide conductive powder ATO particles basically All wrapped or covered with polyaniline. However, when the amount of ATO added increases to a certain amount, polyaniline cannot wrap or cover all ATO particles, so there will be free ATO particles in the ATO/polyaniline conductive polymer composite material.

[0027] In the same way, the conductive powder ATO/polyaniline conductive polymer composites were synthesized when the addition amount of inorganic oxide conductive powder ATO reached 20.0, 25.0, 30.0, 35.0, 40.0 and 50.0% of aniline, respectively. It is 1.4, 0.6, 0.4, 0.3, 0.3, 0.2S/cm, which are lower than the conductivity of ordinary chemical oxidation in-situ polymerized polyaniline synthesized without adding ATO, but higher than pure inorganic oxide conductive powder The electrical conductivity of ATO, and the yield of the obtained inorganic oxide conductive powder ATO/polyaniline conductive polymer composite material is 83-95%. The particle surface morphology of the obtained inorganic oxide conductive powder ATO/polyaniline conductive polymer composites was analyzed by scanning electron microscopy, and it was found that with the increasing amount of ATO added, more and more polyaniline could not be wrapped or covered with ATO particles. There are also more and more ATO particles partially encapsulated or covered by polyaniline and bare or free ATO particles not substantially encapsulated or covered by polyaniline.

[0028] In the same way, using the same molar ratio of sodium persulfate or potassium persulfate instead of ammonium persulfate has no obvious effect on the yield and conductivity of the synthesized conductive powder ATO/polyaniline conductive polymer composite material. It's just that ammonium persulfate is relatively cheap and easy to remove during washing. However, the use of the most preferred amount of potassium dichromate or ammonium dichromate instead of ammonium persulfate has no obvious effect on the yield and conductivity of the synthesized conductive powder ATO/polyaniline conductive polymer composite material.

[0029] In the same way, whether the inorganic oxide conductive powder ATO used is nano-scale, sub-micron or ultra-fine particle powder, its particle size is compared with the added amount. The effect of yield and conductivity was not significant.

[0030] Example 2:

[0031] 14g of aniline was weighed and dissolved in 140g of water, and 35.4g of camphorsulfonic acid was dissolved in 100ml of water and added to the reactor, and stirred on an electric mixer (the rotation speed range was 1000 to 1500 rpm); after half an hour of emulsification, inorganic Oxide conductive powder ATO (antimony doped tin oxide) 1.4g; after stirring for another half an hour, the mixed solution is milky white. Weigh 32.9g of ammonium persulfate and dissolve it in 274g of water, then dropwise into the reactor, ice water bath to control the reaction When the temperature is 0~10℃, the reaction occurs immediately. After 1h of dropwise addition, the reaction is carried out under stirring for 24h. The reaction solution changes from milky white to yellow-green, light blue, blue, blue-green, and green, and the final solution is dark green latex. , filtered, separated, washed with distilled water until no sulfate radicals were detected in the filtrate; vacuum dried at 75°C to constant weight to obtain conductive powder ATO/camphorsulfonic acid-doped polyaniline conductive polymer composite material. The yield of the composite material was 82.0 wt %, and the conductivity was 14.0 S/cm measured by a four-probe digital conductivity tester from Suzhou Telecommunications Instrument Factory.

[0032] In the same way, the general chemical oxidation in-situ polymerization of camphorsulfonic acid-doped polyaniline synthesized without adding ATO has an electrical conductivity of only about 0.5-1 S/cm, and the yield of the obtained polyaniline is 72-75% .

[0033] In the same way, the conductive powder ATO/camphorsulfonic acid doped polyaniline conductive polymer composites were synthesized when the addition amount of inorganic oxide conductive powder ATO reached 2.5, 5.0, 7.5, 12.5, 15.0 and 17.5% of aniline, respectively. , the electrical conductivity is 1.5, 2.7, 5.1, 4.6, 2.8, 1.1 S/cm, respectively, which are higher than those of camphorsulfonic acid-doped polyaniline synthesized by ordinary chemical oxidation in situ polymerization without adding ATO. , and the yield of the obtained inorganic oxide conductive powder ATO/polyaniline conductive polymer composite material is 81-89%.

[0034] In the same way, the conductive powder ATO/camphorsulfonic acid doped polyaniline conductive polymer composite was synthesized when the addition amount of inorganic oxide conductive powder ATO reached 20.0, 25.0, 30.0, 35.0, 40.0 and 50.0% of aniline, respectively. Material. The electrical conductivity is 0.8, 0.4, 0.3, 0.3, 0.2, 0.2 S/cm, respectively, which are lower than those of ordinary chemical oxidation in-situ polymerization of camphorsulfonic acid-doped polyaniline synthesized without adding ATO, but The conductivity is higher than that of pure inorganic oxide conductive powder ATO, and the yield of the obtained inorganic oxide conductive powder ATO/camphorsulfonic acid-doped polyaniline conductive polymer composite material is 82-94%. Moreover, the addition amount of conductive powder ATO and the conductivity and yield of the ATO/polyaniline conductive polymer composite doped with camphorsulfonic acid have similar variation rules to those in Example 1.

[0035] The particle surface morphology of the obtained inorganic oxide conductive powder ATO/camphorsulfonic acid-doped polyaniline conductive polymer composite material was analyzed by scanning electron microscopy, and the law was similar to that of Example 1.

[0036] Example 3:

[0037] 14g of aniline was weighed and dissolved in 140g of water, 35.4g of camphorsulfonic acid or 42.5g of dodecylbenzenesulfonic acid was dissolved in 100ml [HCL]=2mol/L mixed acid solution and added to the reactor together, and stirred on an electric mixer (The speed range is 1000-1500 rpm); after half an hour of emulsification, add 1.4 g of inorganic oxide conductive powder ITO (indium-doped tin oxide); after stirring for another half an hour, the mixed solution is milky white. Weigh 27.4g of ammonium persulfate and dissolve it in 274g of water, then add it dropwise into the reactor. The ice-water bath controls the reaction temperature from 0 to 10°C. The reaction occurs immediately. Yellow-green, light blue, blue, blue-green, green, the final solution is dark green latex, filtered, separated, washed with distilled water until no sulfate radicals were detected in the filtrate; vacuum dried at 75°C to constant weight , that is, the conductive powder ITO/polyaniline conductive polymer composite material is obtained. The yield of the composite material was 80 wt %, and the conductivity was measured to be 15.0 S/cm using a four-probe digital conductivity tester from Suzhou Telecommunications Instrument Factory.

[0038] In the same way, using camphorsulfonic acid or dodecylbenzenesulfonic acid-sulfuric acid mixed acid solution instead of camphorsulfonic acid or dodecylbenzenesulfonic acid-hydrochloric acid mixed acid solution, the synthesized conductive powder ITO/polyaniline conductive polymer composite material The yield is slightly increased, but the conductivity is low, similar to Example 1.

[0039] In the same way, the doped polyaniline synthesized by ordinary chemical oxidation in situ polymerization without adding ITO has an electrical conductivity of only about 1.0-2.0 S/cm, and the yield of the obtained polyaniline is 72-75%. In addition, the addition amount of the inorganic oxide conductive powder ITO, the conductivity and the yield of the ITO/polyaniline conductive polymer composite material have similar variation rules to those in Example 1 and Example 2. Usually, the amount of inorganic oxide conductive powder ITO added is in the range of 8-12% of aniline, and the conductivity of the composite is the highest. When the added amount of ITO exceeds about 16-20%, the conductivity is lower than that of the conventional chemical oxidation in situ polymerization doped polyaniline synthesized without adding ITO. The variation law of the yield is also similar to that of Example 1 and Example 2.

[0040] The particle surface morphology of the obtained inorganic oxide conductive powder ITO/doped polyaniline conductive polymer composite material was analyzed by scanning electron microscopy, and it was also found that there were similar rules to those in Example 1 and Example 2.

[0041] In the same way, using the same molar ratio of sodium persulfate or potassium persulfate instead of ammonium persulfate has no obvious effect on the yield and conductivity of the synthesized conductive powder ITO/polyaniline conductive polymer composites. However, using the most preferred amount of potassium dichromate or ammonium dichromate instead of ammonium persulfate has no obvious effect on the yield and conductivity of the synthesized conductive powder ITO/polyaniline conductive polymer composites.

[0042] In the same way, whether the inorganic oxide conductive powder ITO used is nano-scale, sub-micron or ultra-fine powder, its particle size is compared with the added amount, which is very important for the synthesized conductive powder ITO/polyaniline conductive polymer composite material. The effect of yield and conductivity was not significant.