CN103084126B - Microspheres with high tap density and conductivity and preparation method thereof - Google Patents
Microspheres with high tap density and conductivity and preparation method thereof Download PDFInfo
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- CN103084126B CN103084126B CN201310020845.2A CN201310020845A CN103084126B CN 103084126 B CN103084126 B CN 103084126B CN 201310020845 A CN201310020845 A CN 201310020845A CN 103084126 B CN103084126 B CN 103084126B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004005 microsphere Substances 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000767 polyaniline Polymers 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 5
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000012792 core layer Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229920001940 conductive polymer Polymers 0.000 description 9
- 239000002322 conducting polymer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides microspheres with high tap density and conductivity and a preparation method thereof. The preparation method comprises the steps as follows: dispersing 3,4-ethylenedioxythiophene monomer in a mixed medium of water and ethanol, adding a water-soluble oxidant in the presence of an emulsifier, and ultrasonically reacting until a blue turbid matter appears; adding a phenylamine monomer, and continuing to ultrasonically react so as to form microspheres of a polyaniline/poly 3,4-ethylenedioxythiophene copolymer; placing into a sulfuric acid solution, and heating for 30-45 min under the microwave condition to obtain the microspheres with high tap density and conductivity, wherein the microspheres are of a core-shell type structure, a core layer comprises a high-conductivity 3,4-ethylenedioxythiophene oligomer, and a shell layer comprises the polyaniline and poly-3,4-ethylenedioxythiophene copolymer. The tap density of the polymer microspheres is 3.5-4.0 g/cm<2>, and the microspheres can be used as a new generation of conductive material, electrode material, high-performance battery anode material and anode material for nonferrous metal electro-deposition by utilizing high conductivity and tap density.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, relate to and a kind of there is microballoon of high-tap density and electric conductivity and preparation method thereof.
Background technology
At present, conducting polymer, owing to having special structure and excellent physical and chemical performance, therefore has a wide range of applications and receives much concern in opto-electronic device, the energy, information, sensor and anti-corrosion of metal, electromagnetic shielding and anode material etc.But these application all need film or the bulk of preparing conducting polymer.As, a kind of Conductive Polymer Materials-PAN (PANI) conventional at present not only has excellent stability to environment, and itself has adjustable different state of oxidation, controls its electric conductivity by doping/dedoping, be easy to synthesis, raw material is cheap to be easy to get.In addition, poly-3,4-ethene dioxythiophene (PEDOT) is as the novel conductive polymer in a kind of polythiofuran derivative class, it is high that its doping state has conductance, the features such as environmental stability is good, redox reaction can occur electric field induce and electrochemically stable, have become the research emphasis that conducting polymer is new.By by conducting polymer composite and copolymerization combine with technique, many new chemistry and physical property can be brought, thus expand its application further, become the focus of recent conducting polymer research.Synthesis and applications as polyaniline microsphere just receives the concern of people gradually.At present, polyaniline microsphere is generally by the method preparation of hard template (as polystyrene microsphere) or soft template (as parents' molecule micella), and these method flows are complicated, and the component that can affect microballoon is formed, cause monodispersity bad wait not enough.For this reason, industry is thirsted for developing a kind of easy conducting polymer microballoon preparing high-tap density, high conductivity fast for a long time always.
Summary of the invention
Technical problem to be solved by this invention is to provide polymer microsphere of a kind of polyaniline/poly-3,4-rthylene dioxythiophene copolymer with high conductivity, high-tap density and even particle size distribution and preparation method thereof.
The present invention is realized by following technical proposal: a kind of microballoon with high-tap density and electric conductivity, its structure is core-shell type, and the oligomer that core gathers 3,4-rthylene dioxythiophene by high conductivity forms, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
Another object of the present invention is to provide a kind of preparation method with the microballoon of high-tap density and electric conductivity, through following each step:
(1) by 3, the volume ratio of the blending agent of 4-ethene dioxythiophene monomer and water and ethanol is 1 ~ 20:100, by 3,4-ethene dioxythiophene monomer dispersion is in the blending agent of water and ethanol, again under emulsifying agent existent condition, adding water-soluble oxidizers ultrasonic reaction at 15 ~ 25 DEG C of temperature, after 2 ~ 2.5 hours, occurs blue muddy;
(2) in the mixture of step (1), add aniline monomer, to continue at 15 ~ 25 DEG C of temperature ultrasonic reaction 2 ~ 6 hours, form the microballoon of polyaniline/poly-3,4-rthylene dioxythiophene copolymer;
(3) be the sulfuric acid solution that 15 ~ 45:100 is placed in 0.15 ~ 2.5mol/L by the microballoon of step (2) by solid-to-liquid ratio, be the heated under microwave conditions 30 ~ 45 minutes of 50W again at power, namely the microballoon with high-tap density and electric conductivity is obtained, its structure is core-shell type, core is by high conductivity poly-3, the oligomer composition of 4-ethene dioxythiophene, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
The water of described step (1) and the blending agent of ethanol are the mixed solutions of water and ethanol 1:1 in mass ratio.
The emulsifying agent of described step (1) is polyvinylpyrrolidone and cetyl ammonium bromide is the mixture of 4:1 in molar ratio.
The emulsifying agent of described step (1) and the mol ratio of 3,4-rthylene dioxythiophene are 1:10 ~ 1:5.
The water-soluble oxidizers of described step (1) is ammonium persulfate and iron chloride.
The water-soluble oxidizers of described step (1) and the mol ratio of 3,4-rthylene dioxythiophene monomer are: the mol ratio of 3,4-rthylene dioxythiophene monomer and ammonium persulfate is 1:1 ~ 1:2.5; The mol ratio of 3,4-rthylene dioxythiophene and iron chloride is 1:1 ~ 1:1.5.
The aniline monomer of described step (2) and the mol ratio of 3,4-rthylene dioxythiophene monomer are 8:1 ~ 4:1.
Compared with prior art, beneficial effect of the present invention is: in liquid-phase system, epigranular is prepared by an one-step template-free, polyaniline/poly-3 of high conductivity and high-tap density, the microballoon of 4-ethene dioxythiophene copolymer, thus when effectively overcoming that in the crosslinked and prior art in polyaniline polymerization process, dura mater plate or soft template prepare conducting polymer microballoon, complex process, easily affect the component formation of microballoon and the deficiency etc. of dispersiveness.
The present invention is first by 3,4-ethene dioxythiophene is after initator and adulterant coexist lower ultrasonic disperse initiated polymerization, introduce aniline monomer again, polymerization obtains polyaniline/poly-3, the microballoon of 4-ethene dioxythiophene copolymer, under microwave condition, carry out doping reaction subsequently again to microballoon, make this copolymer have high conductivity and high-tap density.The inventive method is simple and easy to operate, and controllability is strong.Polymer microsphere provided by the invention, tap density is at 3.5 ~ 4.0g/cm
2 ,the electric conductivity utilizing it high and high-tap density, can be used as the conductive material of a new generation, electrode material, heavy-duty battery anode material and non-ferrous metal electrodeposition anode material.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of embodiment 3 thus obtained microsphere.
Detailed description of the invention
Below by embodiment, the present invention will be further described.
Embodiment 1
(1) by 3, the volume ratio of the blending agent of 4-ethene dioxythiophene monomer and water and ethanol is 20:100, by 3,4-ethene dioxythiophene monomer dispersion is in the blending agent of water and ethanol, be 1:8 by the mol ratio of emulsifying agent and 3,4-rthylene dioxythiophene again, under emulsifying agent existent condition, adding water-soluble oxidizers (ammonium persulfate and iron chloride) ultrasonic reaction at 15 DEG C of temperature, after 2.5 hours, occurs blue muddy; Wherein, the mixed solution of water and ethanol 1:1 in mass ratio; Emulsifying agent is polyvinylpyrrolidone and cetyl ammonium bromide is the mixture of 4:1 in molar ratio; The mol ratio of water-soluble oxidizers and 3,4-rthylene dioxythiophene monomer is: the mol ratio of 3,4-rthylene dioxythiophene monomer and ammonium persulfate is 1:1; The mol ratio of 3,4-rthylene dioxythiophene and iron chloride is 1:1.2;
(2) be 8:1 by the mol ratio of aniline monomer and 3,4-rthylene dioxythiophene monomer, in the mixture of step (1), add aniline monomer, to continue at 25 DEG C of temperature ultrasonic reaction 4 hours, form the microballoon of polyaniline/poly-3,4-rthylene dioxythiophene copolymer;
(3) be the sulfuric acid solution that 30:100 is placed in 0.15mol/L by the microballoon of step (2) by solid-to-liquid ratio, be the heated under microwave conditions 45 minutes of 50W again at power, namely the microballoon with high-tap density and electric conductivity is obtained, its structure is core-shell type, core is by high conductivity poly-3, the oligomer composition of 4-ethene dioxythiophene, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
Embodiment 2
(1) by 3, the volume ratio of the blending agent of 4-ethene dioxythiophene monomer and water and ethanol is 10:100, by 3,4-ethene dioxythiophene monomer dispersion is in the blending agent of water and ethanol, be 1:10 by the mol ratio of emulsifying agent and 3,4-rthylene dioxythiophene again, under emulsifying agent existent condition, adding water-soluble oxidizers (ammonium persulfate and iron chloride) ultrasonic reaction at 20 DEG C of temperature, after 2.2 hours, occurs blue muddy; Wherein, the mixed solution of water and ethanol 1:1 in mass ratio; Emulsifying agent is polyvinylpyrrolidone and cetyl ammonium bromide is the mixture of 4:1 in molar ratio; The mol ratio of water-soluble oxidizers and 3,4-rthylene dioxythiophene monomer is: the mol ratio of 3,4-rthylene dioxythiophene monomer and ammonium persulfate is 1:2.5; The mol ratio of 3,4-rthylene dioxythiophene and iron chloride is 1:1;
(2) be 6:1 by the mol ratio of aniline monomer and 3,4-rthylene dioxythiophene monomer, in the mixture of step (1), add aniline monomer, to continue at 20 DEG C of temperature ultrasonic reaction 6 hours, form the microballoon of polyaniline/poly-3,4-rthylene dioxythiophene copolymer;
(3) be the sulfuric acid solution that 15:100 is placed in 1.5mol/L by the microballoon of step (2) by solid-to-liquid ratio, be the heated under microwave conditions 35 minutes of 50W again at power, namely the microballoon with high-tap density and electric conductivity is obtained, its structure is core-shell type, core is by high conductivity poly-3, the oligomer composition of 4-ethene dioxythiophene, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
Embodiment 3
(1) by 3, the volume ratio of the blending agent of 4-ethene dioxythiophene monomer and water and ethanol is 1:100, by 3,4-ethene dioxythiophene monomer dispersion is in the blending agent of water and ethanol, be 1:5 by the mol ratio of emulsifying agent and 3,4-rthylene dioxythiophene again, under emulsifying agent existent condition, adding water-soluble oxidizers (ammonium persulfate and iron chloride) ultrasonic reaction at 25 DEG C of temperature, after 2 hours, occurs blue muddy; Wherein, the mixed solution of water and ethanol 1:1 in mass ratio; Emulsifying agent is polyvinylpyrrolidone and cetyl ammonium bromide is the mixture of 4:1 in molar ratio; The mol ratio of water-soluble oxidizers and 3,4-rthylene dioxythiophene monomer is: the mol ratio of 3,4-rthylene dioxythiophene monomer and ammonium persulfate is 1:2; The mol ratio of 3,4-rthylene dioxythiophene and iron chloride is 1:1.5;
(2) be 4:1 by the mol ratio of aniline monomer and 3,4-rthylene dioxythiophene monomer, in the mixture of step (1), add aniline monomer, to continue at 15 DEG C of temperature ultrasonic reaction 2 hours, form the microballoon of polyaniline/poly-3,4-rthylene dioxythiophene copolymer;
(3) be the sulfuric acid solution that 45:100 is placed in 2.5mol/L by the microballoon of step (2) by solid-to-liquid ratio, be the heated under microwave conditions 30 minutes of 50W again at power, namely the microballoon with high-tap density and electric conductivity is obtained, its structure is core-shell type, core is by high conductivity poly-3, the oligomer composition of 4-ethene dioxythiophene, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
Claims (5)
1. there is a preparation method for the microballoon of high-tap density and electric conductivity, it is characterized in that through following each step:
(1) by 3, the volume ratio of the blending agent of 4-ethene dioxythiophene monomer and water and ethanol is 1 ~ 20:100, by 3,4-ethene dioxythiophene monomer dispersion is in the blending agent of water and ethanol, again under emulsifying agent existent condition, add water-soluble oxidizers ultrasonic reaction after 2 ~ 2.5 hours at 15 ~ 25 DEG C of temperature, occur blue muddy, wherein emulsifying agent is polyvinylpyrrolidone and cetyl ammonium bromide is the mixture of 4:1 in molar ratio, and water-soluble oxidizers is ammonium persulfate and iron chloride;
(2) in the mixture of step (1), add aniline monomer, to continue at 15 ~ 25 DEG C of temperature ultrasonic reaction 2 ~ 6 hours, form the microballoon of polyaniline/poly-3,4-rthylene dioxythiophene copolymer;
(3) be the sulfuric acid solution that 15 ~ 45:100 is placed in 0.15 ~ 2.5mol/L by the microballoon of step (2) by solid-to-liquid ratio, be the heated under microwave conditions 30 ~ 45 minutes of 50W again at power, namely the microballoon with high-tap density and electric conductivity is obtained, its structure is core-shell type, core is by high conductivity poly-3, the oligomer composition of 4-ethene dioxythiophene, shell is the copolymer composition of polyaniline and poly-3,4-rthylene dioxythiophene.
2. the preparation method with the microballoon of high-tap density and electric conductivity according to claim 1, is characterized in that: the water of described step (1) and the blending agent of ethanol are the mixed solutions of water and ethanol 1:1 in mass ratio.
3. the preparation method with the microballoon of high-tap density and electric conductivity according to claim 1, is characterized in that: the emulsifying agent of described step (1) and the mol ratio of 3,4-rthylene dioxythiophene are 1:10 ~ 1:5.
4. the preparation method with the microballoon of high-tap density and electric conductivity according to claim 1, it is characterized in that: the water-soluble oxidizers and 3 of described step (1), the mol ratio of 4-ethene dioxythiophene monomer is: the mol ratio of 3,4-rthylene dioxythiophene monomer and ammonium persulfate is 1:1 ~ 1:2.5; The mol ratio of 3,4-rthylene dioxythiophene and iron chloride is 1:1 ~ 1:1.5.
5. the preparation method with the microballoon of high-tap density and electric conductivity according to claim 1, is characterized in that: the aniline monomer of described step (2) and the mol ratio of 3,4-rthylene dioxythiophene monomer are 8:1 ~ 4:1.
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|---|---|---|---|---|
| CN101284927A (en) * | 2008-06-02 | 2008-10-15 | 南京大学 | Method for preparing electric-conducting high molecule complex particles of polystyrol/poly 3, 4-ethylenedioxy-thiophene |
| CN102344650A (en) * | 2010-08-02 | 2012-02-08 | 中国科学院理化技术研究所 | Preparation method of Fe3O4-poly (3, 4-ethylenedioxythiophene) core-shell structured composite microspheres |
| CN102443251A (en) * | 2011-09-21 | 2012-05-09 | 中国科学院理化技术研究所 | Preparation method of iron oxide/poly (3, 4-dioxoethyl) thiophene composite nanorods |
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|---|---|---|---|---|
| CN101284927A (en) * | 2008-06-02 | 2008-10-15 | 南京大学 | Method for preparing electric-conducting high molecule complex particles of polystyrol/poly 3, 4-ethylenedioxy-thiophene |
| CN102344650A (en) * | 2010-08-02 | 2012-02-08 | 中国科学院理化技术研究所 | Preparation method of Fe3O4-poly (3, 4-ethylenedioxythiophene) core-shell structured composite microspheres |
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| Title |
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| 朱维.复合乳化剂浓度对PANI /PEDOT 复合阳极.《昆明理工大学学报(自然科学版)》.2011,第36卷(第5期), * |
| 聚3,4-乙烯二氧噻吩/聚苯胺复合材料的制备与性能;黄惠等;《过程工程学报》;20120831;第12卷(第4期);第672页右栏第17行至第675页右栏第15行，图7 * |
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