CN101298698B - Method for surface in situ synthesis of conductive polyaniline PANi by using four acicular type zinc oxide crystal whisker T-ZnOw - Google Patents
Method for surface in situ synthesis of conductive polyaniline PANi by using four acicular type zinc oxide crystal whisker T-ZnOw Download PDFInfo
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- CN101298698B CN101298698B CN2008100452499A CN200810045249A CN101298698B CN 101298698 B CN101298698 B CN 101298698B CN 2008100452499 A CN2008100452499 A CN 2008100452499A CN 200810045249 A CN200810045249 A CN 200810045249A CN 101298698 B CN101298698 B CN 101298698B
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Abstract
The invention discloses a method for T-ZnOw surface in-situ synthesizing conductive PANi. The method includes the steps: tetrapod zinc oxide whisker T-ZnOw is dried for 2 to 8 hours under temperature of 100 to 140 DEG C and then is dispersed into an absolute ethyl alcohol solution, silane coupling agent is added into the solution, and then the solution is stirred for 0.5 to 3 hours, heated to 70 to 95 DEG C, stirred and returned for 8 to 12 hours under constant temperature; the reaction product is washed by alcohol and water and then is dried and dispersed into the absolute ethyl alcohol, then aniline monomer and 0.5mol/ L hydrochloric acid solution are added, and then the mixture is stirred for 30 minutes in icy bathing water and the temperature is preserved between 0 and 5 DEG C; while in stirring, a solution formed by ammonium persulfate and distilled water is dropped into the mixture and the reaction is preserved for 6 to 8 hours under the temperature of 0 to 5 DEG C; the reaction product is filtered and washed by water and ketone and then is dried to obtain the T-ZnOw coated by PANi; the product is put into hydrochloric acid solution (the PH of which is equal to 0 to 2) for 6 to 18 hours of reaction with stirring, and then the solution is filtered and dried in vacuum to obtain the conductive PANi/T-ZnOw mixed with hydrochloric acid. The conductivity of the product is controlled through controlling the mixing.
Description
Technical field
The present invention relates to material modification technical field, particularly conductive polymers and inorganic composite materials technical field.
Background technology
By the microcosmic of two kinds or more of materials compound can obtain having concurrently each constituent materials performance, possess the matrix material of unique characteristics such as light, electricity, magnetic and catalysis simultaneously.Wherein, conductive polymers/inorganic particle composite material receives publicity day by day owing to combine the advantage of polymkeric substance and inorganic particulate material.
Four acicular type zinc oxide crystal whisker (T-ZnOw) is a kind of multi-function metal oxide material, its microtexture comprises a central point and four whiskers bodies from the emitting shape extension in three-dimensional space of same central point, the length 10-200 μ m of needles, base diameter 0.1-5 μ m (as shown in Figure 1); It is except having semi-conductor, piezoelectricity and the antibacterial similar to common ZnO powder body material, also because the singularity of its structure shows functional performances such as high strength, high-modulus, high temperature resistant, wear-resisting, suction ripple.But, lower (less than 10 without the T-ZnOw electric conductivity of modification
-6S/cm), limited its application in some field.By mixing, though can improve conductivity to a certain extent, doping condition (as high temperature) can destroy its tip and single crystal structure, influences the performance of some function.So, composite modified by surface deposition or coating etc., might realize its multifunction application.A kind of method that obtains magnetic composite at four acicular type zinc oxide crystal whisker surface in situ synthesizing nano magnetic particle is disclosed as Chinese patent 200510020865.5.
Polyaniline is as studying one of conductive polymers the most widely at present, when possessing characteristics such as little, the easy preparation of traditional macromolecular material density, good processability, possess some unique physicochemical property again, particularly can control the characteristics of its molecular structure, electric conductivity and color, and become the research and development emphasis of intelligent macromolecule material by mixing.Because polyaniline need be under strong acidic condition be obtained by causing aniline polymerization, and this condition tends to the structure of disruptive oxidation zinc or even react and make its dissolving.Preparing zinc oxide/polyaniline composite material by the aniline in-situ polymerization and do not see that so far report is arranged, is not that nuclear, conductive polymers are the report that shell prepares nucleocapsid structure ZnOw/polyaniline composite material with four zinc oxide acicular structure whiskers more.
Summary of the invention
Above shortcoming in view of prior art, the object of the invention is to provide a kind of original position synthesis technique to prepare the method for special nucleus shell structure PANi/T-ZnOw matrix material, forms the silane coupled agent molecule of one deck on the ZnOw surface with four acicular structures by chemical reaction; Then the in-situ polymerization of polyaniline takes place and obtain the four acicular type zinc oxide crystal whisker that polyaniline coats on its surface; Doping by to T-ZnOw surface polyaniline obtains specific conductivity 10
-6～10
3The PANi/T-ZnOw matrix material of control and adjusting between the S/cm.
The object of the present invention is achieved like this:
The method of a kind of four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi comprises following steps:
(a). four acicular type zinc oxide crystal whisker T-ZnOw is distributed in the ethanol solution after 100-140 ℃ of drying, adds silane coupling agent, be warming up to 70-95 ℃, constant temperature stirring and refluxing 8-12h behind the stirring 0.5-3h; After reaction finishes, filter the gained solid and be placed in the 40-100 ℃ of baking oven freeze-day with constant temperature 10-24 hour with dehydrated alcohol and distilled water wash successively;
(b). go up the step products therefrom and be distributed in the dehydrated alcohol, add aniline monomer, the 0.5mol/L hydrochloric acid soln stirs 30min in ice-water bath, and keeps 0-5 ℃; Under whipped state, add the solution of ammonium persulphate and distilled water composition by the dropping mode; Keep 0-5 ℃ of reaction 6-8h; Reaction product after filtration with distilled water, washing with acetone after, drying obtains PANi and coats the T-ZnOw product under 60 ℃ of conditions in vacuum drying oven;
C). (b) product that obtains of step stirring reaction 6-18h under the room temperature condition in the hydrochloric acid soln of PH=0-2, filter the back at 50 ℃ of following vacuum-drying 8-48h, obtain the conduction PANi/T-ZnOw of doped hydrochloride.
Adopt technical scheme of the present invention: at first form the silane coupled agent molecule of one deck by chemical reaction on ZnOw surface with four acicular structures, this makes T-ZnOw be protected on the one hand, improves its stability in the acid system of aniline polymerization reaction take place; Make the T-ZnOw surface become the oleophylic state on the other hand, help organic polymer monomers such as hydrophobic oil loving aniline in the T-ZnOw surface attachment by hydrophily.Then, the in-situ polymerization of aniline takes place and obtain the four acicular type zinc oxide crystal whisker that polyaniline coats on its surface.At last, by T-ZnOw surface in situ synthetic polyaniline is mixed, obtain specific conductivity 10
-6～10
3Controlled PANi/T-ZnOw matrix material between the S/cm.
Description of drawings
Fig. 1 is technological line figure of the present invention
Fig. 2 is the microscopic appearance of the used four acicular type zinc oxide crystal whisker of the present invention;
Fig. 3 is an embodiment of the invention gained PANi/T-ZnOw matrix material microscopic appearance;
Fig. 4 is the PANi/T-ZnOw matrix material microscopic appearance that comparative example (not using silane coupler modified) obtains
The PANi/T-ZnOw matrix material Fourier transform infrared spectroscopy that Fig. 5 obtains for the embodiment of the invention;
The PANi/T-ZnOw matrix material X ray diffracting spectrum that Fig. 6 obtains for the embodiment of the invention.
Embodiment
Below the inventive method is described in detail.Raw materials used equal operational analysis is pure.
Embodiment
1, with the 10g four acicular type zinc oxide crystal whisker in air dry oven in 120 ℃ of following freeze-day with constant temperature 4h.
2, above-mentioned dried T-ZnOw is distributed in the 100mL ethanol solution, adds 0.3g silane coupling agent (KH-550) again, be warming up to 80 ℃, constant temperature stirring and refluxing 10h behind the stirring 1h.Question response cleans repeatedly with dehydrated alcohol, distilled water after finishing, and product is placed in 80 ℃ of baking ovens through suction filtration, freeze-day with constant temperature 24h.
3, will add the 200mL ethanol solution by the T-ZnOw after the processing in 2 steps, and add the 4.8ml aniline monomer again, 0.5mol/L hydrochloric acid soln 10mL stirs 30min in ice-water bath, make it be cooled to 2 ℃; Take by weighing the 14.7g ammonium persulphate and add 50ml distilled water and fully dissolving; Dropwise drip the ammonium persulfate aqueous solution that will prepare in above-mentioned reaction system, constantly stir in the reaction process, temperature of reaction maintains 0-5 ℃, reaction 7h.Reaction product, is transferred in the vacuum drying oven and is dried to constant weight in 60 ℃ repeatedly behind the suction filtration through distilled water, acetone.
4, in 39.14 milliliters of 3.5mol/L hydrochloric acid solns (containing HCl 5g), add the PANi coating T-ZnOw that 100g step 3 obtains, stirring reaction is 10 hours under the room temperature, product filters the back 50 ℃ of following vacuum-dryings, obtain the conduction PANi/T-ZnOw matrix material of doped hydrochloride, its fibrous texture as shown in Figure 3, recording its specific conductivity with four probe method is 4.8 * 10
2S/cm.
Comparative example:
Save the step 1 and 2 among the embodiment, directly aniline monomer is added in the dispersion liquid of T-ZnOw and dehydrated alcohol, and 0.5mol/L hydrochloric acid soln consumption is reduced to 3mL, and (zinc oxide is intermediate oxide, the hydrochloric acid consumption is too many, four acicular structures of T-ZnOw can be destroyed), other conditionally complete is identical, obtains simple mix products as shown in Figure 4, and recording its specific conductivity with four probe method is 1.6 * 10
-5S/cm.
Adopt the general planning of present method, the change condition and the optimum condition of certain limit arranged in concrete enforcement, ancillary test shows, every needles length of four acicular type zinc oxide crystal whisker T-ZnOw 5-200 micron, preferably 10-50 micron; Whisker base diameter 0.1-10 micron, preferably 0.5-5 micron; Described silane coupling agent is KH-550, KH-560, a kind of among the Si-69; The mass ratio of described silane coupling agent and T-ZnOw is 0.2-8: 100, and 0.5-4 preferably: 100; The mass percent that described aniline monomer, ammonium persulphate, 0.5mol/L hydrochloric acid soln account for T-ZnOw is respectively: 30-80% (best (40-50%), 60-150% (preferably 50-100%), 35-75% (preferably 45-60%); Described doping concentration of hydrochloric acid solution is 1-5mol/L, preferably 2-3mol/L; Pure HCl consumption is the 1-10% of PANi/T-ZnOw, preferably 2-5%.In such process parameters range, all can reach basic effect of the present invention.
Claims (5)
1. the method for a four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi is characterized in that, comprises following steps:
(a). four acicular type zinc oxide crystal whisker T-ZnOw is distributed in the ethanol solution after 100-140 ℃ of drying, adds silane coupling agent, be warming up to 70-95 ℃, constant temperature stirring and refluxing 8-12h behind the stirring 0.5-3h; After reaction finishes, filter the gained solid and be placed in the 40-100 ℃ of baking oven freeze-day with constant temperature 10-24 hour with dehydrated alcohol and distilled water wash successively; Described silane coupling agent is KH-550, KH-560, and a kind of among the Si-69, the mass ratio of silane coupling agent and T-ZnOw is 0.5-4: 100;
(b). go up the step products therefrom and be distributed in the dehydrated alcohol, add aniline monomer, the 0.5mol/L hydrochloric acid soln stirs 30min in ice-water bath, and keeps 0-5 ℃; Under whipped state, add the solution of ammonium persulphate and distilled water composition by the dropping mode; Keep 0-5 ℃ of reaction 6-8h; Reaction product after filtration with distilled water, washing with acetone after, drying obtains PANi and coats the T-ZnOw product under 60 ℃ of conditions in vacuum drying oven;
(c). (b) product that obtains of step stirring reaction 6-18h under the room temperature condition in the hydrochloric acid soln of PH=0-2, filter the back at 50 ℃ of following vacuum-drying 8-48h, obtain the conduction PANi/T-ZnOw of doped hydrochloride.
2. according to the method for the described four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi of claim 1, it is characterized in that every needles length of described four acicular type zinc oxide crystal whisker T-ZnOw 10-50 micron, base diameter 0.5-5 micron.
3. according to the method for the described four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi of claim 1, it is characterized in that, in (b) step, the mass percent that described aniline monomer, ammonium persulphate, 0.5mol/L hydrochloric acid soln account for T-ZnOW is respectively: 30-80%, 60-150%, 35-75%.
4. according to the method for the described four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi of claim 1, it is characterized in that concentration of hydrochloric acid solution is 1-3.5mol/L in the described doped hydrochloride, pure HCl consumption is the 1-5% of PANi/T-ZnOw.
5. according to the method for the described four acicular type zinc oxide crystal whisker T-ZnOw surface in situ compositing conducting polyaniline PANi of claim 4, it is characterized in that the T-ZnOW electric conductivity behind the PANi surface in situ synthesis modification can be by the doping level of surperficial polyaniline, 10
-6-10
3Control and adjusting between the S/cm.
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| CN102586881A (en) * | 2010-10-29 | 2012-07-18 | 北京矿冶研究总院 | Preparation method of zinc oxide whisker containing metal nickel copper |
| CN102134326B (en) * | 2010-11-08 | 2012-08-08 | 上海大学 | Preparation method of polyaniline/zinc oxide flexible composite electrode material |
| CN102437791B (en) * | 2011-08-30 | 2014-06-18 | 东北师范大学 | Preparation method of photoinduction nano alternative-current power generator |
| CN102945689A (en) * | 2012-10-09 | 2013-02-27 | 安徽联硕实业有限公司 | Copper aluminum alloy wire |
| CN103170369A (en) * | 2013-02-28 | 2013-06-26 | 安徽大学 | Preparation method of zinc oxide/polyaniline composite photocatalyst |
| CN103276476B (en) * | 2013-04-09 | 2015-03-25 | 西南交通大学 | Method for preparing nano-carbon fibers by T-ZnOw surface in-situ polymerization |
| CN103594631B (en) * | 2013-06-25 | 2016-04-27 | 北京科技大学 | A kind of Novel self-driven ultraviolet detector and preparation method thereof |
| CN108939741A (en) * | 2018-08-03 | 2018-12-07 | 太仓曌信金属制品有限公司 | A kind of air filtration cotton of the high-strength absorption of containing diatomite |
| CN110371950B (en) * | 2019-08-12 | 2023-06-23 | 苏州大学 | Preparation method of hollow carbon material |
| CN112878057B (en) * | 2021-02-25 | 2021-12-17 | 杭州昂普信息技术有限公司 | Skin-feel fabric and preparation method thereof |
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| CN1821315A (en) * | 2006-01-24 | 2006-08-23 | 南京航空航天大学 | Polyaniline coated nano TiO2 and poly aniline coated TiO2 whisker and their preparing method |
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