CN101284927B - Method for preparing electric-conducting high molecule complex particles of polystyrol/poly 3, 4-ethylenedioxy-thiophene - Google Patents
Method for preparing electric-conducting high molecule complex particles of polystyrol/poly 3, 4-ethylenedioxy-thiophene Download PDFInfo
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- CN101284927B CN101284927B CN2008100242908A CN200810024290A CN101284927B CN 101284927 B CN101284927 B CN 101284927B CN 2008100242908 A CN2008100242908 A CN 2008100242908A CN 200810024290 A CN200810024290 A CN 200810024290A CN 101284927 B CN101284927 B CN 101284927B
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- 239000002245 particle Substances 0.000 title claims abstract description 41
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title abstract description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229930192474 thiophene Natural products 0.000 claims abstract description 52
- 239000004793 Polystyrene Substances 0.000 claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011246 composite particle Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Polymers C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004816 latex Substances 0.000 abstract description 2
- 229920000126 latex Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 4
- 239000005977 Ethylene Substances 0.000 abstract 4
- 229910001882 dioxygen Inorganic materials 0.000 abstract 4
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/79—Post-treatment doping
- C08G2261/792—Post-treatment doping with low-molecular weight dopants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/79—Post-treatment doping
- C08G2261/794—Post-treatment doping with polymeric dopants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/96—Applications coating of particles
- C08G2261/962—Applications coating of particles coating of organic particles
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a method for preparing a polystyrene/poly 3,4-ethylene dioxygen thiophene conductive macromolecular composite particle. The method is as follows: 3,4-ethylene dioxygen thiophene and polystyrene particle latex are mixed; after the mixture is stirred for a plurality of hours, oxidant is added into the mixture at a temperature of between 50 and 80 DEG C; while stirring, acids are dripped and mixed into the mixture; after reaction for 18 to 24 hours, centrifugal washing by utilization of methanol and water is performed for a plurality of times until the upper layer solution is achromatic; after secondary separation and drying, the polystyrene/poly 3,4-ethylene dioxygen thiophene conductive macromolecular composite particle is obtained; the thickness range of a poly 3,4-ethylene dioxygen thiophene shell is between 50 and 100 nm.
Description
(1) technical field:
The invention belongs to technical field of polymer materials, be specifically related to a kind of polystyrene with nucleocapsid structure/poly-3, the preparation method of 4-enedioxy thiophene conductive, high molecular compound particles.
(2) technical background:
Conductive polymers latex nano-complex particle material integrates the functional of the electroconductibility of polymer self and nano particle, having molecular structure can design, specific conductivity can be regulated and advantage such as morphological specificity may command, and its colloid dispersive characteristic is expected to improve the shortcoming of the ubiquitous processing difficulties of conducting polymer, thereby at electric driven color-changing part, electroluminescent cell, the bio-medical transmitter, anticorrosive and the antistatic coating in metallic surface, novel wave-absorbing and camouflage coating, rechargeable battery, the petroleum cracking catalyzer, aspects such as supramolecule self-assembly have the potential application prospect.
Poly-3,4-enedioxy thiophene is the latter halves eighties 20th century, the conductive polymers of new generation that Bayer A.G successfully develops, and it has excellent conductivity, and is transparent good, is difficult for oxidizedly, and environmental stability is good, and advantage such as cheap.Particularly, the special performance of high conductivity and ultrastability perfect adaptation makes it to have a very application prospects industrial.Therefore, synthetic to gather 3,4-enedioxy thiophene is that conducting function component and the matrix material with nanostructure have very important and practical meanings.Polystyrene/poly-3,4-enedioxy thiophene core-shell type complex particle are one of common complex method and material shape.With regard to present situation, common preparation method is in the presence of the polystyrene moulding thing, carries out 3, the chemical oxidising polymerisation of 4-enedioxy thiophene, and it is deposited on the template particles surface, thus form mixture.S.P.Armes etc. utilize dispersion polymerization processes to make the polystyrene particle of the stable micron level of Polyvinylpyrolidone (PVP) earlier; The polystyrene particle emulsion joined be equipped with in certain water gaging round-bottomed flask, induction stirring, logical nitrogen deoxygenation; Add oxygenant tosic acid iron then; Heat temperature raising is to temperature of reaction; Again with syringe with a certain amount of 3, the methanol solution of 4-enedioxy thiophene joins in the flask, makes 3, the concentration of 4-enedioxy thiophene in total system is 1% volume ratio; Isothermal reaction 24 hours; What oxypolymerization at last produced gathers 3, and 4-enedioxy thiophene is deposited in the formation of polystyrene particle surface and gathers 3, and 4-enedioxy thiophene layer (reference 1:Langmuir, 1999,15,3469-3475).In order to improve composite effect, also there is p-poly-phenyl ethene particle to carry out surface treatment earlier, to strengthen particle and 3, the interaction between the 4-enedioxy thiophene impels 3, and the polymerization of 4-enedioxy thiophene occurs in the way on the surface of polystyrene particle as much as possible.In the crosslinked polystyrene particle emulsion that makes through letex polymerization, add Witco 1298 Soft Acid as Han etc., make it be adsorbed on the surface of particle, utilize its with sulfonic acid group strengthen the polystyrene particle surface with 3, the interaction of 4-enedioxy thiophene monomer, thereby improve composite structure and efficient (reference 2:Adv. Mater., 2004,16,231-234).Above-mentioned preparation method's something in common is, one, and 3,4-enedioxy thiophene is polymerization in the medium outside polystyrene particle; Its two, the inducibility that improves the polystyrene particle surface is very important to strengthening sedimentation, improve composite structure and improving composite efficiency.
(3) summary of the invention:
The objective of the invention is to propose the polystyrene that a kind of preparation has nucleocapsid structure/poly-3, the novel method of 4-enedioxy thiophene conductive, high molecular compound particles.
The present invention has adopted equally by polystyrene particle emulsion and conductive polymers monomer 3, the water medium system that 4-enedioxy thiophene is formed, by 3, the preparation of the chemical oxidising polymerisation of 4-enedioxy thiophene gathers 3, the polystyrene nucleocapsid composite particles that 4-enedioxy thiophene coats.Method proposed by the invention is characterised in that, adopted following preparation process: at first with 3,4-enedioxy thiophene monomer swelling in advance is in the polystyrene particle emulsion of 4-6% at solid content, under temperature of reaction 50-80 ℃, add oxygenant chlorination iron, then with the dopant acid of 0.1-1.0M with the 0.25-2.5 mmole/minute speed be added drop-wise in the system, the reaction back obtains to coat uniform polystyrene/poly-3,4-enedioxy thiophene composite particles, gather 3,4-enedioxy thiophene shell thickness is 50-100nm.
Characteristics of the present invention are that process is simple, product structure and excellent property and controlled, are specially: 1. the seed particles that is adopted need not to pass through finishing, functionalization or other special design; 2. the acid of using in the polymerization process is not only and is gathered 3, and the doping agent of 4-enedioxy thiophene also has been endowed the function that the control monomer spreads; 3. can pass through multiple means controlled polymerization process easily, and then control the structure of composite particles effectively, final acquisition shell is evenly complete, the hud typed polystyrene of controllable thickness (controlled range is 50-100nm)/gather 3,4-enedioxy thiophene composite particles.
Polystyrene proposed by the invention/gather 3, the synthetic method and the concrete steps thereof of 4-enedioxy thiophene core-shell particles are as follows:
1. with 3,4-enedioxy thiophene joins in the water medium system of polystyrene particle emulsion of solid content 4-6%, ultrasonic agitation a few hours.In the system 3, the mass ratio of the particle in 4-enedioxy thiophene and the polystyrene particle emulsion is 1: 3-1: 12.
2. composite particles is synthetic: add oxygenant with after the mixed solution stirred for several that makes in the step 1 hour.In mixed solution with the 0.25-2.5 mmole/minute speed drip the dopant acid solution of 0.1-1.0M.After dropwising, at 50-80 ℃ of following isothermal reaction 18-24 hour.Behind the stopped reaction, use repeatedly centrifuge washing of methyl alcohol, water respectively, till the solution on upper strata becomes colorless, again through separation, the Powdered polystyrene of dry acquisition/gather 3,4-enedioxy thiophene composite particles.
In the system, oxygenant and 3, the mol ratio of 4-enedioxy thiophene is about 2.33: 1, dopant acid and 3, the mol ratio of 4-enedioxy thiophene is 2: 1-6: 1.
Among the present invention, used oxygenant is a kind of in iron(ic) chloride, ceric sulfate, ceric ammonium nitrate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate, the potassium bichromate.
Among the present invention, used dopant acid be tosic acid ,-a kind of in naphthene sulfonic acid, D-camphorsulfonic acid, poly-sulfonated phenylethylene, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, the methacrylic acid.
(4) embodiment:
Embodiment 1:
With 0.080g 3, it is in 5.74% the polystyrene particle emulsion that 4-enedioxy thiophene joins the 8.903g solid content, mechanical stirring is after a few hours under the ultrasonication, add iron(ic) chloride 0.357g, stir after 5 minutes, with 0.22 mmole/minute speed drip the tosic acid aqueous solution of 22.5ml, its concentration is 0.1M.Reacted 24 hours down at 65 ℃.Behind the stopped reaction, use repeatedly centrifuge washing of methyl alcohol, distilled water respectively, till upper solution becomes colorless, through centrifugal throw out is separated with supernatant liquid again, after vacuum-drying obtains powdered samples.The sample appearance of gained is black-and-blue, and transmission electron microscope is observed down, and particle is slick surface, has hud typed structure, gathers 3, and 4-enedioxy thiophene shell thickness is about 70nm.
Embodiment 2:
With 0.0902g 3, it is in 5.74% the polystyrene particle emulsion that 4-enedioxy thiophene joins the 10.041g solid content, mechanical stirring is after a few hours under the ultrasonication, add iron(ic) chloride 0.400g, stir after 5 minutes, with 0.25 mmole/minute speed drip the tosic acid aqueous solution of 25ml, its concentration is 0.1M.Reacted 24 hours down at 75 ℃.Behind the stopped reaction, use repeatedly centrifuge washing of methyl alcohol, distilled water respectively, till upper solution becomes colorless, through centrifugal throw out is separated with supernatant liquid again, after vacuum-drying obtains powdered samples.The sample appearance of gained is black-and-blue, and transmission electron microscope is observed down, and particle is uniform concavo-convex surface, has hud typed structure, gathers 3, and 4-enedioxy thiophene shell thickness is about 80nm.
Embodiment 3:
With 0.150g 3, it is in 5.74% the polystyrene particle emulsion that 4-enedioxy thiophene adds the 10.450g solid content, mechanical stirring is after a few hours under the ultrasonication, add and contain iron(ic) chloride 0.667g, stir after 5 minutes, with 0.42 mmole/minute speed drip the tosic acid aqueous solution of 42ml, its concentration is 0.1M.Reacted 24 hours down at 75 ℃.Behind the stopped reaction, use repeatedly centrifuge washing of methyl alcohol, distilled water respectively, till upper solution becomes colorless, through centrifugal throw out is separated with supernatant liquid again, after vacuum-drying obtains powdered samples.The sample appearance of gained is black-and-blue, and transmission electron microscope is observed down, and particle surface has uniform fine, soft fur thorn-like projection, has hud typed structure, gathers 3, and 4-enedioxy thiophene shell thickness is about 100nm.
Embodiment 4:
With 0.1018g 3, it is 5.74% polystyrene particle emulsion that 4-enedioxy thiophene joins the 10.662g solid content, mechanical stirring is after a few hours under the ultrasonication, add iron(ic) chloride 0.453g, stir after 5 minutes, with 0.3 mmole/minute speed drip the tosic acid aqueous solution of 6ml, its concentration is 0.5M.Reacted 24 hours down at 75 ℃.Behind the stopped reaction, use repeatedly centrifuge washing of methyl alcohol, distilled water respectively, till upper solution becomes colorless, through centrifugal throw out is separated with supernatant liquid again, after vacuum-drying obtains powdered samples.The sample appearance of gained is black-and-blue, and transmission electron microscope is observed down, and the slightly irregular projection of particle surface has hud typed structure, gathers 3, and 4-enedioxy thiophene shell thickness is about 50nm.
Claims (3)
1. polystyrene/poly-3, the preparation method of 4-enedioxy thiophene conductive, high molecular compound particles, adopt polystyrene particle emulsion and conductive polymers monomer 3, the water medium system that 4-enedioxy thiophene is formed, it is characterized in that 3,4-enedioxy thiophene mixes with polystyrene emulsion earlier, stirred for several hour treats 3, after 4-enedioxy thiophene swells in polystyrene particle, add oxygenant down at 50～80 ℃, under stirring state with 0.25～2.5 mmole/minute speed drip the dopant acid of 0.1～1.0M, stirring reaction was used methyl alcohol respectively after 18～24 hours, water is centrifuge washing repeatedly, till the solution on upper strata becomes colorless, separate again, drying obtains Powdered polystyrene/poly-3,4-enedioxy thiophene composite particles, gather 3,4-enedioxy thiophene shell thickness is 50～100nm; The solid content of polystyrene particle emulsion is 4～6%, and in the system 3, the mass ratio of 4-enedioxy thiophene and polystyrene particle is 1: 3～1: 12, oxygenant and 3, the mol ratio of 4-enedioxy thiophene is 2.33: 1, dopant acid and 3, and the mol ratio of 4-enedioxy thiophene is 2: 1～6: 1.
2. according to the described polystyrene of claim 1/poly-3, the preparation method of 4-enedioxy thiophene conductive, high molecular compound particles is characterized in that oxygenant is a kind of in iron(ic) chloride, ceric sulfate, ceric ammonium nitrate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide, Potassium Iodate, iron trichloride, Potcrate, the potassium bichromate.
3. according to the described polystyrene of claim 1/poly-3, the preparation method of 4-enedioxy thiophene conductive, high molecular compound particles is characterized in that dopant acid is a kind of in tosic acid, beta-naphthalenesulfonic-acid, D-camphorsulfonic acid, poly-sulfonated phenylethylene, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, vinylformic acid, the methacrylic acid.
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| CN105336867B (en) * | 2015-09-30 | 2017-12-01 | 华南理工大学 | A kind of naphthalene sulfonic acid-formaldehyde condensation product disperses poly- 3,4 ethylenedioxy thiophene electrically conductive composite and preparation and application |
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