CN102443250B - Crosslinkable poly-(3,4-ethylenedioxythiophene) aqueous dispersoid and preparation method thereof - Google Patents
Crosslinkable poly-(3,4-ethylenedioxythiophene) aqueous dispersoid and preparation method thereof Download PDFInfo
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- CN102443250B CN102443250B CN 201110215262 CN201110215262A CN102443250B CN 102443250 B CN102443250 B CN 102443250B CN 201110215262 CN201110215262 CN 201110215262 CN 201110215262 A CN201110215262 A CN 201110215262A CN 102443250 B CN102443250 B CN 102443250B
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- 0 CC1OCC[O+]C1* Chemical compound CC1OCC[O+]C1* 0.000 description 2
- AXIULCJVSMKUPB-UHFFFAOYSA-N CC(C)C1OCCOC1(C)C Chemical compound CC(C)C1OCCOC1(C)C AXIULCJVSMKUPB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a crosslinkable poly-(3,4-ethylenedioxythiophene) aqueous dispersoid and a preparation method thereof, relating to the fields of organic semiconductor material preparation technology and application thereof. The crosslinkable (3,4-ethylenedioxythiophene) aqueous dispersoid is prepared by carrying out reaction on monomer, oxidant, a catalyst, a template and adulterant in de-ionized water, wherein the template and the adulterant functionalize sodium polystyrene sulfonate and blocking aqueous polyurethane; the aqueous dispersoid is dark blue in color, and the prepared aqueous dispersoid is subjected to post treatment in a centrifuging manner; and the film formed from the dispersoid can be deblocked and crosslinked at high temperature, so that the water-absorbing capacity of the film is greatly reduced and the film-forming effect is improved. Ultraviolet spectrophotometer tests show that the formed film has no obvious absorption in the visible wavelength range, thereby ensuring that the formed film is suitable for being used as a transparent electrode.
Description
Technical field
The present invention relates to organic semiconductor material technology of preparing and Application Areas thereof, relating to functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer is poly-(3,4-ethene dioxythiophene) water dispersion of crosslinkable of template and doping agent and preparation method thereof.
Background technology
Poly-(3,4-ethene dioxythiophene) (PEDOT) with its photoelectric properties, environmental stability, environment friendly preferably, causes researchist's extensive concern and research.It is found that the insoluble infusibility of itself, its application is restricted, classical treatment process is to add this water-soluble polymers of poly (sodium 4-styrenesulfonate) (PSS) as template and doping agent, this problem is resolved, but PSS rigid structure, make and have only and 3,4-ethene dioxythiophene (EDOT) usage ratio is during greater than a certain numerical value, the film-formation result that just has, and PSS's do not have electroconductibility, wishes that logical low template and the doping agent consumption of reducing improves the PEDOT/PSS specific conductivity and do not influence film-formation result and become problem thereby make.
The invention provides a kind of is poly-(3 of template and doping agent with functional polystyrene sodium sulfonate and polyurethane copolymer, the 4-ethene dioxythiophene) water dispersion and preparation method thereof, the dispersion of this kind polymkeric substance, good film-forming property, water regain is little after the film forming, have environmental stability and environment friendly simultaneously, and specific conductivity is improved to a certain extent also.
Summary of the invention
The invention provides a kind of crosslinkable, water regain is low, film forming properties is good poly-(3,4-ethene dioxythiophene) water dispersion and preparation method thereof.
A kind of crosslinkable poly-(3,4-ethene dioxythiophene) water dispersion, its structural formula is as follows:
Wherein the C segment at high temperature can deblocking, with the hydroxyl generation crosslinking reaction in the R segment among the B;
Wherein A is poly-(3,4-ethene dioxythiophene) segment;
Wherein B is the functional polystyrene sodium sulfonate as template and doping agent, and R structure wherein is as follows:
Wherein R ' is
Or
Or
R ' '-CH
3For or-H,
C is the end-sealed type aqueous polyurethane as template and doping agent, wherein R
1Be polyethers or polyester segment,
R
1The polyether structure formula be
R
1The polyester construction formula be:
Z is (5～45); M is (4～35); Y is (4～35);
The preparation method of above-mentioned a kind of crosslinkable poly-(3,4-ethene dioxythiophene) water dispersion carries out according to following steps:
(1) preparation of functional polystyrene sodium sulfonate
Concrete preparation method is as follows:
Sodium styrene sulfonate (SSS), esters of acrylic acid, initiator, solvent place the four-hole boiling flask that fills magneton and reflux condensate device according to a certain percentage, vacuumize logical nitrogen or argon gas, be heated to 90 ℃, stirring reaction 3～5 hours obtains faint yellow clarification thick liquid.With prepared material ethanol sedimentation, obtain white cotton-shaped solid, again dissolve with deionized water again, repeat 3～4 final white flockss of said process with ethanol and deionized water again and use 60 ℃～80 ℃ dryings of vacuum drying oven 10 hours, obtain the final white solid product.
Wherein said esters of acrylic acid comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, and glycidyl methacrylate, vinylformic acid hydroxy butyl ester etc., the mol ratio of add-on and Sodium styrene sulfonate is 1:(1～10);
Wherein said initiator is persulphate, comprises Sodium Persulfate, and ammonium persulphate, Potassium Persulphate, consumption are 0.001～0.005 times of integral molar quantity;
Wherein said solvent is deionized water, and consumption is 80% of reaction system total mass
The functional polystyrene sodium sulfonate structural formula for preparing is as follows:
Wherein R ' is
Or
Or
R ' '-CH
3For or-H,
X wherein, the ratio of y is (0.1～10): 1,
Functionalization Sodium styrene sulfonate molecular weight is 20000～3200000.
(2) end-sealed type Synthesis of Waterborne Polyurethane:
Be divided into two kinds of situations:
(a) can adopt masked non-ionic type Synthesis of Waterborne Polyurethane:
Polyvalent alcohol and hydrophilic monomer be placed at according to a certain percentage be equipped with in the agitator four-hole boiling flask, after 140 ℃ of high-temperature stirring dewater, be cooled to below 65 ℃, add vulcabond, be warming up to 80 ℃ of isothermal reactions after two hours viscosity strengthen, add a small amount of solvent reduce react 2 hours again after the viscosity after, be cooled to 70 ℃ and add end-capping reagent, isothermal reaction 1～2 hour is cooled under 40 ℃ and adds gauge water, and preparation is finished.
Wherein said polyvalent alcohol is polyoxyethylene glycol (PEG) and polyether glycol (N220).Both use simultaneously, and mass ratio is 10%～90%;
Wherein said hydrophilic monomer is dimethylol propionic acid (DMPA), and the DMPA add-on is 2%～20% of polyvalent alcohol quality;
Wherein said solvent is butanone;
Wherein said vulcabond is TDI, IPDI, MDI, DADI, LDI, HDI, XDI, and consumption and polyvalent alcohol integral molar quantity ratio are (1.1～2): 1;
Wherein end-capping reagent is phenols, alcohols, secondary (uncle) amine, the bisulfite salt, oximes, imidazoles, be specially: para-chlorophenol, p-NP, cresols, phenol, pyrocatechol, methoxyphenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, 1,1,1,3,3,3-chlordene-2-propyl alcohol, Acetanilide, the N-methylacetamide, hexanolactam, succimide, di-t-butyl amine, pentanoic, Potassium hydrogen sulfite, sodium bisulfite, Sodium Pyrosulfite, ammonium bisulfite, boric acid, cyclohexanone-oxime, methyl ethyl ketoxime, the diphenylmethyl ketoxime, Diacetylmonoxime, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline etc.Consumption be with the vulcabond molar weight than (0.1～1): 1;
Product is finally made the aqueous solution of solid content 50%.
(b) or adopt the preparation of end-sealed type anion-type water-thinned polyurethane:
Polyvalent alcohol and hydrophilic monomer be placed at according to a certain percentage be equipped with in the agitator four-hole boiling flask, after 140 ℃ of high-temperature stirring dewater, be cooled to 50 ℃～below 60 ℃, add vulcabond, be warming up to 80 ℃ of isothermal reactions two hours, add end-capping reagent again, be warming up to 70 ℃ ~ 75 ℃ reaction 2 ~ 2.5h, be cooled to room temperature and add triethylamine (TEA), keep 10min that it is stirred, add acetone and regulate viscosity, last high-speed stirring is scattered in the water, makes solid content and be 30% end-sealed type anion-type water-thinned polyurethane.
Wherein said polyvalent alcohol is polypropylene glycol (PPG-N220), polyoxyethylene glycol, polypropylene glycol and glycol copolymer, polytetrahydrofuran, polyester polyol etc.;
Wherein said hydrophilic monomer is DMPA, and usage quantity is 2%～20% of polyvalent alcohol quality;
Wherein said vulcabond can be TDI, IPDI, MDI, DADI, LDI, HDI, XDI, and consumption and polyvalent alcohol molar weight ratio are (1.1～2): 1;
Wherein end-capping reagent is phenols, alcohols, secondary (uncle) amine, the bisulfite salt, oximes, imidazoles, be specially: para-chlorophenol, p-NP, cresols, phenol, pyrocatechol, methoxyphenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, 1,1,1,3,3,3-chlordene-2-propyl alcohol, Acetanilide, the N-methylacetamide, hexanolactam, succimide, di-t-butyl amine, pentanoic, Potassium hydrogen sulfite, sodium bisulfite, Sodium Pyrosulfite, ammonium bisulfite, boric acid, cyclohexanone-oxime, methyl ethyl ketoxime, the diphenylmethyl ketoxime, Diacetylmonoxime, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline etc.Consumption is and vulcabond molar ratio (0.1～1): 1;
Wherein triethylamine consumption and DMPA mol ratio are 1:1,
Product is finally made solid content 30% solution..
(3) preparation of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer is divided into two kinds of situations:
When adopting masked non-ionic type aqueous polyurethane, with functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane according to certain mass than mixing, namely obtain a kind of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer as PEDOT water dispersion template and doping agent, wherein the solid masses of two components is than being (1～10): 1;
When adopting the end-sealed type anion-type water-thinned polyurethane, with functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane according to certain mass than mixing, namely obtain a kind of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer as PEDOT water dispersion template and doping agent, wherein the solid masses of two components is than being (1～10): 1;
(4) poly-(3,4-ethene dioxythiophene) (PEDOT) preparation of water dispersion
In the preparation of poly-(3,4-ethene dioxythiophene) water dispersion, be template and doping agent with sodium polystyrene sulfonate and the end-sealed type aqueous polyurethane multipolymer for preparing, wherein said template and doping agent are product in the step 3
Concrete preparation method is as follows,
EDOT, template and doping agent, oxygenant, catalyzer join in the four-hole boiling flask that fills deionized water and magneton according to a certain percentage, stir fast, react 12～24 hours under 30 ℃ of conditions, finally obtain the mazarine dispersion liquid.
Wherein said template and doping agent are sodium polystyrene sulfonate and end-sealed type aqueous polyurethane multipolymer; Template and doping agent and EDOT mass ratio are (0.01～50): 1;
Wherein said oxygenant is persulphate, comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate, with the EDOT mol ratio be (0.5～4): 1;
Wherein above-mentioned catalyzer is ferric sulfate, and consumption and EDOT mol ratio are (0.001～0.005): 1;
Wherein the add-on of above-mentioned deionized water is for making m(EDOT+ template and doping agent)/m (EDOT+ template and doping agent+H
2O)=1%～15%.
The PEDOT water dispersion that finally makes carries out aftertreatment with centrifugal, impurity is removed in centrifugal back, leave and take precipitation with distilled water diluting after dispersing and dissolving again, same again mode is centrifugal, 3 times repeatedly, last precipitate with deionized water dilution back ultra-sonic dispersion got final product in 1 hour.
The present invention has following advantage and effect:
The present invention utilizes functionalization Sodium styrene sulfonate and end-sealed type aqueous polyurethane multipolymer to prepare the PEDOT water dispersion as template and doping agent, and it is little to have a particle diameter, and dispersion stability is good, and film forming properties is good, crosslinkable and have high conductance under the high temperature.
Embodiment
Below come foregoing invention is specifically described with embodiment, but be not limited to the embodiment content.
Embodiment 1The preparation of poly-(3,4-ethene dioxythiophene) (being PEDOT) water dispersion I
Template and doping agent are functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane multipolymer in the PEDOT water dispersion I, wherein the functional polystyrene sodium sulfonate is that acrylate hydroxyl ethyl ester and Sodium styrene sulfonate mol ratio are the 1:4 multipolymer, and its initiator amount and two monomer integral molar quantity ratios are 0.001:1; Masked non-ionic type aqueous polyurethane R(NCO/OH)=1.1, PEG content 90%, functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane copolymerization mass ratio are 1:1; Template and doping agent and EDOT mass ratio are 0.1:1; In the water dispersion preparation process, oxygenant, catalyzer and EDOT mol ratio are respectively 1.5:1 and 0.005:1.
Concrete preparation method and step are as follows:
1, SSS(8.2685g, 0.040mol), Hydroxyethyl acrylate (HEA, 1.5467g, 0.013mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0121g, 5.3 * 10
-5Mol), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio Hydroxyethyl acrylate type functional polystyrene sodium sulfonate
2, electronic balance accurately takes by weighing PEG N220(45.000g, 0.0225mol), polyether glycol N220(5.0000g, 0.0025mol), DMPA(1.0700g, 0.008mol) place the 250ml four-hole boiling flask that agitator is housed, be heated to 140 ℃ of moisture of removing in the raw material with temperature adjustable electrically heated device while stirring.Be cooled to below 65 ℃ and add TDI(6.3162g, 0.0363mol), be warming up to 80 ℃ of isothermal reactions again about two hours, be cooled to 70 ℃ and add Diacetylmonoxime (0.5742g, 0.0066mol), isothermal reaction stops heating after 1.5 hours, be cooled to 40 ℃ and add deionized water, finally makes the end-blocking non-ionic water-based urethane of solid content 50% under this R value.
3, weigh in the balance and get in 1 functional polystyrene sodium sulfonate 2.0000g and be dissolved in and take by weighing masked non-ionic type aqueous polyurethane 4.0000g in 2 in the beaker that fills the 8.0000g deionized water again, be positioned in the beaker, add appropriate amount of deionized water and make the solution of solid content 20%, stirring gets final product
4, with the template and the doping agent (1.0435g that make in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (95.1941g) and magneton, add EDOT (2.0584g again, 0.0147mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (4.8169,0.02113mol) and ferric sulfate (0.0294g, 7.35 * 10
-5Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is 3.2 k Ω/ after the seasoning, and square resistance is 1.1k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein R ' is in the B segment
R ' ' is-CH
3The ratio of y and x is 1:4;
Wherein B segment molecule amount is 50000
R in the C segment wherein
1Polyether segment z=45, m=0.
Wherein the mass ratio of B and C is 1:1; B, C total mass and A mass ratio are 0.1:1.
Embodiment 2(preparation of PEDOT water dispersion II)
Template and doping agent are Propylene glycol monoacrylate type functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane multipolymer in the PEDOT water dispersion II, wherein Propylene glycol monoacrylate and Sodium styrene sulfonate mol ratio are the multipolymer of 1:1 in the functional polystyrene sodium sulfonate, and wherein initiator amount and two total moles monomer ratios are 0.005:1; R(NCO/OH in the masked non-ionic type aqueous polyurethane)=1.6, PEG content 60%; Functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane copolymerization mass ratio are 10:1; Thing template and doping agent and EDOT mass ratio are 3:1; In the water dispersion preparation process, oxygenant, catalyzer and EDOT monomer mole ratio are respectively 4:1 and 0.001:1.
Concrete preparation method and step are as follows:
1, SSS(8.2685g, 0.040mol), Propylene glycol monoacrylate (HPA, 6.9141g, 0.041mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the ammonium persulphate ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0912g, 4 * 10
-4Mol), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio Propylene glycol monoacrylate type functional polystyrene sodium sulfonate
2, electronic balance accurately takes by weighing PEG(Mn=200) (3.0000g, 0.015mol), polyether glycol (Mn=200) (2.0000g, 0.010mol), DMPA(1.0700g, 0.008mol) place the 250ml four-hole boiling flask that agitator is housed, be heated to 140 ℃ of moisture of removing in the raw material with temperature adjustable electrically heated device while stirring.Be cooled to below 65 ℃ and add TDI(9.1900g, 0.0528mol), be cooled to 70 ℃ and add Diacetylmonoxime (4.1600g, 0.0198mol), isothermal reaction stops heating after 1.5 hours, be cooled to 40 ℃ and add deionized water, finally make the end-blocking non-ionic water-based urethane of solid content 50% under this R value.
3, weigh in the balance and get that functional polystyrene sodium sulfonate 5.0000g is dissolved in the beaker that fills the 15.0000g deionized water in 1, take by weighing masked non-ionic type aqueous polyurethane 1.0000g in 2 again, be positioned in the beaker, add appropriate amount of deionized water again and make solid content 20% solution stirring and evenly get final product
4, with template and doping agent (5.0135g in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (90.1941g) and magneton, add EDOT (0.3416g again, 0.0024mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (1.8240,0.008mol) and ferric sulfate (0.0005g, 2 * 10
-6Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is 107 k Ω/ after the seasoning, and square resistance is 77 k Ω/ after 140 ℃ of bakings.
Finally making the product structure formula is:
Wherein in the B segment in the R structure R ' be
R ' ' is-CH
3The ratio of y and x is 1:1
Wherein B segment molecule amount is 20000;
R in the C segment wherein
1Polyether segment z=5, m=0;
Wherein B and C segment mass ratio are 10:1; The total mass of B and C and the mass ratio of A are 3:1.
Embodiment 3The preparation of poly-(3,4-ethene dioxythiophene) (being PEDOT) water dispersion III
Template and doping agent are functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane multipolymer in the PEDOT water dispersion III, wherein the functional polystyrene sodium sulfonate is that acrylate hydroxyl ethyl ester and Sodium styrene sulfonate mol ratio are the 1:4 multipolymer, and its initiator amount and two monomer integral molar quantity ratios are 0.002:1; Masked non-ionic type aqueous polyurethane R(NCO/OH)=1.2, PEG content 10%, functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane copolymerization mass ratio are 5:1; Template and doping agent and EDOT mass ratio are 3:1; In the water dispersion preparation process, oxygenant, catalyzer and EDOT mol ratio are respectively 1.5:1 and 0.002:1.
Concrete preparation method and step are as follows:
1, SSS(8.2685g, 0.040mol), Hydroxyethyl acrylate (HEA, 1.5467g, 0.013mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0242g, 1.0 * 10
-4Mol), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio Hydroxyethyl acrylate type functional polystyrene sodium sulfonate
2, electronic balance accurately takes by weighing PEG N220(5.0000g, 0.0025mol), polyether glycol N220(45.0000g, 0.0225mol), DMPA(1.0700g, 0.008mol) place the 250ml four-hole boiling flask that agitator is housed, be heated to 140 ℃ of moisture of removing in the raw material with temperature adjustable electrically heated device while stirring.Be cooled to below 65 ℃ and add TDI(6.8904g, 0.0396mol), be warming up to 80 ℃ of isothermal reactions again about two hours, be cooled to 70 ℃ and add Diacetylmonoxime (1.1484g, 0.0132mol), isothermal reaction stops heating after 1.5 hours, be cooled to 40 ℃ and add deionized water, finally makes the end-blocking non-ionic water-based urethane of solid content 50% under this R value.
3, weigh in the balance and get in 1 functional polystyrene sodium sulfonate 2.5000g and be dissolved in and take by weighing masked non-ionic type aqueous polyurethane 1.0000g in 2 in the beaker that fills the 8.0000g deionized water again, be positioned in the beaker, add appropriate amount of deionized water and make the solution of solid content 20%, stirring gets final product.
4, with the template and the doping agent (5.0135g that make in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (95.1941g) and magneton, add EDOT (0.3416g again, 0.0024mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (0.8208g, 0.0036mol) and ferric sulfate (0.0019g, 4.8 * 10
-6Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is 99k Ω/ after the seasoning, and square resistance is 52k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein R ' is in the B segment
R ' ' is-CH
3The ratio of y and x is 1:4;
Wherein B segment molecule amount is 60000
R in the C segment wherein
1Polyether segment z=45, m=0;
Wherein the mass ratio of B and C is 5:1; B, C total mass and A mass ratio are 3:1.
Embodiment 4(preparation of PEDOT water dispersion IV)
Template and doping agent are functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane multipolymer in the PEDOT water dispersion IV, wherein the functional polystyrene sodium sulfonate is that Propylene glycol monoacrylate and Sodium styrene sulfonate mol ratio are the multipolymer of 1:8, and wherein initiator and two monomer integral molar quantity ratios are 0.002:1; The R of end-sealed type anion-type water-thinned polyurethane (NCO/OH)=1.6, DMPA content 20%; Functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane copolymerization mass ratio are 3:1; Thing template and doping agent and EDOT mass ratio are 50:1; Oxygenant, catalyzer and EDOT monomer molar amount ratio are respectively 1.5:1 and 0.002:1 in the dispersion preparation process.
Concrete preparation method and step are as follows:
1, SSS(9.1073g, 0.044mol), Propylene glycol monoacrylate (HPA, 0.8270g, 0.006mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0228g), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio Propylene glycol monoacrylate type functional polystyrene sodium sulfonate
2, DMPA (10.0000g, 0.075mol) and PPG N220(40.0000g, 0.020mol) join in the four-hole boiling flask that agitator is housed, being warming up to 140 ℃ ~ 160 ℃ about 10min goes out behind the moisture in the raw material, be cooled to 50 ℃ ~ 60 ℃, add TDI(26.4480g, 0.152mol), be warming up to 80 ~ 85 ℃ of reaction 2 ~ 2.5h, be cooled to room temperature, add 0.35mol butanone regulation system viscosity, add MEKO(9.9180g again, 0.114mol), stable be warming up to 70 ~ 75 ℃ of reaction 2 ~ 2.5h, add TEA(7.5750g, 0.075mol), keep 10min that it is stirred, add 0.20mol acetone and regulate viscosity, last high-speed stirring is scattered in certain water gaging, gets solid content and be 30% end-sealed type anion aqueous polyurethane
3, weigh in the balance and get that functional polystyrene sodium sulfonate 1.5000g is dissolved in the beaker that fills 10.0000g water in 1, take by weighing end-sealed type anion-type water-thinned polyurethane 1.0000g in 2 again, be positioned in the beaker, add appropriate amount of deionized water again and make the solution stirring of solid content 20% and evenly get final product
4, with template and doping agent (25.0135g in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (90.1941g) and magneton, add EDOT (0.1028g again, 0.0007mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (0.2394,0.0011mol) and ferric sulfate (0.0009g, 2.1 * 10
-6Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is after the seasoning, 159 k Ω/, and square resistance is 88k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein in the B segment in the R structure R ' be
R ' ' is-CH
3The mass ratio of y and x is 8:1;
Wherein B segment molecule amount is 320000;
R in the C segment wherein
1Polyether segment z is that 0, m is 35;
Wherein the mass ratio of B and C is 3:1; The total mass of B and C and the mass ratio of A are 50:1.
Embodiment 5(preparation of PEDOT water dispersion V)
Template and doping agent are functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane multipolymer in the PEDOT water dispersion V, wherein the functional polystyrene sodium sulfonate is that Propylene glycol monoacrylate and Sodium styrene sulfonate mol ratio are the multipolymer of 1:8, and wherein initiator and two monomer integral molar quantity ratios are 0.002:1; The R of end-sealed type anion-type water-thinned polyurethane (NCO/OH)=1.6, DMPA content 10%; Functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane copolymerization mass ratio are 3:1; Thing template and doping agent and EDOT mass ratio 3:1; Oxygenant, catalyzer and EDOT monomer molar amount ratio are respectively 1.5:1 and 0.002:1 in the dispersion preparation process.
Concrete preparation method and step are as follows:
1, SSS(9.1073g, 0.044mol), Propylene glycol monoacrylate (HPA, 0.8270g, 0.006mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0228g), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio Propylene glycol monoacrylate type functional polystyrene sodium sulfonate
2, DMPA (5.0000g, 0.0375mol) and PPG (Mn=200) (4.0000g, 0.020mol) join in the four-hole boiling flask that agitator is housed, being warming up to 140 ℃ ~ 160 ℃ about 10min goes out behind the moisture in the raw material, be cooled to 50 ℃ ~ 60 ℃, add TDI(16.0080g, 0.092mol), be warming up to 80 ~ 85 ℃ of reaction 2 ~ 2.5h, be cooled to room temperature, add 0.35mol butanone regulation system viscosity, add MEKO(6.003g again, 0.069mol), stable be warming up to 70 ~ 75 ℃ of reaction 2 ~ 2.5h, add TEA(7.5750g, 0.075mol), keep 10min that it is stirred, add 0.20mol acetone and regulate viscosity, last high-speed stirring is scattered in certain water gaging, gets solid content and be 30% end-sealed type anion aqueous polyurethane
3, weigh in the balance and get that functional polystyrene sodium sulfonate 1.5000g is dissolved in the beaker that fills 10.0000g water in 1, take by weighing end-sealed type anion-type water-thinned polyurethane 1.0000g in 2 again, be positioned in the beaker, add appropriate amount of deionized water again and make the solution stirring of solid content 20% and evenly get final product
4, with template and doping agent (1.5421g in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (90.1941g) and magneton, add EDOT (0.1028g again, 0.0007mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (0.2394,0.0011mol) and ferric sulfate (0.0009g, 2.1 * 10
-6Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is after the seasoning, 149 k Ω/, and square resistance is 79k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein in the B segment in the R structure R ' be
R ' ' is-CH
3The mass ratio of y and x is 8:1;
Wherein B segment molecule amount is 320000;
R in the C segment wherein
1Polyether segment z is that 0, m is 4;
Wherein the mass ratio of B and C is 3:1; The total mass of B and C and the mass ratio of A are 3:1.
Embodiment 6(preparation of PEDOT water dispersion VI)
Template and doping agent are functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane multipolymer in the PEDOT water dispersion VI, wherein the functional polystyrene sodium sulfonate is that glycidyl methacrylate vinylformic acid and Sodium styrene sulfonate mol ratio are the multipolymer of 1:4, and wherein initiator and two monomer integral molar quantity ratios are 0.002:1; The R of end-sealed type anion-type water-thinned polyurethane (NCO/OH)=2.0, DMPA content 5%; Functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane copolymerization mass ratio are 5:1; Thing template and doping agent and EDOT mass ratio are 0.01:1; Oxygenant, catalyzer and EDOT monomer mole ratio are respectively 0.5:1 and 0.002:1 in the water dispersion preparation process.
Concrete preparation method and step are as follows:
1, SSS(9.0351g, 0.0439mol), glycidyl methacrylate (GMA, 1.8684g, 0.0144mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0266g), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio glycidyl methacrylate functional polystyrene sodium sulfonate
2, DMPA (1.9048g, 0.014mol) and polyester polyol N220(40.0000g, 0.020mol) join in the four-hole boiling flask that agitator is housed, being warming up to 140 ℃ ~ 160 ℃ about 10min goes out behind the moisture in the raw material, be cooled to 50 ℃ ~ 60 ℃, add TDI(2.9580g, 0.017mol), be warming up to 80 ~ 85 ℃ of reaction 2 ~ 2.5h, be cooled to room temperature, add 0.35mol butanone regulation system viscosity, add MEKO(2.9580g again, 0.034mol), stable be warming up to 70 ℃ ~ 75 ℃ reaction 2 ~ 2.5h, add TEA(1.4140g, 0.014mol), keep 10min that it is stirred, add 0.20mol acetone and regulate viscosity, last high-speed stirring is scattered in the 84.0000g water, gets solid content and be 30% end-sealed type anion aqueous polyurethane
3, weigh in the balance and get that functional polystyrene sodium sulfonate 2.5000g is dissolved in the beaker that fills 10.0000g water in 1, take by weighing end-sealed type anion-type water-thinned polyurethane 1.0000g in 2 again, be positioned in the beaker, add appropriate amount of deionized water again and make the solution stirring of solid content 20% and evenly get final product
4, with template and doping agent (0.1035g in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (95.1941g) and magneton, add EDOT (2.0584g again, 0.0147mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (1.6058,0.0072mol) and ferric sulfate (0.0118g, 2.9 * 10
-5Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is 0.2k Ω/ after the seasoning, and square resistance is 0.09k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein in the B segment in the R structure R ' be
R ' ' is-H; The ratio of y and x is 4:1
Wherein B segment molecule amount is 200000;
R in the C segment wherein
1Polyester segment y is 35.
Wherein the mass ratio of B and C is 5:1; The total mass of B and C and the mass ratio of A are 0.01:1.
Embodiment 7(preparation of PEDOT water dispersion VII)
Template and doping agent are functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane multipolymer in the PEDOT water dispersion VII, wherein the functional polystyrene sodium sulfonate is that glycidyl acrylate and Sodium styrene sulfonate mol ratio are the multipolymer of 1:10, and wherein initiator and two monomer integral molar quantity ratios are 0.002:1; R in the end-sealed type anion-type water-thinned polyurethane (NCO/OH)=1.2, DMPA content 2%; Functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane copolymerization mass ratio are 10:1; Thing template and doping agent and EDOT mass ratio are 0.25:1; Oxygenant, catalyzer and EDOT monomer molar amount ratio are respectively 1.5:1 and 0.002:1 in the dispersion preparation process.
Concrete preparation method and step are as follows:
1, SSS(10.922g, 0.0532mol), glycidyl methacrylate (GMA, 0.6996g, 0.0053mol), H
2O (35.0000g) places the four-hole boiling flask that reflux condensate device, temperature are taken into account magneton is housed, and vacuumizes logical nitrogen or argon gas, is warming up to about 85 ℃, adds the initiator ((NH that is dissolved in the 4.0000g deionized water
4)
2S
2O
8, 0.0266g), be warming up to 90 ℃ of isothermal reactions and stop after 4 hours, with prepared product repeatedly resolution of precipitate of ethanol and water, vacuum drying treatment obtains the final white solid, i.e. this ratio glycidyl methacrylate functional polystyrene sodium sulfonate
2, DMPA (0.8163g, 0.0061mol) and polyester polyol (Mn=200) (40.0000g, 0.20mol) join in the four-hole boiling flask that agitator is housed, being warming up to 140 ℃ ~ 160 ℃ about 10min goes out behind the moisture in the raw material, be cooled to 50 ~ 60 ℃, add TDI(43.0337g, 0.2473mol), be warming up to 80 ~ 85 ℃ of reaction 2 ~ 2.5h, be cooled to room temperature, add 0.35mol butanone regulation system viscosity, add MEKO(7.1688g again, 0.0824mol), stable be warming up to 70 ~ 75 ℃ of reaction 2 ~ 2.5h, add TEA(0.6162g, 0.0061mol), keep 10min that it is stirred, add 0.20mol acetone and regulate viscosity, last high-speed stirring is scattered in certain water gaging, gets solid content and be 30% end-sealed type anion aqueous polyurethane
3, weigh in the balance and get that functional polystyrene sodium sulfonate 5.0000g is dissolved in the beaker that fills the 15.0000g deionized water in 1, take by weighing end-sealed type anion-type water-thinned polyurethane 1.0000g in 2 again, be positioned in the beaker, add appropriate amount of deionized water again and make solid content 20% solution stirring and evenly get final product
4, with template and doping agent (1.2516g in 3,20%) is dissolved in the four-hole boiling flask that fills deionized water (94.1941g) and magneton, add EDOT (1.0284g again, 0.007mol), be stirred to fast be uniformly dispersed after, add the ammonium persulphate be dissolved in the 5.0000g deionized water (2.3940,0.0105mol) and ferric sulfate (0.0084g, 2.1 * 10
-5Mol), keep stirring and be heated to 30 ℃ fast, react after 18～20 hours, obtain dark blue solution.Drip after the centrifugal treating and be coated with film forming, the four-point probe measurment square resistance is 44 k Ω/ after the seasoning, and square resistance is 20k Ω/ after 140 ℃ of bakings
Finally making the product structure formula is:
Wherein B segment molecule amount is 250000;
R in the C segment wherein
1Polyester segment y is 4;
Wherein the mass ratio of B and C is 10:1; The total mass of B and C and the mass ratio of A are 0.25:1.
Claims (4)
1. the preparation method of crosslinkable poly-(3,4-ethene dioxythiophene) water dispersion is characterized in that carrying out according to following steps:
(1) preparation of functional polystyrene sodium sulfonate, concrete preparation method is as follows:
Sodium styrene sulfonate, esters of acrylic acid, initiator, solvent place the four-hole boiling flask that fills magneton and reflux condensate device according to a certain percentage, vacuumize logical nitrogen or argon gas, be heated to 90 ℃, stirring reaction 3～5 hours, obtain faint yellow clarification thick liquid, with prepared material ethanol sedimentation, obtain white cotton-shaped solid, again dissolve with deionized water again, repeat 3～4 final white flockss of said process with ethanol and deionized water again and use 60 ℃～80 ℃ dryings of vacuum drying oven 10 hours, obtain the final white solid product;
(2) end-sealed type Synthesis of Waterborne Polyurethane:
(a) masked non-ionic type Synthesis of Waterborne Polyurethane:
Polyvalent alcohol and hydrophilic monomer be placed at according to a certain percentage be equipped with in the agitator four-hole boiling flask, after 140 ℃ of high-temperature stirring dewater, be cooled to below 65 ℃, add vulcabond, be warming up to 80 ℃ of isothermal reactions after two hours, be cooled to 70 ℃ and add end-capping reagent, isothermal reaction 1～2 hour, be cooled under 40 ℃ and add gauge water, preparation is finished; Product is finally made the aqueous solution of solid content 50%;
(3) preparation of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer:
With functional polystyrene sodium sulfonate and masked non-ionic type aqueous polyurethane according to certain mass than mixing, namely obtain a kind of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer as PEDOT water dispersion template and doping agent, wherein the solid masses of two components is than being (1～10): 1;
(4) preparation of poly-(3,4-ethene dioxythiophene) water dispersion:
In the preparation of poly-(3,4-ethene dioxythiophene) water dispersion, be template and doping agent with sodium polystyrene sulfonate and the end-sealed type aqueous polyurethane multipolymer for preparing, wherein said template and doping agent are product in the step (3), and concrete preparation method is as follows:
3,4-ethene dioxythiophene, template and doping agent, oxygenant, catalyzer join in the four-hole boiling flask that fills deionized water and magneton according to a certain percentage, stir fast, react 12～24 hours under 30 ℃ of conditions, finally obtain the mazarine dispersion liquid;
Poly-(3, the 4-ethene dioxythiophene) water dispersion that finally makes is with centrifugal aftertreatment, the centrifugal back removal impurity of carrying out, leave and take precipitation with distilled water diluting after dispersing and dissolving again, same again mode is centrifugal, and 3 times repeatedly, last precipitate with deionized water dilution back ultra-sonic dispersion got final product in 1 hour;
Wherein esters of acrylic acid comprises Hydroxyethyl acrylate described in the step (1), Propylene glycol monoacrylate, glycidyl methacrylate, vinylformic acid hydroxy butyl ester, the mol ratio of add-on and Sodium styrene sulfonate is 1:(1～10), the preparation molecular weight of product is at 20000～320000; Wherein said initiator is Sodium Persulfate, and ammonium persulphate, Potassium Persulphate, consumption are 0.001～0.005 times of integral molar quantity; Wherein said solvent is deionized water, and consumption is 80% of reaction system total mass;
Wherein polyvalent alcohol described in (a) is polyoxyethylene glycol and polyether glycol in the step (2), and both use simultaneously, and mass ratio is 10%～90%; Wherein said hydrophilic monomer is dimethylol propionic acid, and its add-on is 2%～20% of polyvalent alcohol quality; Wherein said solvent is butanone; Wherein said vulcabond is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, dimethoxy-biphenyl vulcabond, methyl caproate-2,6-vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, consumption and polyvalent alcohol integral molar quantity ratio are (1.1～2): 1; Wherein end-capping reagent is para-chlorophenol, p-NP, cresols, phenol, pyrocatechol, methoxyphenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, 1,1,1,3,3,3-chlordene-2-propyl alcohol, Acetanilide, the N-methylacetamide, hexanolactam, succimide, di-t-butyl amine, pentanoic, Potassium hydrogen sulfite, sodium bisulfite, Sodium Pyrosulfite, ammonium bisulfite, boric acid, cyclohexanone-oxime, methyl ethyl ketoxime, the diphenylmethyl ketoxime, Diacetylmonoxime, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline, consumption be with the vulcabond molar weight than (0.1～1): 1.
2. according to claim 1 crosslinkable poly-(3, the 4-ethene dioxythiophene) preparation method of water dispersion, it is characterized in that also can adopting in the step (2) wherein the preparation of (b) end-sealed type anion-type water-thinned polyurethane: polyvalent alcohol and hydrophilic monomer are placed at according to a certain percentage are equipped with in the agitator four-hole boiling flask, after 140 ℃ of high-temperature stirring dewater, be cooled to 50 ℃～below 60 ℃, add vulcabond, be warming up to 80 ℃ of isothermal reactions two hours again, add end-capping reagent again, be warming up to 70 ℃ ~ 75 ℃ reaction 2 ~ 2.5h, be cooled to room temperature and add triethylamine, keep 10min that it is stirred, add acetone and regulate viscosity, last high-speed stirring is scattered in the water, makes solid content and be 30% end-sealed type anion-type water-thinned polyurethane product; Wherein said polyvalent alcohol is polypropylene glycol (PPG-N220), polyoxyethylene glycol, polypropylene glycol and glycol copolymer, polytetrahydrofuran, polyester polyol;
Wherein said hydrophilic monomer is dimethylol propionic acid (DMPA), and usage quantity is 2%～20% of polyvalent alcohol quality;
Wherein said vulcabond is tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), dimethoxy-biphenyl vulcabond (DADI), methyl caproate-2,6-vulcabond (LDI)), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), consumption and polyvalent alcohol molar weight ratio are (1.1～2): 1;
Wherein end-capping reagent is para-chlorophenol, p-NP, cresols, phenol, pyrocatechol, methoxyphenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, 1,1,1,3,3,3-chlordene-2-propyl alcohol, Acetanilide, the N-methylacetamide, hexanolactam, succimide, di-t-butyl amine, pentanoic, Potassium hydrogen sulfite, sodium bisulfite, Sodium Pyrosulfite, ammonium bisulfite, boric acid, cyclohexanone-oxime, methyl ethyl ketoxime, the diphenylmethyl ketoxime, Diacetylmonoxime, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline, consumption are and vulcabond molar ratio (0.1～1): 1; Wherein triethylamine consumption and DMPA mol ratio are 1:1.
3. according to claim 1 crosslinkable poly-(3, the 4-ethene dioxythiophene) preparation method of water dispersion, it is characterized in that wherein adopting in the step (3) with functional polystyrene sodium sulfonate and end-sealed type anion-type water-thinned polyurethane according to certain mass than mixing, namely obtain a kind of functional polystyrene sodium sulfonate and end-sealed type aqueous polyurethane multipolymer as PEDOT water dispersion template and doping agent, wherein the solid masses of two components is than being (1～10): 1.
4. the preparation method of crosslinkable poly-(3,4-ethene dioxythiophene) water dispersion according to claim 1 is characterized in that wherein the wherein said template of step (4) and doping agent are sodium polystyrene sulfonate and end-sealed type aqueous polyurethane multipolymer; Template and doping agent and EDOT mass ratio are (0.01～50): 1;
Wherein said oxygenant is ammonium persulphate, Sodium Persulfate, Potassium Persulphate, with the EDOT mol ratio be (0.5～4): 1; Wherein above-mentioned catalyzer is ferric sulfate, and consumption and EDOT mol ratio are (0.001～0.005): 1; Wherein the add-on of above-mentioned deionized water is for making m(3,4-ethene dioxythiophene+template and doping agent)/m (3,4-ethene dioxythiophene+template and doping agent+deionized water)=1%～15%.
5. according to resulting crosslinkable poly-(3, the 4-ethene dioxythiophene) water dispersion of the described preparation method of one of claim 1-4.
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