CN107955137A - It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof - Google Patents
It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof Download PDFInfo
- Publication number
- CN107955137A CN107955137A CN201711161474.4A CN201711161474A CN107955137A CN 107955137 A CN107955137 A CN 107955137A CN 201711161474 A CN201711161474 A CN 201711161474A CN 107955137 A CN107955137 A CN 107955137A
- Authority
- CN
- China
- Prior art keywords
- emulsifying agent
- pss
- aqueous dispersion
- macromole emulsifying
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 C*CSC([C@](*1)C2OCCOC2=C1C(SC**)=C1OCCO[*@]1Cc1ccc(C(CC(C2*C2)C(*)(*)Cl)CC(CC2C(C)(C)SC(S*)=S)c3ccc(*)cc3)cc1)=C1OCCO[C@@]1I(CI(C)C)[*-]c1ccc2cc1 Chemical compound C*CSC([C@](*1)C2OCCOC2=C1C(SC**)=C1OCCO[*@]1Cc1ccc(C(CC(C2*C2)C(*)(*)Cl)CC(CC2C(C)(C)SC(S*)=S)c3ccc(*)cc3)cc1)=C1OCCO[C@@]1I(CI(C)C)[*-]c1ccc2cc1 0.000 description 2
Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- 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
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Colloid Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to it is a kind of using macromole emulsifying agent as template poly- 3,4 dioxyethylene thiophene aqueous dispersions and preparation method thereof.First using RAFT polymerization synthetic macromolecule emulsifying agent R PSS, then using macromole emulsifying agent R PSS as template, PEDOT is synthesized:PSS dispersions.The beneficial effects of the invention are as follows：On the one hand a kind of method of synthetic macromolecule emulsifying agent polyvinylbenzenesulfonic acid sodium is provided；On the other hand compared to traditional PEDOT:PSS aqueous dispersions, using different macromole emulsifying agent R PSS as template, the PEDOT of preparation:The electric conductivity and filming performance of PSS aqueous dispersions become more preferable.
Description
Technical field
The invention belongs to conducting polymer technical field, and in particular to a kind of macromole emulsifying agent is poly- 3, the 4- bis- of template
Ethylene oxide thiophene aqueous dispersion and preparation method thereof
Background technology
In recent years, since conducting polymer shows excellent electrochemistry, machining property and environmental stability, and cause
The extensive concern of researcher and research.Wherein, poly- 3.4- dioxyethylene thiophenes (PEDOT) are because conductive high, saturating
The features such as bright property is good, can be widely applied to the fields such as solar cell, electrochromism, anti-static coatings.But due to PEDOT
Insoluble insoluble shortcoming, again limits its application, therefore, it is particularly important that to the study on the modification of PEDOT.
In general, it is insoluble not molten scarce to improve PEDOT by adding a certain proportion of polyvinylbenzenesulfonic acid sodium (PSS)
Point.PSS and PEDOT can form a kind of PEDOT of stabilization:PSS suspension, on the one hand the effect of PSS is as corresponding anion
To keep the charge balance on PEDOT main chains, another aspect PSS preferably can be dispersed in water PEDOT as template.Cause
This, changes the structure or molecular weight of template PSS, it is more likely that can influence the dispersivenesses of PEDOT in water, may finally make
PEDOT:The electric conductivity of PSS films is affected.At present, there is substantial amounts of document report on changing template PSS structures, it is right
PEDOT:The influence of PSS film performances.For example, CN104151565A is disclosed by introducing new template PSS-APEG so that
PEDOT dispersion liquids are more stablized, and film forming is more preferable, final obtained PEDOT:PSS-APEG films are not influencing the feelings of transmitance
Under condition, electric conductivity significantly improves.But it is typically all to utilize commonly certainly to use polyvinylbenzenesulfonic acid sodium and its copolymer
Obtained by base polymerization, random coil form is presented in they in water, this can influence the film forming of PEDOT aqueous dispersions, lead
The performance such as electrical.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of side of synthetic macromolecule emulsifying agent R-PSS
Method, they exist with micelle state in water.This method is polymerize using RAFT, to synthesize different macromole emulsifying agent R-PSS.
Second technical problem to be solved by this invention is to provide one kind using macromole emulsifying agent R-PSS as template,
Synthesize PEDOT:The preparation method of PSS dispersions.
Poly- 3,4- dioxyethylene thiophenes of the present invention using macromole emulsifying agent polyvinylbenzenesulfonic acid sodium as template
Aqueous dispersion is just like lower structure：
Wherein：R1For C4~C18Aliphatic or aromatic series alkane；R2For H or CH3；X：Y=(1~20)：1.
PEDOT aqueous dispersion and its preparation of the macromole emulsifying agent polyvinylbenzenesulfonic acid sodium of the present invention for template
Method, follows these steps to carry out：
First, the synthesis of macromole emulsifying agent polyvinylbenzenesulfonic acid sodium
(1), vinylbenzenesulfonic acid sodium (SSNa) and deionization are first added in the four-hole boiling flask equipped with magneton and thermometer
Water, dissolved solution, adds the RAFT reagents containing aliphatic long-chain of dissolving in organic solvent, in N2Under protection, by temperature
Degree is heated to 55~85 DEG C, fully dissolving.
(2), initiator is added, certain mass sample is taken when often 1 is small excessively, with weight method, conversion ratio is measured, until conversion ratio
Reach more than 90% stopping reaction.
(3), after reaction by product ethanol precipitation, drying, obtains macromole emulsifying agent alkyl polyvinyl benzene sulphur
Sour sodium.Its structure is as follows：
Wherein：R1For C4~C18Aliphatic or aromatic series alkane；R2For H or CH3。
Further, the RAFT reagents described in step (1) are dithioesters class, in three thio esters, xanthic acid esters
One or more.
Further, the molar ratio of the RAFT reagents described in step (1) and vinylbenzenesulfonic acid sodium is 1：2~250.
Further, the organic solvent described in step (1) is：Ethanol, methanol, acetonitrile, dimethyl sulfoxide (DMSO), tetrahydrochysene furan
Mutter, the one or more in N,N-dimethylformamide, dioxane, isopropanol.
Further, initiator is described in step (2)：Azo-bis-isobutyrate hydrochloride (AIBA), two isobutyl miaow of azo
One or more in oxazoline hydrochloride (AIBI), ammonium persulfate, potassium peroxydisulfate.The molar ratio of SSNa and initiator is 1000:
(1~20).
2nd, different macromole emulsifying agent polyvinylbenzenesulfonic acid sodium are the PEDOT of template:The preparation of PSS aqueous dispersions
(1), macromole emulsifying agent alkyl made from addition step 1 gathers in the four-hole boiling flask equipped with magneton and thermometer
Vinylbenzenesulfonic acid sodium R-PSS, EDOT and deionized water, 30~50 DEG C are heated to by temperature, fully dissolving.
(2), after being completely dissolved, oxidant, catalyst and isopropanol (IPA) are added, reacts 8~24h, reaction process timing
Sampling, measures conversion ratio, obtains navy blue aqueous dispersion after reaction.Its structure is as follows：
Wherein：R1For C4~C18Aliphatic or aromatic series alkane；R2For H or CH3；X：Y=(1~20)：1.
Further：The mass ratio of R-PSS and EDOT described in step (1) are (0.5~10):1.
Further：Oxidant described in step (2) is ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or several
Kind.Catalyst is the one or more in ferric sulfate, ferric nitrate, iron chloride or p-methyl benzenesulfonic acid iron.
Further：The molar ratio of oxidant and EDOT described in step (2) is (0.5~4):1.Catalyst and EDOT's
Molar ratio is (0.001~0.005):1.The mass ratio of IPA and EDOT is 1:1, the solid content of aqueous dispersion is 1~10%.
The PEDOT finally obtained by the method for the invention:PSS forming thin films and electric conductivity are carried well
It is high.
The beneficial effects of the present invention are：
On the one hand a kind of method of synthetic macromolecule emulsifying agent alkyl polyvinylbenzenesulfonic acid sodium is provided；Another aspect phase
Than in traditional PEDOT:PSS aqueous dispersions, using macromole emulsifying agent R-PSS as template, the PEDOT of preparation:PSS moisture dissipates
The electric conductivity and filming performance of body become more preferable.
Embodiment
With reference to specific embodiment, the present invention is furture elucidated, but embodiment the present invention is not made it is any type of
Limit.
Embodiment 1：
PSS molecular weight is the synthesis of 2000 macromole emulsifying agent R-PSS and its preparation of PEDOT aqueous dispersions
First, molecular weight is that the structure of 2000 macromole emulsifying agent R-PSS is as follows：
2nd, it is that template prepares PEDOT aqueous dispersions by 2000 macromole emulsifying agent R-PSS of molecular weight
1st, molecular weight is the synthesis of 2000 macromole emulsifying agent R-PSS
(1), first added in the 250ml four-hole boiling flasks equipped with magneton and thermometer 10.31g SSNa and 36.33g go from
Sub- water, dissolved solution, adds RAFT reagents (2- [(dodecyl sulfanyl) Thioacyl]-sulfanyl propionic acid) solution
(1.8g RAFT reagents are dissolved in 12.11g absolute ethyl alcohols), in N2Under protection, temperature is heated to 55 DEG C, fully dissolving.
(2), 0.0271g azo-bis-isobutyrate hydrochlorides (AIBA) initiator is added, certain mass sample is taken when often 1 is small excessively
Product, with weight method, measure conversion ratio, until conversion ratio reaches more than 90% stopping reaction.
(3), product is come out with ethanol precipitation after reaction, puts oven for drying, obtain the R- that molecular weight is 2000
PSS.Its critical micelle concentration (cmc) is measured as 2.69 × 10-6g/ml。
2nd, it is that template prepares PEDOT by 2000 macromole emulsifying agent R-PSS of molecular weight:PSS aqueous dispersions
(1), in the four-hole boiling flask equipped with magneton and thermometer add 1g steps 1 made from R-PSS, 0.4g EDOT and
68.6g deionized waters, 30 DEG C are heated to by temperature, fully dissolving.
(2), after being completely dissolved, 0.32g oxidants ammonium persulfate, 0.001g catalyst sulfuric acids iron and 0.4g isopropanols are added
(IPA), 8h is reacted, reaction process timing sampling, measures conversion ratio, obtain navy blue aqueous dispersion after reaction.
Embodiment 2：
PSS molecular weight is the synthesis of 5000 macromole emulsifying agent R-PSS and its preparation of PEDOT aqueous dispersions
First, molecular weight is that the structure of 5000 macromole emulsifying agent R-PSS is as follows：
2nd, it is that template prepares PEDOT aqueous dispersions by 5000 R-PSS macromole emulsifying agents of molecular weight
1st, molecular weight is the synthesis of 5000 macromole emulsifying agent R-PSS
(1), first added in the 250ml four-hole boiling flasks equipped with magneton and thermometer 10.31g SSNa and 33.03g go from
Sub- water, dissolved solution, adds RAFT reagents (2- [(dodecyl sulfanyl) Thioacyl]-sulfanyl propionic acid) solution
(0.7g RAFT reagents are dissolved in 11.01gDMSO), in N2Under protection, temperature is heated to 65 DEG C, fully dissolving.
(2), two isobutyl imidazoline hydrochloride (AIBI) initiator of 0.028g azos is added, certain mass is taken when often 1 is small excessively
Sample, with weight method, measures conversion ratio, until conversion ratio reaches more than 90% stopping reaction.
(3), product is come out with ethanol precipitation after reaction, puts oven for drying, obtain the R- that molecular weight is 5000
PSS.Its critical micelle concentration (cmc) is measured as 3.14 × 10-6g/ml。
2nd, it is that template prepares PEDOT by 5000 macromole emulsifying agent R-PSS of molecular weight:PSS aqueous dispersions
(1), R-PSS, 0.4g EDOT made from 0.2g steps 1 are added in the four-hole boiling flask equipped with magneton and thermometer
With 14.4g deionized waters, temperature is heated to 35 DEG C, fully dissolving.
(2), after being completely dissolved, 0.76g oxidants potassium peroxydisulfate, 0.001g catalyst ferric nitrate and 0.4g isopropanols are added
(IPA), 12h is reacted, reaction process timing sampling, measures conversion ratio, obtain navy blue aqueous dispersion after reaction.
Embodiment 3：
PSS molecular weight is the synthesis of 10000 macromole emulsifying agent R-PSS and its preparation of PEDOT aqueous dispersions
First, molecular weight is that the structure of 10000 macromole emulsifying agent R-PSS is as follows：
2nd, it is that template prepares PEDOT aqueous dispersions by 10000 macromole emulsifying agent R-PSS of molecular weight
1st, molecular weight is the synthesis of 10000 macromole emulsifying agent R-PSS
(1), first added in the 250ml four-hole boiling flasks equipped with magneton and thermometer 10.31g SSNa and 30.02g go from
Sub- water, dissolved solution, addition RAFT reagent S-1- dodecyls-S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate
Solution (0.364g RAFT reagents are dissolved in 10.67gDMF), in N2Under protection, temperature is heated to 75 DEG C, fully dissolving.
(2), 0.068g ammonium persulfate initiators are added, certain mass sample is taken when often 1 is small excessively, with weight method, measure turns
Rate, until conversion ratio reaches more than 90% stopping reaction.
(3), product is come out with ethanol precipitation after reaction, puts oven for drying, obtain the R- that molecular weight is 10000
PSS.Its critical micelle concentration (cmc) is measured as 9.38 × 10-6g/ml。
2nd, it is that template prepares PEDOT by 10000 macromole emulsifying agent R-PSS of molecular weight:PSS aqueous dispersions
(1), R-PSS, 0.4g EDOT made from 0.4g steps 1 are added in the four-hole boiling flask equipped with magneton and thermometer
With 12.5g deionized waters, temperature is heated to 40 DEG C, fully dissolving.
(2), after being completely dissolved, 1.34g oxidants sodium peroxydisulfate, 0.001g catalyst iron chloride and 0.4g isopropanols are added
(IPA), 16h is reacted, reaction process timing sampling, measures conversion ratio, obtain navy blue aqueous dispersion after reaction.
Embodiment 4：
PSS molecular weight is the synthesis of 20000 macromole emulsifying agent R-PSS and its preparation of PEDOT aqueous dispersions
First, molecular weight is that the structure of 20000 macromole emulsifying agent R-PSS is as follows：
2nd, it is that template prepares PEDOT aqueous dispersions by 20000 macromole emulsifying agent R-PSS of molecular weight
1st, molecular weight is the synthesis of 20000 macromole emulsifying agent R-PSS
(1), first added in the 250ml four-hole boiling flasks equipped with magneton and thermometer 10.31g SSNa and 31.48g go from
Sub- water, dissolved solution, addition RAFT reagent S-1- dodecyls-S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate
Solution (0.182g RAFT reagents are dissolved in 10.49g dioxane), in N2Under protection, temperature is heated to 85 DEG C, fully
Dissolving.
(2), 0.108g potassium peroxydisulfate initiators are added, certain mass sample is taken when often 1 is small excessively, with weight method, measure turns
Rate, until conversion ratio reaches more than 90% stopping reaction.
(3), product is come out with ethanol precipitation after reaction, puts oven for drying, obtain the R- that molecular weight is 20000
PSS.Its critical micelle concentration (cmc) is measured as 2.38 × 10-5g/ml。
2nd, it is that template prepares PEDOT by 20000 macromole emulsifying agent R-PSS of molecular weight:PSS aqueous dispersions
(1), R-PSS, 0.4g EDOT made from 1.6g steps 1 are added in the four-hole boiling flask equipped with magneton and thermometer
With 23g deionized waters, temperature is heated to 45 DEG C, fully dissolving.
(2), after being completely dissolved, add 2.56g oxidants ammonium persulfates, 0.0076g catalyst p-methyl benzenesulfonic acid iron and
0.4g isopropanols (IPA), react 20h, reaction process timing sampling, measures conversion ratio, obtain navy blue moisture after reaction
Granular media.
Embodiment 5：
The preparation of the PSS and its PEDOT aqueous dispersions synthesized by general radical polymerization
First, the structure of the PSS synthesized by general radical polymerization is as follows：
Wherein：N is 250~1000.
2nd, PEDOT aqueous dispersions are prepared as template using the PSS of general radical polymerization synthesis
1st, PSS is synthesized by general radical polymerization
(1), first added in the 250ml four-hole boiling flasks equipped with magneton and thermometer 10.31g SSNa and 41.24g go from
Sub- water, dissolved solution, in N2Under protection, temperature is heated to 70 DEG C, fully dissolving.
(2), 0.054g azo-bis-isobutyrate hydrochlorides (AIBA) initiator is added, certain mass sample is taken when often 1 is small excessively,
With weight method, conversion ratio is measured, until conversion ratio reaches more than 90% stopping reaction.
(3), product is come out with ethanol precipitation after reaction, puts oven for drying, obtain PSS.
2nd, PEDOT is prepared as template using the PSS of general radical polymerization synthesis:PSS aqueous dispersions
(1), in the four-hole boiling flask equipped with magneton and thermometer add 1g steps 1 made from PSS, 0.4g EDOT and
68.6g deionized waters, 40 DEG C are heated to by temperature, fully dissolving.
(2), after being completely dissolved, it is different that 0.9632g oxidants ammonium persulfate, 0.0024g catalyst sulfuric acids iron and 0.4g are added
Propyl alcohol (IPA), reacts 12h, reaction process timing sampling, measures conversion ratio, obtain navy blue aqueous dispersion after reaction.
Measure the PEDOT of embodiment 1~5:The square resistance such as following table of PSS aqueous dispersion films：
It can be seen from the above that the PEDOT prepared using macromole emulsifying agent PSS as template:PSS aqueous dispersion electrical conductivity has obtained bright
Aobvious raising.
Claims (9)
1. a kind of poly- 3,4- dioxyethylene thiophenes aqueous dispersion using macromole emulsifying agent as template, its structure are：
Wherein：R1For C4~C18Aliphatic or aromatic series alkane；R2For H or CH3；X：Y=(1~20)：1.
A kind of 2. poly- 3,4- dioxyethylene thiophenes aqueous dispersion preparation method using macromole emulsifying agent as template, it is characterized in that bag
Include following steps：
(1) vinylbenzenesulfonic acid sodium (SSNa) and deionized water are first added in the four-hole boiling flask equipped with magneton and thermometer, often
The lower dissolving of temperature, adds the RAFT reagents containing aliphatic or aromatic series long-chain of dissolving in organic solvent, in N2, will under protection
Temperature is heated to 55~85 DEG C, fully dissolving；
(2) initiator is added, certain mass sample is taken when often 1 is small excessively, with weight method, conversion ratio is measured, until conversion ratio reaches
More than 90% stops reaction；
(3) after reaction by product ethanol precipitation, drying, obtains macromole emulsifying agent alkyl polyvinylbenzenesulfonic acid sodium.
(4) macromole emulsifying agent alkyl polyvinylbenzenesulfonic acid made from being added in the four-hole boiling flask equipped with magneton and thermometer
Sodium R-PSS, EDOT and deionized water, 30~50 DEG C are heated to by temperature, fully dissolving；
(5) after being completely dissolved, addition oxidant, catalyst and isopropanol (IPA), 8~24h of reaction, reaction process timing sampling,
Conversion ratio is measured, obtains navy blue aqueous dispersion after reaction.
3. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：In the step (1) RAFT reagents be aliphatic or aromatic series dithioesters class, three thio esters,
One or more in xanthic acid esters.
4. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：The molar ratio of RAFT reagents and vinylbenzenesulfonic acid sodium described in the step (1) is 1：2~
250。
5. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：Organic solvent is in the step (1)：Ethanol, methanol, acetonitrile, dimethyl sulfoxide (DMSO), tetrahydrofuran,
One or more in N,N-dimethylformamide, dioxane, isopropanol.
6. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：Initiator is in the step (2)：Azo-bis-isobutyrate hydrochloride (AIBA), two isobutyl miaow of azo
One or more in oxazoline hydrochloride (AIBI), ammonium persulfate, potassium peroxydisulfate.The molar ratio of SSNa and initiator is 1000:
(1~20).
7. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：The mass ratio of R-PSS and EDOT is (0.5~10) in the step (4):1.
8. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：Oxidant is ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or several in the step (5)
Kind.Catalyst is the one or more in ferric sulfate, ferric nitrate, iron chloride or p-methyl benzenesulfonic acid iron.
9. a kind of macromole emulsifying agent according to claim 2 is poly- 3, the 4- dioxyethylene thiophenes aqueous dispersion system of template
Preparation Method, it is characterized in that：The molar ratio of oxidant and EDOT are (0.5~4) in the step (5):1.Catalyst and EDOT
Molar ratio be (0.001~0.005):1.The mass ratio of IPA and EDOT is 1:1, the solid content of aqueous dispersion is 1~10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711161474.4A CN107955137A (en) | 2017-11-21 | 2017-11-21 | It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711161474.4A CN107955137A (en) | 2017-11-21 | 2017-11-21 | It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107955137A true CN107955137A (en) | 2018-04-24 |
Family
ID=61964973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711161474.4A Pending CN107955137A (en) | 2017-11-21 | 2017-11-21 | It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107955137A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013082196A1 (en) * | 2011-11-28 | 2013-06-06 | The Regents Of The University Of California | bFGF-POLYMER CONJUGATES, METHODS FOR MAKING THE SAME AND APPLICATIONS THEREOF |
| CN104211969A (en) * | 2014-09-10 | 2014-12-17 | 万星光电子(东莞)有限公司 | Preparation method of PEDOT/PSS dispersion liquid and preparation method of high pressure solid capacitor |
| CN105899547A (en) * | 2013-10-31 | 2016-08-24 | 阿科玛法国公司 | Stable compositions comprising poly (3,4-ethylenedioxythiophene) and anionic stabilisers with limited acidity |
-
2017
- 2017-11-21 CN CN201711161474.4A patent/CN107955137A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013082196A1 (en) * | 2011-11-28 | 2013-06-06 | The Regents Of The University Of California | bFGF-POLYMER CONJUGATES, METHODS FOR MAKING THE SAME AND APPLICATIONS THEREOF |
| CN105899547A (en) * | 2013-10-31 | 2016-08-24 | 阿科玛法国公司 | Stable compositions comprising poly (3,4-ethylenedioxythiophene) and anionic stabilisers with limited acidity |
| CN104211969A (en) * | 2014-09-10 | 2014-12-17 | 万星光电子(东莞)有限公司 | Preparation method of PEDOT/PSS dispersion liquid and preparation method of high pressure solid capacitor |
Non-Patent Citations (1)
| Title |
|---|
| 唐宝坤等: "以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能", 《道客巴巴》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5869880B2 (en) | Composite conductive polymer solution and method for producing the same | |
| JP5738178B2 (en) | Composite conductive polymer composition, production method thereof, solution containing the composition, and use of the composition | |
| TWI573781B (en) | High purity p-styrene sulfonic acid (salt), polystyrene sulfonic acid (salt) used, and polystyrene sulfonic acid (salt): dispersant, conductive polymer dopant, nanocarbon Aqueous dispersion, conductive polymer aqueous dispersion; and polystyrene sulfonic acid (salt) | |
| EP2627712B1 (en) | Dispersions comprising polythiophenes with a defined content of thiophene monomer | |
| US8920681B2 (en) | Electrically conductive polymers with enhanced conductivity | |
| JP5869881B2 (en) | Composite conductive polymer solution and method for producing the same | |
| JP5435436B2 (en) | Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition | |
| TWI470001B (en) | Conductive polymercomposition and process for producing the same | |
| Shao et al. | Structural investigation of lignosulfonate doped polyaniline | |
| JP2017141409A (en) | Conductive polymer aqueous solution, and conductive polymer film | |
| CN105399873B (en) | Water-soluble azo initiator and acrylamide polymer and its preparation method and application | |
| Orekhov et al. | Molecular brushes based on copolymers of alkoxy oligo (ethylene glycol) methacrylates and dodecyl (meth) acrylate: features of synthesis by conventional free radical polymerization | |
| US8691117B2 (en) | Organic solvent dispersible conductive polymer and method for manufacture thereof | |
| JP3977289B2 (en) | Conductive composition | |
| Tang et al. | Synthesis of poly (sodium styrene sulfonate)-b-poly (butyl acrylate) block copolymers via RAFT emulsifier-free emulsion polymerization and their application in PEDOT aqueous dispersions | |
| Conejo-Dávila et al. | Selective polymerization of a new bifunctional monomer via free radical polymerization and oxidative route | |
| CN108530621B (en) | Soluble conductive polymer and preparation method thereof | |
| JP2020183493A (en) | Complex composed of polythiophene-polystyrene sulfonate copolymer, and water dispersion containing the same | |
| CN107955137A (en) | It is a kind of using macromole emulsifying agent as PEDOT aqueous dispersions of template and preparation method thereof | |
| González-Iñiguez et al. | Synthesis of polypyrrole nanoparticles by batch and semicontinuous heterophase polymerizations | |
| CN105273168B (en) | A kind of preparation method of polymeric dispersions and obtained polymeric dispersions and application thereof | |
| CN108164687B (en) | PEDOT solvent type dispersion with amphiphilic block copolymer PSS-b-PBA as template and preparation method thereof | |
| CN108148185B (en) | PEDOT aqueous dispersion with amphiphilic block copolymer PSS-b-PBA as template and preparation method thereof | |
| Hong et al. | A reactive nitrile-rich phosphonium polyelectrolyte derived from toxic PH3 tail gas: Synthesis, post-polymerization modifications, and unexpected LCST behaviour in DMF solution | |
| CN104341703B (en) | Macromolecular material and its preparation method and contact panel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180424 |
|
| WD01 | Invention patent application deemed withdrawn after publication |