CN107722657A - The biocatalysis preparation method of poly- (3,4 ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid - Google Patents
The biocatalysis preparation method of poly- (3,4 ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/18—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms containing at least two hetero rings condensed among themselves or condensed with a common carbocyclic ring system, e.g. rifamycin
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
Abstract
The invention provides a kind of biocatalysis preparation method of poly- (3,4 ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid, including：Using peroxidase as catalyst, hydrogen peroxide is oxidant, trigger monomer 3,4 ethylenedioxy thiophenes carry out primary first-order equation, secondary response and third-order reaction, then purified with zwitterion resin, then add ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO), mixed, homogenization is carried out again, is cooled to room temperature.The present invention uses biological enzyme polymerisation, high catalytic efficiency, reaction condition are gentle, be advantageous to control reaction speed, reduce poly- (3,4 ethylenedioxy thiophenes) reunion between/lignin sulfonic acid compound, prepare a kind of electrical conductivity is high, dispersion stabilization is good, machinability is strong poly- (3,4 ethylenedioxy thiophenes) dispersion liquid, production cost can also be reduced using the present invention, 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 biocatalysis preparation method of poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid of kind, 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 biology of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid
Preparation method is catalyzed, it uses the generation of biological enzyme polymerisation, and high catalytic efficiency, reaction condition are gentle, are advantageous to control
Reaction speed processed, the reunion between poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound is reduced, effectively improves poly- (3,4-
Ethylenedioxy thiophene)/lignin sulfonic acid dispersion liquid electric conductivity, prepare that a kind of electrical conductivity is high, dispersion stabilization is good, can process
Property strong poly- (3,4-ethylene dioxythiophene) dispersion liquid, while also reduce production cost, economize on resources, alleviate papermaking wastewater pair
The pollution of 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- enedioxy thiophenes
Fen)/lignin sulfonic acid dispersion liquid biocatalysis preparation method, comprise the following steps：
Step 1：It is 2.8 according to mass ratio:1:2:2.5 ratio weigh lignin sulfonic acid, 3,4- ethylenedioxy thiophenes,
Sodium tartrate and sodium oxalate add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 25 DEG C of water baths,
30min is stirred under 6000rpm rotating speeds, while the pH for adding NaAc_HAc buffer solution regulation mixed liquor is 6, then side is stirred
Mix side and add peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, continue stirring reaction 24h, primary first-order equation liquid is made；
Step 2：It is 1.5 according to mass ratio:1:2:2.5 ratio weighs above-mentioned primary first-order equation liquid, 3,4- enedioxy thiophenes
Fen, sodium tartrate and sodium oxalate add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C of water baths,
30min is stirred under 7000rpm rotating speeds, then adds peroxidase while stirring, then hydrogenperoxide steam generator is slowly added dropwise,
Stirring reaction 30h under 6000rpm rotating speeds, mass ratio is added as 2:2:1 odium stearate, enuatrol and isopropanol, uses frequency
For 500MHz ultrasonication 3min, suspend 1min, repeat above-mentioned ultrasonication 3 times, secondary response liquid is made；It is described
The total addition level of odium stearate, enuatrol and isopropanol is 3~5wt%；
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, sodium butylnaphthalenesulfonate and octodecyl betaine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in
In 20 DEG C of water baths, 30min is stirred under 7000rpm rotating speeds, then adds peroxidase while stirring, then be slowly added dropwise
Hydrogenperoxide steam generator, the stirring reaction 36h under 6000rpm rotating speeds, mass ratio is added as 2:1:4 sodium sulphate, methyl-silicone oil
With polyethylene glycol -600, ball-milling treatment, rotational speed of ball-mill 350r/min, ratio of grinding media to material 16 are carried out:1, Ball-milling Time 3h, it is made
Third-order reaction liquid；The total addition level of the sodium sulphate, methyl-silicone oil and polyethylene glycol -600 is 5~8wt%；
Step 4：Resin anion (R.A.) and resin cation are added into above-mentioned third-order reaction liquid, 24h is stirred, with 100 purposes
Filter cloth suction filtering, it is 2 that mass ratio is added into filtrate:1:1 ethylene glycol, dimethyl suflfate 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 is 20~
30MPa, homogenization cycles are 1~2 time, are cooled to room temperature and poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid is made；
The total addition level of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO) is 5~10wt%；
The mol ratio of hydrogen peroxide and 3,4- ethylenedioxy thiophenes is 1 in the hydrogenperoxide steam generator:1；
The preparation method of the lignin sulfonic acid comprises the following steps：
Step a：Lignosulfonates are dissolved in the solution that water is made into 15wt%, taken out after being completely dissolved with the filter cloth of 800 mesh
Filter, filtrate is collected, the pH that NaAc_HAc buffer solution regulation filtrate is added into filtrate is 4.5~6.5；
Step b：It is 1 that mass ratio is added into the filtrate after step a processing:4 n-butanol and positive hexadecanol, add after mixing
Enter mass ratio for 3:1 cellulase and hemicellulase, constant temperature oscillation 48h at 40 DEG C is placed in, saccharomycete is added and is placed in room
The lower fermentation 48h of temperature；The total addition level of the n-butanol and positive hexadecanol is 2~4wt%, the cellulase and hemicellulase
Total addition level be 3~5wt%；
Step c：It is 4 that mass ratio is added in filtrate after being fermented to step b:1 dichloromethane and 95% ethanol solution,
Vibration stands 3h after mixing, collect water layer solution, repeats said process 2 times, merges the water layer solution collected three times；The dichloro
The total addition level of methane and 95% ethanol solution is 15~20wt%；
Step d：Water layer solution after above-mentioned merging is subjected to ultrafiltration, molecular cut off is more than 5000 component, by molecule
Component ultrafiltrate concentrated by rotary evaporation of the amount more than 5000 to solid content is 20~30%, adds resin cation, stirs 24h, is used
The filter cloth suction filtering of 800 mesh, filtrate is collected, by filtrate concentrated by rotary evaporation into the concentrate that solid content is 70~80%, then by concentrate
Lignin sulfonic acid is made in freeze-drying.
Preferably, wherein, the peroxidase is horseradish peroxidase or soybean peroxidase.
Preferably, wherein, the mass fraction of the hydrogenperoxide steam generator is 35%.
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 present invention uses the generation of biological enzyme polymerisation, biological enzyme efficiency high, reaction condition temperature
Be advantageous to control reaction speed, therefore the group between poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound can be reduced
It is poly-, the electric conductivity of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid is effectively improved, and biology enzyme is using
After can natural degradation, it is more green.
(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 wood element sulfonate 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 obtained after being purified by lignosulfonates, is a kind of natural reproducible money
Source, and the polystyrolsulfon acid in poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid dispersion liquid is from increasingly exhausted stone
Oily resource, therefore, compared to poly- (3,4-ethylene dioxythiophene)/polystyrolsulfon acid dispersion liquid, the present invention can alleviate oil money
Source pressure in short supply.
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:1:2:2.5 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, sodium tartrate
High purity water is added with sodium oxalate, the mixed liquor that solid content is 2.5% is made into, is placed in 25 DEG C of water baths, in 6000rpm rotating speeds
Lower stirring 30min, while the pH for adding NaAc_HAc buffer solution regulation mixed liquor is 6, then adds horseradish while stirring
Peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, continue stirring reaction 24h, primary first-order equation liquid is made；It is according to mass ratio
1.5:1:2:It is high-purity that 2.5 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, sodium tartrate and sodium oxalate addition
Water, the mixed liquor that solid content is 2% is made into, is placed in 20 DEG C of water baths, 30min, Ran Houbian is stirred under 7000rpm rotating speeds
Stir side and add horseradish peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, the stirring reaction 30h under 6000rpm rotating speeds, then
It is 2 to add mass ratio:2:1 odium stearate, enuatrol and isopropanol, the ultrasonication 3min for being 500MHz with frequency, temporarily
Stop 1min, repeat above-mentioned ultrasonication 3 times, secondary response liquid is made；The odium stearate, enuatrol and isopropanol it is total
Addition is 3wt%；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Sodium butylnaphthalenesulfonate and octodecyl betaine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C
In water bath, 30min is stirred under 7000rpm rotating speeds, then adds horseradish peroxidase while stirring, then be slowly added dropwise
Hydrogenperoxide steam generator, the stirring reaction 36h under 6000rpm rotating speeds, mass ratio is added as 2:1:4 sodium sulphate, methyl-silicone oil
With polyethylene glycol -600, ball-milling treatment, rotational speed of ball-mill 350r/min, ratio of grinding media to material 16 are carried out:1, Ball-milling Time 3h, it is made
Third-order reaction liquid；The total addition level of the sodium sulphate, methyl-silicone oil and polyethylene glycol -600 is 5wt%；To above-mentioned third-order reaction
Resin anion (R.A.) and resin cation are added in liquid, stirs 24h, with the filter cloth suction filtering of 100 mesh, addition mass ratio is into filtrate
2:1:1 ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO), mix, be heated to 55 DEG C, while be the ultraviolet of 365nm with wavelength
Light irradiates 30min, then carries out homogenization, homogenization pressure 25MPa, and homogenization cycles are 2 times, is cooled to room temperature and is made poly-
(3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid；Total addition of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO)
Measure as 8wt%.
Wherein, the mol ratio of hydrogen peroxide and 3,4-ethylene dioxythiophene is 1 in the hydrogenperoxide steam generator:1, the mistake
The mass fraction of hydrogen peroxide solution is 35%.
The preparation method of the lignin sulfonic acid includes：Lignosulfonates are dissolved in the solution that water is made into 15wt%, it is complete
With the filter cloth suction filtering of 800 mesh after fully dissolved, filtrate is collected, NaAc_HAc buffer solution regulation filtrate is added into filtrate
PH is 4.5；Then it is 1 that mass ratio is added into filtrate:4 n-butanol and positive hexadecanol, it is 3 that mass ratio is added after mixing:1
Cellulase and hemicellulase, constant temperature oscillation 48h at 40 DEG C is placed in, saccharomycete is added and is placed in the 48h that ferments at room temperature；It is described
The total addition level of n-butanol and positive hexadecanol is 2wt%, and the total addition level of the cellulase and hemicellulase is 3wt%；
It is 4 that mass ratio is added into the filtrate after fermentation:1 dichloromethane and 95% ethanol solution, vibration stand 3h after mixing, and receive
Collect water layer solution, repeat said process 2 times, merge the water layer solution collected three times；The dichloromethane and 95% ethanol are molten
The total addition level of liquid is 15wt%；Water layer solution after above-mentioned merging is subjected to ultrafiltration, 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 2>
It is 2.8 according to mass ratio:1:2:2.5 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, sodium tartrate
High purity water is added with sodium oxalate, the mixed liquor that solid content is 2.5% is made into, is placed in 25 DEG C of water baths, in 6000rpm rotating speeds
Lower stirring 30min, while the pH for adding NaAc_HAc buffer solution regulation mixed liquor is 6, then adds horseradish while stirring
Peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, continue stirring reaction 24h, primary first-order equation liquid is made；It is according to mass ratio
1.5:1:2:It is high-purity that 2.5 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, sodium tartrate and sodium oxalate addition
Water, the mixed liquor that solid content is 2% is made into, is placed in 20 DEG C of water baths, 30min, Ran Houbian is stirred under 7000rpm rotating speeds
Stir side and add horseradish peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, the stirring reaction 30h under 6000rpm rotating speeds, then
It is 2 to add mass ratio:2:1 odium stearate, enuatrol and isopropanol, the ultrasonication 3min for being 500MHz with frequency, temporarily
Stop 1min, repeat above-mentioned ultrasonication 3 times, secondary response liquid is made；The odium stearate, enuatrol and isopropanol it is total
Addition is 4wt%；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Sodium butylnaphthalenesulfonate and octodecyl betaine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C
In water bath, 30min is stirred under 7000rpm rotating speeds, then adds horseradish peroxidase while stirring, then be slowly added dropwise
Hydrogenperoxide steam generator, the stirring reaction 36h under 6000rpm rotating speeds, mass ratio is added as 2:1:4 sodium sulphate, methyl-silicone oil
With polyethylene glycol -600, ball-milling treatment, rotational speed of ball-mill 350r/min, ratio of grinding media to material 16 are carried out:1, Ball-milling Time 3h, it is made
Third-order reaction liquid；The total addition level of the sodium sulphate, methyl-silicone oil and polyethylene glycol -600 is 6wt%；To above-mentioned third-order reaction
Resin anion (R.A.) and resin cation are added in liquid, stirs 24h, with the filter cloth suction filtering of 100 mesh, addition mass ratio is into filtrate
2:1:1 ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO), mix, be heated to 60 DEG C, while be the ultraviolet of 365nm with wavelength
Light irradiates 30min, then carries out homogenization, homogenization pressure 20MPa, and homogenization cycles are 2 times, is cooled to room temperature and is made poly-
(3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid；Total addition of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO)
Measure as 5wt%.
Wherein, the mol ratio of hydrogen peroxide and 3,4-ethylene dioxythiophene is 1 in the hydrogenperoxide steam generator:1, the mistake
The mass fraction of hydrogen peroxide solution is 35%.
The preparation method of the lignin sulfonic acid includes：Lignosulfonates are dissolved in the solution that water is made into 15wt%, it is complete
With the filter cloth suction filtering of 800 mesh after fully dissolved, filtrate is collected, NaAc_HAc buffer solution regulation filtrate is added into filtrate
PH is 5.0；Then it is 1 that mass ratio is added into filtrate:4 n-butanol and positive hexadecanol, it is 3 that mass ratio is added after mixing:1
Cellulase and hemicellulase, constant temperature oscillation 48h at 40 DEG C is placed in, saccharomycete is added and is placed in the 48h that ferments at room temperature；It is described
The total addition level of n-butanol and positive hexadecanol is 4wt%, and the total addition level of the cellulase and hemicellulase is 4wt%；
It is 4 that mass ratio is added into the filtrate after fermentation:1 dichloromethane and 95% ethanol solution, vibration stand 3h after mixing, and receive
Collect water layer solution, repeat said process 2 times, merge the water layer solution collected three times；The dichloromethane and 95% ethanol are molten
The total addition level of liquid is 20wt%；Water layer solution after above-mentioned merging is subjected to ultrafiltration, 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.
<Embodiment 3>
It is 2.8 according to mass ratio:1:2:2.5 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, sodium tartrate
High purity water is added with sodium oxalate, the mixed liquor that solid content is 2.5% is made into, is placed in 25 DEG C of water baths, in 6000rpm rotating speeds
Lower stirring 30min, while the pH for adding NaAc_HAc buffer solution regulation mixed liquor is 6, then adds soybean while stirring
Peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, continue stirring reaction 24h, primary first-order equation liquid is made；It is according to mass ratio
1.5:1:2:It is high-purity that 2.5 ratio weighs above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, sodium tartrate and sodium oxalate addition
Water, the mixed liquor that solid content is 2% is made into, is placed in 20 DEG C of water baths, 30min, Ran Houbian is stirred under 7000rpm rotating speeds
Stir side and add soybean peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, the stirring reaction 30h under 6000rpm rotating speeds, then
It is 2 to add mass ratio:2:1 odium stearate, enuatrol and isopropanol, the ultrasonication 3min for being 500MHz with frequency, temporarily
Stop 1min, repeat above-mentioned ultrasonication 3 times, secondary response liquid is made；The odium stearate, enuatrol and isopropanol it is total
Addition is 5wt%；It is 0.5 according to mass ratio:1:1:1 ratio weigh above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes,
Sodium butylnaphthalenesulfonate and octodecyl betaine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C
In water bath, 30min is stirred under 7000rpm rotating speeds, then adds soybean peroxidase while stirring, then be slowly added dropwise
Hydrogenperoxide steam generator, the stirring reaction 36h under 6000rpm rotating speeds, mass ratio is added as 2:1:4 sodium sulphate, methyl-silicone oil
With polyethylene glycol -600, ball-milling treatment, rotational speed of ball-mill 350r/min, ratio of grinding media to material 16 are carried out:1, Ball-milling Time 3h, it is made
Third-order reaction liquid；The total addition level of the sodium sulphate, methyl-silicone oil and polyethylene glycol -600 is 8wt%；To above-mentioned third-order reaction
Resin anion (R.A.) and resin cation are added in liquid, stirs 24h, with the filter cloth suction filtering of 100 mesh, addition mass ratio is into filtrate
2:1:1 ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO), mix, be heated to 65 DEG C, while be the ultraviolet of 365nm with wavelength
Light irradiates 30min, then carries out homogenization, homogenization pressure 30MPa, and homogenization cycles are 1 time, is cooled to room temperature and is made poly-
(3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid；Total addition of the ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO)
Measure as 10wt%.
Wherein, the mol ratio of hydrogen peroxide and 3,4-ethylene dioxythiophene is 1 in the hydrogenperoxide steam generator:1, the mistake
The mass fraction of hydrogen peroxide solution is 35%.
The preparation method of the lignin sulfonic acid includes：Lignosulfonates are dissolved in the solution that water is made into 15wt%, it is complete
With the filter cloth suction filtering of 800 mesh after fully dissolved, filtrate is collected, NaAc_HAc buffer solution regulation filtrate is added into filtrate
PH is 6.5；Then it is 1 that mass ratio is added into filtrate:4 n-butanol and positive hexadecanol, it is 3 that mass ratio is added after mixing:1
Cellulase and hemicellulase, constant temperature oscillation 48h at 40 DEG C is placed in, saccharomycete is added and is placed in the 48h that ferments at room temperature；It is described
The total addition level of n-butanol and positive hexadecanol is 3wt%, and the total addition level of the cellulase and hemicellulase is 5wt%；
It is 4 that mass ratio is added into the filtrate after fermentation:1 dichloromethane and 95% ethanol solution, vibration stand 3h after mixing, and receive
Collect water layer solution, repeat said process 2 times, merge the water layer solution collected three times；The dichloromethane and 95% ethanol are molten
The total addition level of liquid is 18wt%；Water layer solution after above-mentioned merging is subjected to ultrafiltration, 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.
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-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and lignin sulfonic acid with embodiment 1,
Difference is：Resin anion (R.A.) and resin cation are added directly into primary first-order equation liquid, carries out subsequent treatment, without
Secondary and third-order reaction.
<Comparative example 2>
The preparation method of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and lignin sulfonic acid with embodiment 2,
Difference is：Resin anion (R.A.) and resin cation are added directly into secondary response liquid, carries out subsequent treatment, without
Third-order reaction.
<Comparative example 3>
The preparation method of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and lignin sulfonic acid with embodiment 3,
Difference is：Peroxidase is not added in all courses of reaction.
<Comparative example 4>
The preparation method of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and lignin sulfonic acid with embodiment 3,
Difference is：When preparing lignin sulfonic acid using lignosulfonates, by the water layer solution after merging without ultrafiltration,
It is directly added into resin cation and carries out subsequent treatment.
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, in polymerization process by
In coming initiated polymerization, high catalytic efficiency, the reaction condition temperature of peroxidase using Catalyzed Synthesis By Peroxidase hydrogen peroxide
Be advantageous to control reaction speed, reduce the reunion between poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound, effectively
Improve the electric conductivity of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid；So the electrical conductivity of product is higher,
Electric conductivity is relatively good.
Comparative example 1 compared with Example 1, poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and sulfomethylated lignin
The preparation method of acid is identical, and difference is：A polymerisation is only carried out, without carrying out secondary and third-order reaction.
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 once be gathered
When closing reaction, conductive poly (3,4- enedioxy thiophenes in poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid compound of one side
Fen) content it is very low, greatly reduce the quantity of free carrier, and the outer surface of compound is covered with a large amount of nonconducting
Lignin sulfonic acid；The network structure that (3,4- ethylenedioxy thiophenes) chain poly- in another aspect compound is mutually wound compares
It is small, 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 low.
Comparative example 2 compared with Example 2, poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and sulfomethylated lignin
The preparation method of acid is identical, and difference is：Primary and secondary polymerisation is only carried out, without carrying out third-order reaction.
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 once with two
During secondary polymerisation, conductive poly (3,4- enedioxy thiophenes in poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound
Fen) content decrease, the quantity of free carrier is also decreased, while (3,4- enedioxy thiophenes poly- in compound
Fen) the mutual winding degree of chain decreases, and effective transmission of carrier has also been reduced, so the product electricity of comparative example 2
Conductance is less than the product electrical conductivity of embodiment 2, and this also illustrates, on the premise of dispersion stabilization is ensured, appropriate increase polymerization time
Number, the electrical conductivity of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid can be improved.
Comparative example 3 compared with Example 3, poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and sulfomethylated lignin
The preparation method of acid is identical, and difference is：All without addition peroxidase in all courses of reaction.From the energy of upper table 1
Enough find out, the electrical conductivity of comparative example 3 is less than the electrical conductivity of embodiment 3, and this effect for being primarily due to peroxidase is with mistake
Hydrogen oxide is that electron acceptor is catalyzed the oxidation of monomer 3,4-ethylene dioxythiophene, and then initiated polymerization, but if is being polymerize
Peroxidase is not added in reaction, the simple oxidation using hydrogen peroxide is come initiated polymerization, it will makes polymerization anti-
The speed answered substantially reduces, and makes the content of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid compound that ultimately produces also big
It is big to reduce, thus the electrical conductivity of the product prepared is greatly reduced, due to all not adding in all courses of reaction in comparative example 3
Add peroxidase, so the content of poly- (the 3,4-ethylene dioxythiophene)/lignin sulfonic acid compound ultimately produced drops significantly
It is low, it is greatly reduced the electrical conductivity of product.
Comparative example 4 compared with Example 3, poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid and sulfomethylated lignin
The preparation method of acid is identical, and difference is：Water layer solution after merging does not carry out ultrafiltration, and is directly added into cation tree
Fat carries out subsequent treatment.From upper table 1, it can be seen that the electrical conductivity of comparative example 4 be less than embodiment 3 electrical conductivity, this be mainly because
It is water layer solution without Ultrafiltration Purifying, some small molecular weight impurities is also contained in lignosulfonates, these impurity can be right
Polymerisation produces inhibition, reduces the electrical conductivity of dispersion liquid, so the product electrical conductivity of comparative example 4 is less than embodiment 3
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. biocatalysis preparation method of poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid, it is characterised in that Comprise the following steps：Step 1：It is 2.8 according to mass ratio:1:2:2.5 ratio weighs lignin sulfonic acid, 3,4- ethylenedioxy thiophenes, winestone Sour sodium and sodium oxalate add high purity water, are made into the mixed liquor that solid content is 2.5%, are placed in 25 DEG C of water baths, in 6000rpm 30min is stirred under rotating speed, while the pH for adding NaAc_HAc buffer solution regulation mixed liquor is 6, is then added while stirring Peroxidase, then hydrogenperoxide steam generator is slowly added dropwise, continue stirring reaction 24h, primary first-order equation liquid is made；Step 2：It is 1.5 according to mass ratio:1:2:2.5 ratio weigh above-mentioned primary first-order equation liquid, 3,4- ethylenedioxy thiophenes, Sodium tartrate and sodium oxalate add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C of water baths, 30min is stirred under 7000rpm rotating speeds, then adds peroxidase while stirring, then hydrogenperoxide steam generator is slowly added dropwise, Stirring reaction 30h under 6000rpm rotating speeds, mass ratio is added as 2:2:1 odium stearate, enuatrol and isopropanol, uses frequency For 500MHz ultrasonication 3min, suspend 1min, repeat above-mentioned ultrasonication 3 times, secondary response liquid is made；It is described The total addition level of odium stearate, enuatrol and isopropanol is 3~5wt%；Step 3：It is 0.5 according to mass ratio:1:1:1 ratio weighs above-mentioned secondary response liquid, 3,4- ethylenedioxy thiophenes, fourth Base sodium naphthalene sulfonate and octodecyl betaine add high purity water, are made into the mixed liquor that solid content is 2%, are placed in 20 DEG C of water Bathe in environment, 30min is stirred under 7000rpm rotating speeds, then adds peroxidase while stirring, then peroxidating is slowly added dropwise Hydrogen solution, the stirring reaction 36h under 6000rpm rotating speeds, mass ratio is added as 2:1:4 sodium sulphate, methyl-silicone oil and poly- second Glycol -600, carry out ball-milling treatment, rotational speed of ball-mill 350r/min, ratio of grinding media to material 16:1, Ball-milling Time 3h, it is made anti-three times Answer liquid；The total addition level of the sodium sulphate, methyl-silicone oil and polyethylene glycol -600 is 5~8wt%；Step 4：Resin anion (R.A.) and resin cation are added into above-mentioned third-order reaction liquid, 24h is stirred, with the filter cloth of 100 mesh Filter, it is 2 that mass ratio is added into filtrate:1:1 ethylene glycol, dimethyl suflfate and dimethyl sulfoxide (DMSO), mix, it is heated to 55~ 65 DEG C, at the same the ultraviolet light irradiation 30min for being 365nm with wavelength, then homogenization is carried out, homogenization pressure is 20~30MPa, Matter number is 1~2 time, is cooled to room temperature and poly- (3,4-ethylene dioxythiophene)/lignin sulfonic acid dispersion liquid is made；The second two The total addition level of alcohol, dimethyl suflfate and dimethyl sulfoxide (DMSO) is 5~10wt%；The mol ratio of hydrogen peroxide and 3,4- ethylenedioxy thiophenes is 1 in the hydrogenperoxide steam generator:1；The preparation method of the lignin sulfonic acid comprises the following steps：Step a：Lignosulfonates are dissolved in the solution that water is made into 15wt%, with the filter cloth suction filtering of 800 mesh after being completely dissolved, received Collect filtrate, the pH that NaAc_HAc buffer solution regulation filtrate is added into filtrate is 4.5~6.5；Step b：It is 1 that mass ratio is added into the filtrate after step a processing:4 n-butanol and positive hexadecanol, matter is added after mixing Amount is than being 3:1 cellulase and hemicellulase, constant temperature oscillation 48h at 40 DEG C is placed in, saccharomycete is added and is placed at room temperature Ferment 48h；The total addition level of the n-butanol and positive hexadecanol is 2~4wt%, the cellulase and hemicellulase it is total Addition is 3~5wt%；Step c：It is 4 that mass ratio is added in filtrate after being fermented to step b:1 dichloromethane and 95% ethanol solution, vibration 3h is stood after mixing, collects water layer solution, repeats said process 2 times, merges the water layer solution collected three times；The dichloromethane Total addition level with 95% ethanol solution is 15~20wt%；Step d：Water layer solution after above-mentioned merging is subjected to ultrafiltration, molecular cut off is more than 5000 component, and molecular weight is big It is 20~30% in 5000 component ultrafiltrate concentrated by rotary evaporation to solid content, adds resin cation, 24h is stirred, with 800 mesh Filter cloth suction filtering, collect filtrate, by filtrate concentrated by rotary evaporation into the concentrate that solid content is 70~80%, then concentrate freezed dry It is dry that lignin sulfonic acid is made.
- 2. the living things catalysis preparation side of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid as claimed in claim 1 Method, it is characterised in that the peroxidase is horseradish peroxidase or soybean peroxidase.
- 3. the living things catalysis preparation side of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid as claimed in claim 1 Method, it is characterised in that the mass fraction of the hydrogenperoxide steam generator is 35%.
- 4. the living things catalysis preparation side of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid 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 living things catalysis preparation side of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid 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 living things catalysis preparation side of poly- (3,4- ethylenedioxy thiophenes)/lignin sulfonic acid dispersion liquid 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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