CN107722568A - The preparation method of poly- (3,4 the ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid of high conductivity - Google Patents
The preparation method of poly- (3,4 the ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid of high conductivity Download PDFInfo
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Abstract
The invention provides a kind of preparation method of poly- (3,4 the ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid of high conductivity, including：Weigh lignin sulfonic acid, 3,4 ethylenedioxy thiophenes, disodium ethylene diamine tetraacetate and triethanolamine carry out primary first-order equation, secondary response and third-order reaction, then purified with zwitterion resin, ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO) are added again, mix, then carry out homogenization, be cooled to room temperature；Wherein, lignin sulfonic acid is to be made by Wheat Straw Lignin from Alkali Pulping through techniques such as overactivation, grafting condensation, sulfonation and Ultrafiltration Purifyings.Wheat Straw Lignin from Alkali Pulping is modified the lignin sulfonic acid prepared with HMW and high sulfonic group content by the present invention, and then it is prepared for a kind of electrical conductivity is high, dispersion stabilization is good, machinability is strong poly- (3,4 ethylenedioxy thiophenes) dispersion liquid, reduce production cost simultaneously, economize on resources, alleviate pollution of the papermaking wastewater to environment, there is economic and environment-friendly double benefit.
Description
Technical field
The present invention relates to the preparation method of a kind of poly- (3,4- ethylenedioxy thiophenes).It is more particularly related to one
The preparation method of kind poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity, belongs to conducting polymer technology
Field.
Background technology
It is polyaniline compound derivative, polythiophene-based derivatives and multi-metal polypyrrole to study most commonly used conducting polymer at present
Derivative.Wherein, polythiophene and its derivative are the compounds that energy barrier is minimum in conducting polymer.Poly- (3,4- enedioxy thiophenes
Fen) abbreviation PEDOT, it is a kind of new conducting polymer, is the scientists by Bayer A.G earliest in 20th century 80
What the age developed, it is obtained after being polymerize by monomer 3,4-ethylene dioxythiophene (abbreviation EDOT).Gather in numerous conductions
In compound, PEDOT is due to electrical conductivity is high, visible light transmissivity is high, mechanical flexibility is good, oxidation state stability is strong, film
Prepare the advantage such as simple, green non-poisonous and receive significant attention, but conjugation backbone special eigenstate PEDOT causes it
It is insoluble not melt, thus it can not effectively be processed, limit its application.Solves the most directly effective side of this problem
Method is exactly to prepare PEDOT dispersion liquids.
A kind of aqueous-dispersible conductive polymer being most widely used on the market at present is exactly that Bayer A.G has engaged in trade
Poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid (abbreviation PEDOT/PSS) dispersion liquid of industry, is prepared by the dispersion liquid
PEDOT/PSS films have the advantages that electrical conductivity is high, stability is good, visible light permeability is strong, be widely used in antistatic additive,
The fields such as ultracapacitor, Organic Light Emitting Diode, organic solar batteries.But for preparing PEDOT/PSS dispersion liquids
PSS derives from Petroleum Industry, and price is higher, causes it to prepare cost also very high.Lignin sulfonic acid (abbreviation LS) is a kind of
Natural reproducible resource, presently mainly from the lignosulfonates in acid polishing waste liquid through cation resin exchange or
Alkali lignin modified in soda pulping process papermaking wastewater obtains, cheap, scattered and adulterate prepared by PEDOT using LS
PEDOT/LS dispersion liquids will be than PEDOT/PSS dispersion liquid advantageously in price.Although patent CN102516784A is utilized
Lignin sulfonic acid is prepared for the PEDOT/LS electrically conductive composites of water dispersible, and solving PEDOT indissoluble infusibilities causes processing difficulties
The problem of；But the electrical conductivity of this PEDOT/LS dispersion liquids is very low, only 10-4S/cm or so, the anti-quiet of low side can only be used as
Electric agent uses, and seriously hinders its application.Therefore, how research effectively improves the electrical conductivity of PEDOT/LS dispersion liquids,
The PEDOT/LS compounds of high conductivity are prepared, are not only played the role of to the application for expanding PEDOT/LS dispersion liquids important；
But also the efficient utilization of lignin can be promoted, both having saved resource reduces preparation cost, alleviates papermaking wastewater again
Discharge the problem of environmental pollution brought.
The content of the invention
It is an object of the present invention to provide a kind of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid of high conductivity to disperse
The preparation method of liquid, Wheat Straw Lignin from Alkali Pulping is carried out graft sulfonation modification and is prepared for HMW and high sulfonic group content by it
Lignin sulfonic acid, then using this lignin sulfonic acid as dispersant and dopant, prepare that a kind of electrical conductivity is high, dispersion stabilization
The dispersion liquid of poly- (3,4-ethylene dioxythiophene) good, machinability is strong, while production cost is reduced, economize on resources, alleviation is made
Pollution of the paper waste liquid to environment, there is economic and environment-friendly double effect.
In order to realize according to object of the present invention and further advantage, there is provided a kind of poly- (3,4- ethylenes of high conductivity
Dioxy thiophene)/lignin sulfonic acid dispersion liquid preparation method, comprise the following steps：
Step 1：It is 2.8 according to mass ratio:1:1:1 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, second
Edetate disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 20 DEG C of water baths
In, 30min is stirred under 6000rpm rotating speeds, oxidant is then added dropwise while stirring, continues stirring reaction 24h, is made once anti-
Answer liquid；
Step 2：It is 1.5 according to mass ratio:1:1:1 ratio weighs above-mentioned primary first-order equation liquid, 3,4- enedioxy thiophenes
Fen, disodium ethylene diamine tetraacetate and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 5 DEG C of water-bath rings
In border, 30min is stirred under 7000rpm rotating speeds, oxidant is then added dropwise while stirring, the stirring reaction under 6000rpm rotating speeds
30h, secondary response liquid is made；
Step 3：It is 0.5 according to mass ratio:1:1:1 ratio weighs above-mentioned secondary response liquid, 3,4- enedioxy thiophenes
Fen, disodium ethylene diamine tetraacetate and triethanolamine add high purity water, are made into the mixed liquor that solid content is 1.5%, repeat step two
In course of reaction, third-order reaction liquid is made；
Step 4：Sodium sulfite stirring reaction 3h is added into above-mentioned third-order reaction liquid, adds resin anion (R.A.) and sun
Ion exchange resin, continue to stir 24h, with the filter cloth suction filtering of 100 mesh, it is 2 that mass ratio is added into filtrate:1:1 ethylene glycol, sulfuric acid
Dimethyl ester and dimethyl sulfoxide (DMSO), mix, be heated to 55~65 DEG C, while the ultraviolet light irradiation 30min for being 365nm with wavelength, then
Homogenization is carried out, homogenization pressure is 20~30MPa, and homogenization cycles are 1~2 time, is cooled to the i.e. obtained high conductivity of room temperature and gathers
(3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid；Total addition of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO)
Measure as 5~10wt%；
The preparation method of the lignin sulfonic acid comprises the following steps：
Step a：Wheat Straw Lignin from Alkali Pulping is dissolved in the solution that water is made into 15wt%, the pH for adjusting solution is 10, is completely dissolved
After filter, take filtrate, the pH for then adjusting filtrate while stirring is 3, then centrifuges, takes filter residue；
Step b：Above-mentioned filter residue is dissolved in the sodium hydroxide solution that pH is 10, it is 4 to add mass ratio:1:1 persulfuric acid
Sodium, n-octyl alcohol and glycerine, the microwave irradiation for being 400W with power, 30min is reacted at 80 DEG C, the alkali that activation is made is wooden
Element；The total addition level of the sodium peroxydisulfate, n-octyl alcohol and glycerine is 5~8wt%；
Step c：It is 6 that mass ratio is added into the alkali lignin of above-mentioned activation:5:1 formaldehyde, dihydroxyacetone (DHA) and propylene
Acid, 1h, then the ultraviolet light irradiation 20min for being 365nm with wavelength are reacted at 80 DEG C；The formaldehyde, dihydroxyacetone (DHA) and propylene
The total addition level of acid is 20~40wt%；
Step d：It is 3 that mass ratio is added into the reaction solution after step c processing:1 hydrogenperoxide steam generator and chlorosulfuric acid,
After reacting 1h at 85 DEG C, the pH for adjusting reaction solution is 10, adds mass ratio as 5:2:1 sodium sulfite, formaldehyde and pi-allyl
Sodium sulfonate, continue to react 2h, then be freeze-dried and sodium lignin sulfonate powder is made；The hydrogenperoxide steam generator and chlorosulfuric acid
Total addition level is 5~8wt%, and the total addition level of the sodium sulfite, formaldehyde and ALS is 20~40wt%；
Step e：By above-mentioned sodium lignin sulfonate powder be dissolved in water be made into 15wt% solution carry out ultrafiltration, molecular cut off
Component more than 5000, it is 20~30% by component ultrafiltrate concentrated by rotary evaporation of the molecular weight more than 5000 to solid content, adds
Resin cation, stir 24h, with the filter cloth suction filtering of 800 mesh, collect filtrate, by filtrate concentrated by rotary evaporation into solid content be 70~
80% concentrate, then lignin sulfonic acid is made in concentrate freeze-drying.The alkali lignin that is activated in step c and formaldehyde,
Dihydroxyacetone (DHA) and acrylic acid can carry out grafting condensation reaction, so as to improve the molecular weight of alkali lignin, reaction solution in step d
Sulfonating reaction can occur in the presence of hydrogenperoxide steam generator and chlorosulfuric acid, so as to introduce sulfonic group on alkali lignin, then
In the presence of sodium sulfite, formaldehyde and ALS, further sulfonation and grafting are condensed, and improve the molecule of alkali lignin
Amount and sulfonic group content, so as to prepare the sodium lignin sulfonate with HMW and high sulfonic group content.
Preferably, wherein, the oxidant is one kind in sodium peroxydisulfate, ammonium persulfate and potassium peroxydisulfate, with 3,4-
The mol ratio of ethylenedioxy thiophene is 1.3:1, oxidant when in use, is first dissolved in high purity water and is made into material by the oxidant
The aqueous solution that concentration is 0.5mol/L is measured, is then dripped in 30min.
Preferably, wherein, in step 4, in addition to mannitol, sorbierite and N, N- dimethyl are added into filtrate
One kind in formamide, addition 8wt%.
Preferably, wherein, the resin anion (R.A.) is polystyrene macroporous strong basic anion exchange resin, is used
Before, 24h is first soaked in 3.0mol/L sodium hydroxide solution, it is 7 to be cleaned again with high purity water to pH after filtering.
Preferably, wherein, the resin cation is polystyrene macropore strong acid cation exchanger resin, is used
Before, 24h is first soaked in 3.0mol/L hydrochloric acid solution, it is 7 to be cleaned again with high purity water to pH after filtering.
Preferably, wherein, the retention model Da=5000 of milipore filter, is made up of polyether sulfone in the ultrafiltration.
The present invention comprises at least following beneficial effect：
(1) because the lignin sulfonic acid used in the present invention is to be made by Wheat Straw Lignin from Alkali Pulping by graft sulfonation is modified,
Grafting condensation reaction can improve the molecular weight of alkali lignin, and sulfonating reaction can improve the sulfonic group content of alkali lignin,
So as to the obtained lignin sulfonic acid with HMW and high sulfonic group content, this lignin sulfonic acid and directly from acid polishing
The lignin sulfonic acid that lignosulfonates in papermaking wastewater obtain after cation resin exchange is compared, and has higher disperse
With doping performance, therefore it can make the dispersion liquid of poly- (3,4-ethylene dioxythiophene) of preparation that there is more preferable electric conductivity and scattered
Stability.
(2) dispersion liquid of poly- (3,4-ethylene dioxythiophene) prepared using the present invention has electrical conductivity height, machinability
By force, the advantages that dispersion stabilization, heat endurance and humidity stability are good, and water-wash resistance is strong.
(3) because the raw material Wheat Straw Lignin from Alkali Pulping used in the present invention derives from papermaking wastewater, therefore raw material is easy to get, price is low
It is honest and clean, it is low with poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid dispersion phase ratio, production cost；Also improve papermaking simultaneously
The utilization rate of waste liquid, reduce pollution of the waste liquid to environment, there is economic and environment-friendly double effect.
(4) lignin sulfonic acid in the present invention is by obtaining after alkali lignin modified, is a kind of natural reproducible resource, and
Polystyrolsulfon acid in poly- (3,4- ethylenedioxy thiophenes)/polystyrolsulfon acid dispersion liquid is from increasingly exhausted oil money
Source, therefore, compared to poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid dispersion liquid, it is tight that the present invention can alleviate petroleum resources
Scarce pressure.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Embodiment
With reference to example, the present invention is described in further detail, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of individual other elements or its combination.
<Embodiment 1>
It is 2.8 according to mass ratio:1:1:1 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 20 DEG C of water baths,
30min is stirred under 6000rpm rotating speeds, sodium peroxydisulfate is then added dropwise while stirring, continues stirring reaction 24h, primary first-order equation is made
Liquid；It is 1.5 according to mass ratio:1:1:1 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 5 DEG C of water baths,
30min is stirred under 7000rpm rotating speeds, sodium peroxydisulfate is then added dropwise while stirring, the stirring reaction 30h under 6000rpm rotating speeds, system
Obtain secondary response liquid；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Disodium ethylene diamine tetraacetate and triethanolamine add high purity water, are made into the mixed liquor that solid content is 1.5%, are placed in 5 DEG C of water-bath rings
In border, 30min is stirred under 7000rpm rotating speeds, sodium peroxydisulfate is then added dropwise while stirring, stirred under 6000rpm rotating speeds anti-
30h is answered, third-order reaction liquid is made；Sodium sulfite stirring reaction 3h is added into above-mentioned third-order reaction liquid, adds anion tree
Fat and resin cation, continue to stir 24h, with the filter cloth suction filtering of 100 mesh, it is 2 that mass ratio is added into filtrate:1:1 second two
Alcohol, dimethyl suflfate and dimethyl sulfoxide (DMSO), while 8wt% mannitol is added, mix, be heated to 55 DEG C, while be with wavelength
365nm ultraviolet light irradiation 30min, then homogenization is carried out, homogenization pressure 25MPa, homogenization cycles are 2 times, are cooled to room
Poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity is made in temperature；The ethylene glycol, dimethyl suflfate and
The total addition level of dimethyl sulfoxide (DMSO) is 5wt%.
Wherein, the mol ratio of sodium peroxydisulfate and 3,4-ethylene dioxythiophene is 1.3:1, before use, first that sodium peroxydisulfate is molten
The aqueous solution that substance withdrawl syndrome is 0.5mol/L is made into high purity water, is then dripped in 30min.
The preparation method of the lignin sulfonic acid includes：Wheat Straw Lignin from Alkali Pulping is dissolved in the solution that water is made into 15wt%, adjusted
The pH for saving solution is 10, is filtered after being completely dissolved, takes filtrate, and the pH for then adjusting filtrate while stirring is 3, then is centrifuged,
Take filter residue；Above-mentioned filter residue is dissolved in the sodium hydroxide solution that pH is 10, it is 4 to add mass ratio:1:It is 1 sodium peroxydisulfate, just pungent
Alcohol and glycerine, the microwave irradiation for being 400W with power, 30min is reacted at 80 DEG C, the alkali lignin of activation is made；The mistake
The total addition level of sodium sulphate, n-octyl alcohol and glycerine is 6wt%；It is 6 that mass ratio is added into the alkali lignin of above-mentioned activation:5:
1 formaldehyde, dihydroxyacetone (DHA) and acrylic acid, 1h, then the ultraviolet light irradiation 20min for being 365nm with wavelength are reacted at 80 DEG C；Institute
The total addition level for stating formaldehyde, dihydroxyacetone (DHA) and acrylic acid is 20wt%；Mass ratio is added as 3:1 hydrogenperoxide steam generator and
Chlorosulfuric acid, after reacting 1h at 85 DEG C, the pH for adjusting reaction solution is 10, adds mass ratio as 5:2:1 sodium sulfite, formaldehyde
And ALS, continue to react 2h, then be freeze-dried and sodium lignin sulfonate powder is made；The hydrogenperoxide steam generator and
The total addition level of chlorosulfuric acid is 6wt%, and the total addition level of the sodium sulfite, formaldehyde and ALS is 30wt%；Will
Above-mentioned sodium lignin sulfonate powder is dissolved in the solution progress ultrafiltration that water is made into 15wt%, and molecular cut off is more than 5000 component,
It is 20% by component ultrafiltrate concentrated by rotary evaporation of the molecular weight more than 5000 to solid content, adds resin cation, stirs 24h,
With the filter cloth suction filtering of 800 mesh, filtrate is collected, by filtrate concentrated by rotary evaporation into the concentrate that solid content is 70%, then concentrate is cold
Lyophilized dry i.e. obtained lignin sulfonic acid.
Wherein, the resin anion (R.A.) is polystyrene macroporous strong basic anion exchange resin, before use, first existing
24h is soaked in 3.0mol/L sodium hydroxide solution, it is 7 to be cleaned again with high purity water to pH after filtering；The resin cation is
Polystyrene macropore strong acid cation exchanger resin, before use, first soaking 24h in 3.0mol/L hydrochloric acid solution, filter
It is 7 to be cleaned again with high purity water to pH afterwards；The retention model Da=5000 of milipore filter, is made up of polyether sulfone in the ultrafiltration.
<Embodiment 2>
It is 2.8 according to mass ratio:1:1:1 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 20 DEG C of water baths,
30min is stirred under 6000rpm rotating speeds, ammonium persulfate is then added dropwise while stirring, continues stirring reaction 24h, primary first-order equation is made
Liquid；It is 1.5 according to mass ratio:1:1:1 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 5 DEG C of water baths,
30min is stirred under 7000rpm rotating speeds, ammonium persulfate is then added dropwise while stirring, the stirring reaction 30h under 6000rpm rotating speeds, system
Obtain secondary response liquid；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Disodium ethylene diamine tetraacetate and triethanolamine add high purity water, are made into the mixed liquor that solid content is 1.5%, are placed in 5 DEG C of water-bath rings
In border, 30min is stirred under 7000rpm rotating speeds, ammonium persulfate is then added dropwise while stirring, stirred under 6000rpm rotating speeds anti-
30h is answered, third-order reaction liquid is made；Sodium sulfite stirring reaction 3h is added into above-mentioned third-order reaction liquid, adds anion tree
Fat and resin cation, continue to stir 24h, with the filter cloth suction filtering of 100 mesh, it is 2 that mass ratio is added into filtrate:1:1 second two
Alcohol, dimethyl suflfate and dimethyl sulfoxide (DMSO), while 8wt% sorbierite is added, mix, be heated to 60 DEG C, while be with wavelength
365nm ultraviolet light irradiation 30min, then homogenization is carried out, homogenization pressure 20MPa, homogenization cycles are 2 times, are cooled to room
Poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity is made in temperature；The ethylene glycol, dimethyl suflfate and
The total addition level of dimethyl sulfoxide (DMSO) is 10wt%.
Wherein, the mol ratio of ammonium persulfate and 3,4-ethylene dioxythiophene is 1.3:1, before use, first that ammonium persulfate is molten
The aqueous solution that substance withdrawl syndrome is 0.5mol/L is made into high purity water, is then dripped in 30min.
The preparation method of the lignin sulfonic acid includes：Wheat Straw Lignin from Alkali Pulping is dissolved in the solution that water is made into 15wt%, adjusted
The pH for saving solution is 10, is filtered after being completely dissolved, takes filtrate, and the pH for then adjusting filtrate while stirring is 3, then is centrifuged,
Take filter residue；Above-mentioned filter residue is dissolved in the sodium hydroxide solution that pH is 10, it is 4 to add mass ratio:1:It is 1 sodium peroxydisulfate, just pungent
Alcohol and glycerine, the microwave irradiation for being 400W with power, 30min is reacted at 80 DEG C, the alkali lignin of activation is made；The mistake
The total addition level of sodium sulphate, n-octyl alcohol and glycerine is 5wt%；It is 6 that mass ratio is added into the alkali lignin of above-mentioned activation:5:
1 formaldehyde, dihydroxyacetone (DHA) and acrylic acid, 1h, then the ultraviolet light irradiation 20min for being 365nm with wavelength are reacted at 80 DEG C；Institute
The total addition level for stating formaldehyde, dihydroxyacetone (DHA) and acrylic acid is 30wt%；Mass ratio is added as 3:1 hydrogenperoxide steam generator and
Chlorosulfuric acid, after reacting 1h at 85 DEG C, the pH for adjusting reaction solution is 10, adds mass ratio as 5:2:1 sodium sulfite, formaldehyde
And ALS, continue to react 2h, then be freeze-dried and sodium lignin sulfonate powder is made；The hydrogenperoxide steam generator and
The total addition level of chlorosulfuric acid is 5wt%, and the total addition level of the sodium sulfite, formaldehyde and ALS is 20wt%；Will
Above-mentioned sodium lignin sulfonate powder is dissolved in the solution progress ultrafiltration that water is made into 15wt%, and molecular cut off is more than 5000 component,
It is 25% by component ultrafiltrate concentrated by rotary evaporation of the molecular weight more than 5000 to solid content, adds resin cation, stirs 24h,
With the filter cloth suction filtering of 800 mesh, filtrate is collected, by filtrate concentrated by rotary evaporation into the concentrate that solid content is 75%, then concentrate is cold
Lyophilized dry i.e. obtained lignin sulfonic acid.
Wherein, the resin anion (R.A.) is polystyrene macroporous strong basic anion exchange resin, before use, first existing
24h is soaked in 3.0mol/L sodium hydroxide solution, it is 7 to be cleaned again with high purity water to pH after filtering；The resin cation is
Polystyrene macropore strong acid cation exchanger resin, before use, first soaking 24h in 3.0mol/L hydrochloric acid solution, filter
It is 7 to be cleaned again with high purity water to pH afterwards；The retention model Da=5000 of milipore filter, is made up of polyether sulfone in the ultrafiltration.
<Embodiment 3>
It is 2.8 according to mass ratio:1:1:1 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 20 DEG C of water baths,
30min is stirred under 6000rpm rotating speeds, potassium peroxydisulfate is then added dropwise while stirring, continues stirring reaction 24h, primary first-order equation is made
Liquid；It is 1.5 according to mass ratio:1:1:1 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, ethylenediamine tetrem
Acid disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 5 DEG C of water baths,
30min is stirred under 7000rpm rotating speeds, potassium peroxydisulfate is then added dropwise while stirring, the stirring reaction 30h under 6000rpm rotating speeds, system
Obtain secondary response liquid；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Disodium ethylene diamine tetraacetate and triethanolamine add high purity water, are made into the mixed liquor that solid content is 1.5%, are placed in 5 DEG C of water-bath rings
In border, 30min is stirred under 7000rpm rotating speeds, potassium peroxydisulfate is then added dropwise while stirring, stirred under 6000rpm rotating speeds anti-
30h is answered, third-order reaction liquid is made；Sodium sulfite stirring reaction 3h is added into above-mentioned third-order reaction liquid, adds anion tree
Fat and resin cation, continue to stir 24h, with the filter cloth suction filtering of 100 mesh, it is 2 that mass ratio is added into filtrate:1:1 second two
Alcohol, dimethyl suflfate and dimethyl sulfoxide (DMSO), while 8wt% DMF is added, mix, be heated to 65 DEG C, together
When be 365nm with wavelength ultraviolet light irradiation 30min, then carry out homogenization, homogenization pressure 30MPa, homogenization cycles 1
It is secondary, it is cooled to room temperature and poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity is made；The ethylene glycol,
The total addition level of dimethyl suflfate and dimethyl sulfoxide (DMSO) is 8wt%.
Wherein, the mol ratio of potassium peroxydisulfate and 3,4-ethylene dioxythiophene is 1.3:1, before use, first that potassium peroxydisulfate is molten
The aqueous solution that substance withdrawl syndrome is 0.5mol/L is made into high purity water, is then dripped in 30min.
The preparation method of the lignin sulfonic acid includes：Wheat Straw Lignin from Alkali Pulping is dissolved in the solution that water is made into 15wt%, adjusted
The pH for saving solution is 10, is filtered after being completely dissolved, takes filtrate, and the pH for then adjusting filtrate while stirring is 3, then is centrifuged,
Take filter residue；Above-mentioned filter residue is dissolved in the sodium hydroxide solution that pH is 10, it is 4 to add mass ratio:1:It is 1 sodium peroxydisulfate, just pungent
Alcohol and glycerine, the microwave irradiation for being 400W with power, 30min is reacted at 80 DEG C, the alkali lignin of activation is made；The mistake
The total addition level of sodium sulphate, n-octyl alcohol and glycerine is 8wt%；It is 6 that mass ratio is added into the alkali lignin of above-mentioned activation:5:
1 formaldehyde, dihydroxyacetone (DHA) and acrylic acid, 1h, then the ultraviolet light irradiation 20min for being 365nm with wavelength are reacted at 80 DEG C；Institute
The total addition level for stating formaldehyde, dihydroxyacetone (DHA) and acrylic acid is 40wt%；Mass ratio is added as 3:1 hydrogenperoxide steam generator and
Chlorosulfuric acid, after reacting 1h at 85 DEG C, the pH for adjusting reaction solution is 10, adds mass ratio as 5:2:1 sodium sulfite, formaldehyde
And ALS, continue to react 2h, then be freeze-dried and sodium lignin sulfonate powder is made；The hydrogenperoxide steam generator and
The total addition level of chlorosulfuric acid is 8wt%, and the total addition level of the sodium sulfite, formaldehyde and ALS is 40wt%；Will
Above-mentioned sodium lignin sulfonate powder is dissolved in the solution progress ultrafiltration that water is made into 15wt%, and molecular cut off is more than 5000 component,
It is 30% by component ultrafiltrate concentrated by rotary evaporation of the molecular weight more than 5000 to solid content, adds resin cation, stirs 24h,
With the filter cloth suction filtering of 800 mesh, filtrate is collected, by filtrate concentrated by rotary evaporation into the concentrate that solid content is 80%, then concentrate is cold
Lyophilized dry i.e. obtained lignin sulfonic acid.
Wherein, the resin anion (R.A.) is polystyrene macroporous strong basic anion exchange resin, before use, first existing
24h is soaked in 3.0mol/L sodium hydroxide solution, it is 7 to be cleaned again with high purity water to pH after filtering；The resin cation is
Polystyrene macropore strong acid cation exchanger resin, before use, first soaking 24h in 3.0mol/L hydrochloric acid solution, filter
It is 7 to be cleaned again with high purity water to pH afterwards；The retention model Da=5000 of milipore filter, is made up of polyether sulfone in the ultrafiltration.
In order to illustrate the effect of the present invention, it is as follows that inventor provides comparative experiments：
<Comparative example 1>
The preparation method of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity and lignin sulfonic acid is same
Embodiment 1, difference is：Sodium sulfite stirring reaction is added directly into primary first-order equation liquid, then carries out subsequent treatment,
No longer carry out secondary and third-order reaction.
<Comparative example 2>
The preparation method of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity and lignin sulfonic acid is same
Embodiment 2, difference is：Sodium sulfite stirring reaction is added directly into secondary response liquid, then carries out subsequent treatment,
No longer carry out third-order reaction.
<Comparative example 3>
The preparation method of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity and lignin sulfonic acid is same
Embodiment 3, difference is：It is 3 that mass ratio is added directly into the alkali lignin of activation:1 hydrogenperoxide steam generator and sulphur
Acyl chlorides, subsequent reactions and processing are carried out, react 1h at 80 DEG C without adding formaldehyde, dihydroxyacetone (DHA) and acrylic acid, without
Ultraviolet light irradiation.
<Comparative example 4>
The preparation method of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity and lignin sulfonic acid is same
Embodiment 3, difference is：Directly the reaction solution after ultraviolet light irradiation is freeze-dried sodium lignin sulfonate powder is made,
Then subsequent treatment is carried out, without adding hydrogenperoxide steam generator and chlorosulfuric acid and sodium sulfite, formaldehyde and ALS
Reacted.
The method that electrical conductivity is determined after film using directly dispersion liquid is made is produced to embodiment 1~3 and comparative example 1~4
The electrical conductivity of product is measured, and this method includes：The glass of clean dried is dropped in a certain amount of testing liquid of rubber head dropper absorption
On piece, spread out, then sheet glass is positioned over to 30min in 80 DEG C of constant temperature convection oven dry or be placed in 24h under room temperature condition
Natural air drying, film is made, determines the square resistance of film, is designated as R, and determine the thickness of corresponding test point, be designated as W, then by
Following equation calculates the electrical conductivity of film, replication 10 times, takes its average value.
σ=107/(RW)
σ-electrical conductivity, S/cm；R-square resistance, Ω/sq；W-sample thickness, nm.
Embodiment 1~3 and the electrical conductivity such as table 1 below of the product of comparative example 1~4 after measured：
[table 1]
From upper table 1, it can be seen that for the electrical conductivity of product in more than 9S/cm, this is due to carry out in embodiment 1~3
Polymerisation three times, on the one hand add conductive poly (3,4- in poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound
Ethylenedioxy thiophene) content, make the quantity of free carrier also accordingly increase；On the other hand (3,4- second poly- in compound is made
Support dioxy thiophene) chain is mutually wound a bigger network structure, and this network structure is advantageous to carrier poly- (3,4-
Ethylenedioxy thiophene) interchain transmission, realize more effective carrier transports；In addition, make in polymerization process
Dispersant and dopant lignin sulfonic acid are to be made by alkali lignin by grafting condensation reaction and sulfonating reaction are modified
, this lignin sulfonic acid from the lignosulfonates in acid polishing waste liquid after cation resin exchange with directly obtaining
To lignin sulfonic acid compare, there is higher molecular weight and sulfonic group content, thus with preferably scattered and doping performance,
So the electrical conductivity of product is higher, electric conductivity is preferable.
Comparative example 1 compared with Example 1, poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity and
The preparation method of lignin sulfonic acid is identical, and difference is：A polymerisation is only carried out, without secondary and anti-three times
Should.From upper table 1, it can be seen that the electrical conductivity of comparative example 1 is far below the electrical conductivity of embodiment 1, this is primarily due to only carry out one
During secondary polymerisation, conductive poly (3,4- ethylenes two in poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid compound of one side
Oxygen thiophene) content it is very low, greatly reduce the quantity of free carrier, and the outer surface of compound is not covered with leading largely
The lignin sulfonic acid of electricity；The network structure ratio that (3,4- ethylenedioxy thiophenes) chain poly- in another aspect compound is mutually wound
It is smaller, it is unfavorable for transmission of the carrier in poly- (3,4-ethylene dioxythiophene) interchain, so the product electrical conductivity of comparative example 1 is very
It is low.
Comparative example 2 compared with Example 2, poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity and
The preparation method of lignin sulfonic acid is identical, and difference is：Primary and secondary polymerisation is only carried out, without carrying out three
Secondary response.From upper table 1, it can be seen that the electrical conductivity of comparative example 2 is less than the electrical conductivity of embodiment 2, this is primarily due to only carry out
During primary and secondary polymerisation, conductive poly (3,4- ethylenes in poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound
Dioxy thiophene) content decrease, the quantity of free carrier is also decreased, while (3,4- ethylenes poly- in compound
Dioxy thiophene) the mutual winding degree of chain decreases, and effective transmission of carrier has also been reduced, so comparative example 2
Product electrical conductivity is less than the product electrical conductivity of embodiment 2, and this also illustrates, on the premise of dispersion stabilization is ensured, appropriate increase
Aggregation number, the electrical conductivity of poly- (3,4-ethylene dioxythiophene) dispersion liquid can be improved.
Comparative example 3 compared with Example 3, poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity and
The preparation method of lignin sulfonic acid is identical, and difference is：Directly hydrogenperoxide steam generator is added into the alkali lignin of activation
And chlorosulfuric acid, subsequent reactions and processing are carried out, is reacted without adding formaldehyde, dihydroxyacetone (DHA) and acrylic acid, also not had
Use ultraviolet light irradiation.From upper table 1, it can be seen that the electrical conductivity of comparative example 3 is less than the electrical conductivity of embodiment 3, this is primarily due to
During alkali lignin modified, do not add formaldehyde, dihydroxyacetone (DHA) and acrylic acid and carry out being grafted condensation reaction to improve alkali
The molecular weight of lignin, make the molecular weight of last obtained lignin sulfonic acid relatively low, so as to reduce its doping and dispersive property,
Make poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound that part dedoping occur, electrical conductivity is reduced, so comparative example
The electrical conductivity of 3 last obtained poly- (3,4- ethylenedioxy thiophenes) dispersion liquids is less than poly- (3,4- enedioxies prepared by embodiment 3
Thiophene) dispersion liquid electrical conductivity.
Comparative example 4 compared with Example 3, poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity and
The preparation method of lignin sulfonic acid is identical, and difference is：Directly the reaction solution after ultraviolet light irradiation is freeze-dried and is made
Sodium lignin sulfonate powder, then carry out subsequent treatment, without add hydrogenperoxide steam generator and chlorosulfuric acid and sodium sulfite,
Formaldehyde and ALS are reacted.From upper table 1, it can be seen that the electrical conductivity of comparative example 4 is less than the conductance of embodiment 3
Rate, this is primarily due to during alkali lignin modified, do not add hydrogenperoxide steam generator and chlorosulfuric acid and sodium sulfite,
Formaldehyde and ALS carry out sulfonating reaction to improve sulfonic content in alkali lignin, make last obtained lignin
Sulfonic content is relatively low in sulfonic acid, reduces its doping and dispersive property, so as to reduce last obtained poly- (3,4- ethylenes
Dioxy thiophene) dispersion liquid electrical conductivity, so in comparative example 4 product electrical conductivity be less than embodiment 3 in product electrical conductivity.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details and shown here as the example with description.
Claims (6)
- A kind of 1. preparation method of poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of high conductivity, it is characterised in that Comprise the following steps：Step 1：It is 2.8 according to mass ratio:1:1:1 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, ethylenediamine Tetraacethyl disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 20 DEG C of water baths, 30min is stirred under 6000rpm rotating speeds, oxidant is then added dropwise while stirring, continues stirring reaction 24h, primary first-order equation is made Liquid；Step 2：It is 1.5 according to mass ratio:1:1:1 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, second Edetate disodium and triethanolamine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 5 DEG C of water baths, 30min is stirred under 7000rpm rotating speeds, oxidant is then added dropwise while stirring, the stirring reaction 30h under 6000rpm rotating speeds, system Obtain secondary response liquid；Step 3：It is 0.5 according to mass ratio:1:1:1 ratio weighs above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes, second Edetate disodium and triethanolamine add high purity water, are made into solid content as 1.5% mixed liquor, anti-in repeat step two Process is answered, third-order reaction liquid is made；Step 4：Sodium sulfite stirring reaction 3h is added into above-mentioned third-order reaction liquid, adds resin anion (R.A.) and cation Resin, continue to stir 24h, with the filter cloth suction filtering of 100 mesh, it is 2 that mass ratio is added into filtrate:1:1 ethylene glycol, dimethyl sulfate Ester and dimethyl sulfoxide (DMSO), mix, be heated to 55~65 DEG C, while the ultraviolet light irradiation 30min for being 365nm with wavelength, then carry out Homogenization, homogenization pressure are 20~30MPa, and homogenization cycles are 1~2 time, are cooled to room temperature and high conductivity poly- (3,4- is made Ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid；The total addition level of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO) is 5 ~10wt%；The preparation method of the lignin sulfonic acid comprises the following steps：Step a：Wheat Straw Lignin from Alkali Pulping is dissolved in the solution that water is made into 15wt%, the pH for adjusting solution is 10, is taken out after being completely dissolved Filter, takes filtrate, and the pH for then adjusting filtrate while stirring is 3, then is centrifuged, and takes filter residue；Step b：Above-mentioned filter residue is dissolved in the sodium hydroxide solution that pH is 10, it is 4 to add mass ratio:1:1 sodium peroxydisulfate, just Octanol and glycerine, the microwave irradiation for being 400W with power, 30min is reacted at 80 DEG C, the alkali lignin of activation is made；It is described The total addition level of sodium peroxydisulfate, n-octyl alcohol and glycerine is 5~8wt%；Step c：It is 6 that mass ratio is added into the alkali lignin of above-mentioned activation:5:1 formaldehyde, dihydroxyacetone (DHA) and acrylic acid, 1h, then the ultraviolet light irradiation 20min for being 365nm with wavelength are reacted at 80 DEG C；The formaldehyde, dihydroxyacetone (DHA) and acrylic acid it is total Addition is 20~40wt%；Step d：It is 3 that mass ratio is added into the reaction solution after step c processing:1 hydrogenperoxide steam generator and chlorosulfuric acid, at 85 DEG C After lower reaction 1h, the pH for adjusting reaction solution is 10, adds mass ratio as 5:2:1 sodium sulfite, formaldehyde and allyl sulphonic acid Sodium, continue to react 2h, then be freeze-dried and sodium lignin sulfonate powder is made；The hydrogenperoxide steam generator and chlorosulfuric acid always add Dosage is 5~8wt%, and the total addition level of the sodium sulfite, formaldehyde and ALS is 20~40wt%；Step e：Above-mentioned sodium lignin sulfonate powder is dissolved in water it is made into 15wt% solution and carry out ultrafiltration, molecular cut off is more than 5000 component, by molecular weight more than 5000 component ultrafiltrate concentrated by rotary evaporation to solid content be 20~30%, add sun from Subtree fat, stir 24h, with the filter cloth suction filtering of 800 mesh, collect filtrate, by filtrate concentrated by rotary evaporation into solid content be 70~80% Concentrate, then lignin sulfonic acid is made in concentrate freeze-drying.
- 2. the preparation side of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity as claimed in claim 1 Method, it is characterised in that the oxidant is one kind in sodium peroxydisulfate, ammonium persulfate and potassium peroxydisulfate, with 3,4- enedioxies The mol ratio of thiophene is 1.3:1, oxidant is dissolved in high purity water when in use, first and is made into substance withdrawl syndrome by the oxidant is The 0.5mol/L aqueous solution, is then dripped in 30min.
- 3. the preparation side of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity as claimed in claim 1 Method, it is characterised in that in step 4, in addition to added into filtrate in mannitol, sorbierite and DMF One kind, addition 8wt%.
- 4. the preparation side of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity as claimed in claim 1 Method, it is characterised in that the resin anion (R.A.) is polystyrene macroporous strong basic anion exchange resin, before use, first existing 24h is soaked in 3.0mol/L sodium hydroxide solution, it is 7 to be cleaned again with high purity water to pH after filtering.
- 5. the preparation side of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity as claimed in claim 1 Method, it is characterised in that the resin cation is polystyrene macropore strong acid cation exchanger resin, before use, first existing 24h is soaked in 3.0mol/L hydrochloric acid solution, it is 7 to be cleaned again with high purity water to pH after filtering.
- 6. the preparation side of poly- (3,4- the ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid of high conductivity as claimed in claim 1 Method, it is characterised in that the retention model Da=5000 of milipore filter in the ultrafiltration, be made up of polyether sulfone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105588A (en) * | 2019-06-11 | 2019-08-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of novel sulfonated lignin |
| CN112993232A (en) * | 2019-12-17 | 2021-06-18 | 深圳新宙邦科技股份有限公司 | Positive electrode material and preparation method thereof, sulfur positive electrode and metal sulfur battery |
-
2017
- 2017-10-31 CN CN201711053974.6A patent/CN107722568A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105588A (en) * | 2019-06-11 | 2019-08-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of novel sulfonated lignin |
| CN112993232A (en) * | 2019-12-17 | 2021-06-18 | 深圳新宙邦科技股份有限公司 | Positive electrode material and preparation method thereof, sulfur positive electrode and metal sulfur battery |
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Application publication date: 20180223 |