CN113979991A - UV conductive prepolymer and preparation method thereof, and transparent conductive UV curing coating and preparation method thereof - Google Patents
UV conductive prepolymer and preparation method thereof, and transparent conductive UV curing coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003848 UV Light-Curing Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 claims description 5
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical group N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012974 tin catalyst Substances 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- NRQHBNNTBIDSRK-YRNVUSSQSA-N (4e)-4-[(4-methoxyphenyl)methylidene]-2-methyl-1,3-oxazol-5-one Chemical compound C1=CC(OC)=CC=C1\C=C\1C(=O)OC(C)=N/1 NRQHBNNTBIDSRK-YRNVUSSQSA-N 0.000 claims description 4
- IFLKEBSJTZGCJG-UHFFFAOYSA-N 3-methylthiophene-2-carboxylic acid Chemical compound CC=1C=CSC=1C(O)=O IFLKEBSJTZGCJG-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- -1 small-molecule polyol Chemical class 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- RCNOGGGBSSVMAS-UHFFFAOYSA-N 2-thiophen-3-ylacetic acid Chemical compound OC(=O)CC=1C=CSC=1 RCNOGGGBSSVMAS-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 14
- 239000011521 glass Substances 0.000 abstract description 7
- 239000002985 plastic film Substances 0.000 abstract description 5
- 229920006255 plastic film Polymers 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012811 non-conductive material Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a UV conductive prepolymer and a preparation method thereof, and the preparation method comprises the following steps: (1) under the protection of inert gas and under the condition of containing solvent and catalyst, reacting micromolecular polyalcohol with thiophene derivative with unit carboxyl on ortho-position or meta-position to prepare resin prepolymer; (2) under the condition of containing catalyst, polymerization inhibitor and solvent, the resin prepolymer and the monomer react to prepare the UV conductive prepolymer, wherein one end of the monomer contains isocyanate and the other end contains acrylate double bond. The invention also provides a transparent conductive UV curing coating and a preparation method thereof. The UV conductive prepolymer contains a polythiophene group and a light-curable photosensitive group, is beneficial to preparing the coating in a UV light curing mode, has better integral transparency and excellent conductive performance, and can be coated on plastic films and glass to prepare conductive films and conductive glass, so that the conductive high-molecular polythiophene material can be really applied to the market to form a commercialized product.
Description
Technical Field
The invention relates to the technical field of conductive high polymer materials, in particular to a UV conductive prepolymer and a preparation method thereof, and a transparent conductive UV curing coating and a preparation method thereof.
Background
Compared with the traditional metal conductive materials, the conductive polymer materials such as Polyaniline (PAN), polypyrrole (PPy), Polythiophene (PT) and the like have quite large application prospects due to the advantages of light weight, good ductility, easiness in processing, corrosion resistance and the like. Conductive polymers as a new class of photoelectric materials have been the focus of research both at home and abroad, have gradually achieved industrialization, and have been widely applied to dye-sensitized solar cells, electroluminescent materials, flexible transparent electrodes, conductive and antistatic coatings, and the like.
The polythiophene has a structure similar to an aromatic ring, has good stability in the environment, and can also maintain the stability in a doped state; different synthetic methods can be adopted to obtain different substituted polythiophene derivatives, thereby realizing different photoelectric characteristics. Therefore, polythiophene materials are the most widely researched and applied in conductive polymer materials.
The polythiophene materials are made into a coating form, so that the polythiophene materials can be coated on a plastic film, and the insulating plastic surface has conductive performance, which is an important direction of research. However, the cohesion performance, dissolution/fusion performance, weather resistance and stable conductivity maintaining performance of the polythiophene materials are poor, and the development of the polythiophene materials in the direction of conductive coatings is restricted.
For example, korean SKC corporation patents CN 101389710B and CN 101848962B disclose a method for preparing a transparent conductive coating material based on a polythiophene system, which is prepared by mixing materials such as a polythiophene aqueous solution, an aprotic polar solvent, an alcohol solvent, a melamine resin, and a binder. Chinese patent CN 101665616B is a conductive coating prepared by mixing polythiophene aqueous solution, polar solvent, alcohol solvent, film-forming resin, coupling agent, surfactant and other materials.
The technology adopts the polythiophene aqueous solution as the basic material of the conductive coating, can realize the conductivity and the transparency of the coating and meet partial requirements. Its disadvantages are low surface strength, easy abrasion, and poor weatherability and stable conductivity. The possible reasons are: the polythiophene is a high polymer with poor cohesive strength, and in order to simply meet the transparency of the technology, an aqueous system is adopted, multiple components are simply mixed, and part of the strength performance of the coating resin is sacrificed, so that the surface strength of the coating is not high, the coating is easy to wear, and the coating is easy to fall off after long-time sunlight irradiation. In addition, a large amount of non-conductive materials are added in the system, so that the overall conductive performance of the coating is reduced. Therefore, the transparent conductive coating adopts a water-based polythiophene system, can be used as a permanent antistatic coating, but has a certain gap from the transparent conductive coating which really meets the requirements of commercial application.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a UV conductive prepolymer and a preparation method thereof, and a transparent conductive UV curing coating and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a UV conductive prepolymer, comprising the steps of:
(1) under the protection of inert gas and under the condition of containing solvent and catalyst, reacting micromolecular polyalcohol with thiophene derivative with unit carboxyl on ortho-position or meta-position to prepare resin prepolymer;
(2) under the condition of containing catalyst, polymerization inhibitor and solvent, the resin prepolymer and monomer are reacted to prepare UV conductive prepolymer,
wherein one end of the monomer contains isocyanate and the other end contains an acrylate double bond.
Preferably, the small molecule polyol is at least one selected from ethylene glycol, glycerol, trimethylolpropane, trimethylolethane and pentaerythritol.
Preferably, the thiophene derivative is selected from any one of 2-thiophenecarboxylic acid, 3-methyl-2-thiophenecarboxylic acid, 3-thiophenecarboxylic acid and 3-thiopheneacetic acid.
Preferably, in step (1) and step (2), the solvent may be at least one selected from ethyl acetate, toluene, butyl acetate, butanone, methyl isobutyl ketone, and N-methyl pyrrolidone.
Preferably, the inert gas in step (1) can be, but is not limited to, nitrogen or carbon dioxide.
Preferably, in the step (1), the catalyst is selected from at least one of p-toluenesulfonic acid and tetrabutyl titanate;
in the step (2), the catalyst is selected from organic tin catalysts, and specifically, but not limited to, dibutyltin dilaurate.
Preferably, the molar ratio of the organic tin catalyst to the isocyanate in the monomer is 0.05-0.1%, and the molar ratio of the polymerization inhibitor to the acrylic double bond in the monomer is 0.1-0.5%.
Preferably, the monomer is selected from isocyanate ethyl acrylate or isocyanate ethyl methacrylate.
Preferably, the polymerization inhibitor is selected from p-hydroxyanisole or hydroquinone.
Specifically, the thiophene derivative is a UV conductive prepolymer which is prepared from 3-thiophenecarboxylic acid, micromolecular polyol and isocyanate ethyl methacrylate, and is named as a compound 1, and the reaction principle is as follows:
the small molecular polyol is selected from trihydric alcohol and tetrahydric alcohol, and the compound 2 and the compound 3 can be respectively obtained by the same synthetic steps as follows:
when the monomer is selected from isocyanate ethyl acrylate, the compound 4, the compound 5 and the compound 6 can be obtained by the same synthetic steps, and the following steps are adopted:
wherein R is the inner core of the polyol.
The invention provides a UV conductive prepolymer, which is prepared by the preparation method.
Preferably, the UV conductive prepolymer can be, but is not limited to, compounds 1-6.
The invention provides a transparent conductive UV curing coating in a third aspect, which is prepared from the following raw materials:
preferably, the UV reactive diluent is selected from mono-functional acrylate and multi-functional acrylate which are matched according to the mass ratio of 1: 1; wherein, the monofunctional acrylate can be selected from at least one of hydroxyethyl methacrylate (HEMA) and isobornyl acrylate (IBOA), and the multifunctional acrylate can be selected from at least one of 1, 6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA) and pentaerythritol triacrylate (PETA).
Preferably, the length of the silver nanowire is 5-30 μm, and the diameter is 10-100 nm.
Preferably, the photoinitiator is at least one of 1173 photoinitiator, 184 photoinitiator, TPO photoinitiator, ITX photoinitiator, 907 photoinitiator, 369 photoinitiator.
Preferably, the leveling agent is at least one of BYK-333, Tego-100, hum 810 and Efka-3883.
Preferably, the dispersant is at least one of BYK-105, Tego-710, hum 912, Efka-4800.
Preferably, the solvent is at least one of ethyl acetate, butyl acetate, butanone and methyl isobutyl ketone.
The invention provides a preparation method of a transparent conductive UV curing coating, which comprises the following steps:
firstly, stirring and dispersing the nano silver wires and the dispersing agent uniformly in 10-30 parts of solvent, then adding the photoinitiator, stirring and dissolving, then adding the UV conductive prepolymer, the UV active diluent and the rest solvent, stirring uniformly, finally adding the leveling agent, stirring uniformly, and filtering by a filter element to obtain the transparent conductive UV curing coating.
The invention has the following beneficial effects:
(1) the UV conductive prepolymer disclosed by the invention contains a polythiophene group and a light-curable photosensitive group, is beneficial to preparing a coating in a UV light curing mode, has better integral transparency and excellent conductive performance, can be coated on plastic films and glass and can be prepared into conductive films and conductive glass, so that the conductive high-molecular polythiophene material can be really applied to the market to form a commercialized product.
(2) The UV conductive prepolymer realizes that the coating adopts a UV photocuring mode, has high crosslinking strength, improves the surface strength and the cohesive strength of the conductive coating, and has the advantages of strong wear resistance and weather resistance, difficult shedding and good stability; also has the advantages of high curing speed, convenient use and good adhesive force on substrates such as metal, plastic films, glass and the like.
(3) One end of the monomer contains isocyanate and the other end contains acrylate double bond, so that the preparation process is greatly simplified, and the proportion of the photocuring unit is higher, thereby being beneficial to the curing of the subsequent coating.
(4) The nano silver wire is added into the coating, so that the influence of a non-conductive material in a system on the conductivity is compensated, the overall conductivity of the coating is improved, and the overall transparency of the coating is not reduced. The addition of the nano silver wire also forms an organic/inorganic nano composite material system, thereby improving the strength of the coating.
(5) The production condition of the coating is simple and mild, no special high-temperature environment or special high-pressure condition is used, the production efficiency is high, and the cost is low.
(6) The paint can be coated on plastic films and glass, and can be made into conductive films and conductive glass.
Detailed Description
The following examples are intended to illustrate the present invention, but not to limit the scope of the claims of the present invention.
Example 1
A preparation method of a UV conductive prepolymer comprises the following steps:
(1) under the protection of nitrogen, mixing ethylene glycol and 3-thiophenecarboxylic acid according to the molar ratio of 1: 1 in a reaction kettle, starting stirring at normal temperature,
dissolving p-methyl benzene sulfonic acid which is 1-3 percent of the total mass of reactants in N-methyl pyrrolidone to prepare a catalyst solution with the concentration of 1 percent,
and dropwise adding the catalyst solution into the reaction kettle, heating to 110-150 ℃ after dropwise adding is finished in 30-60 min, starting a condensation reflux device, and stirring for reacting for 6-8 h. Water generated by alcohol acid condensation in the reaction process forms an azeotrope with the solvent, the solvent evaporates to carry water out of the reaction through the condensation reflux process, the solvent flows back to the reaction kettle again after oil-water separation of the water separator, and the resin prepolymer is prepared after the reaction is finished;
adding isocyanate ethyl methacrylate into a resin prepolymer, adding the isocyanate ethyl methacrylate and the resin prepolymer according to the molar ratio of 1: 1, setting the reaction temperature at 70-80 ℃, then dropwise adding an organic tin catalyst solution (with the concentration of 0.05%) and a p-hydroxyanisole solution (with the concentration of 1%), wherein the solvent is N-methyl pyrrolidone, the molar ratio of the organic tin catalyst to isocyanate in a monomer is 0.05-0.1%, the molar ratio of the polymerization inhibitor to acrylic double bonds in the monomer is 0.1-0.5%, the total dropwise adding time is 3 hours, and reacting for 5-6 hours to prepare the UV conductive prepolymer, namely the compound 1.
Example 2
This example is the same as example 1 except that in this example, a small molecule polyol is selected from glycerin to make a UV conductive prepolymer, compound 2. The rest is the same as in example 1 and is not described in detail here.
Example 3
This example is the same as example 1 except that in this example, the monomer was selected from the group consisting of isocyanate ethyl acrylate to make a UV conductive prepolymer, compound 4. The rest is the same as in example 1 and is not described in detail here.
Example 4
This example is the same as example 1 except that in this example, the small molecule polyol is selected from glycerol and the monomer is selected from isocyanate ethyl acrylate to produce a UV conductive prepolymer, compound 5. The rest is the same as in example 1 and is not described in detail here.
Example 5
A transparent conductive UV-curable coating is prepared from the following raw materials:
the UV-reactive diluent is selected from the group consisting of hydroxyethyl methacrylate (HEMA) and 1, 6-hexanediol diacrylate (HDDA).
Examples 6 to 8
Examples 6 to 8 are substantially the same as example 5 except that the UV-conductive prepolymers of examples 6 to 8 are compound 2, compound 4 and compound 5, respectively, and the rest are the same as example 1 and will not be described in detail.
Comparative example 1
A transparent conductive UV-curable coating is prepared from the following raw materials:
the UV-reactive diluent is selected from the group consisting of hydroxyethyl methacrylate (HEMA) and 1, 6-hexanediol diacrylate (HDDA).
Application test methods and results:
coating the coating on a PET film with the thickness of 50 mu m by a wire rod, drying for 2min in an oven at the temperature of 120 ℃ to volatilize the solvent, and then irradiating under the UV illumination condition with the wavelength of 280-395 nm, wherein the illumination energy is 300-600 mJ/cm2And completely curing the coating to prepare the transparent conductive film, and performing related tests, wherein the test results are shown in table 1.
The electric conductivity is measured according to the test standard GB/T11007-2008;
the square resistance is tested according to the standard GB/T17473.3-2008;
the light transmittance and the haze are measured according to GB/T2410-2008;
and (4) an adhesion test with the test standard of GB/T33049-2016.
TABLE 1 test results
The test results in table 1 show that the transparent conductive UV curing coating which has good overall transparency, excellent conductive performance, stability and low possibility of falling off can be obtained by the UV conductive prepolymer according to the technical scheme of the application.
The data of comparative example 1 show that the introduction of the nano silver wire in the technical scheme of the application can compensate the influence of the non-conductive material in the system on the conductivity, improve the overall conductivity of the coating, and simultaneously does not significantly reduce the overall transparency of the coating.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a UV conductive prepolymer is characterized by comprising the following steps:
(1) under the protection of inert gas and under the condition of containing solvent and catalyst, reacting micromolecular polyalcohol with thiophene derivative with unit carboxyl on ortho-position or meta-position to prepare resin prepolymer;
(2) under the condition of containing catalyst, polymerization inhibitor and solvent, the resin prepolymer and monomer are reacted to prepare UV conductive prepolymer,
wherein one end of the monomer contains isocyanate and the other end contains an acrylate double bond.
2. The method of claim 1, wherein the small-molecule polyol is at least one selected from the group consisting of ethylene glycol, glycerol, trimethylolpropane, trimethylolethane, and pentaerythritol.
3. The method of preparing a UV conductive prepolymer according to claim 1, wherein the thiophene derivative is any one selected from the group consisting of 2-thiophenecarboxylic acid, 3-methyl-2-thiophenecarboxylic acid, 3-thiophenecarboxylic acid and 3-thiopheneacetic acid.
4. The method of preparing a UV conductive prepolymer according to claim 1, wherein in step (1) and step (2), the solvent is at least one selected from the group consisting of ethyl acetate, toluene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and N-methylpyrrolidone.
5. The method for preparing a UV conductive prepolymer according to claim 1, wherein,
in the step (1), the catalyst is at least one selected from p-toluenesulfonic acid and tetrabutyl titanate;
in the step (2), the catalyst is selected from organic tin catalysts.
6. The method of preparing a UV conductive prepolymer according to claim 1 wherein the monomer is selected from the group consisting of isocyanate ethyl acrylate and isocyanate ethyl methacrylate.
7. The method of preparing a UV conductive prepolymer according to claim 1 wherein the polymerization inhibitor is selected from the group consisting of p-hydroxyanisole and hydroquinone.
8. A UV conductive prepolymer prepared by the method of any one of claims 1 to 7.
9. The transparent conductive UV curing coating is characterized by comprising the following preparation raw materials:
100 parts of the UV conductive prepolymer as claimed in claim 8;
10. a method for preparing the transparent conductive UV curable coating of claim 9, comprising the steps of:
firstly, stirring and dispersing the nano silver wires and the dispersing agent uniformly in 10-30 parts of solvent, then adding the photoinitiator, stirring and dissolving, then adding the UV conductive prepolymer, the UV active diluent and the rest solvent, stirring uniformly, finally adding the leveling agent, stirring uniformly, and filtering by a filter element to obtain the transparent conductive UV curing coating.
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| CN115160908A (en) * | 2022-07-06 | 2022-10-11 | 海利得新材料研究(上海)有限公司 | Solvent-free UV (ultraviolet) matte coating and preparation method thereof |
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| CN103642383A (en) * | 2013-12-04 | 2014-03-19 | 江南大学 | Preparation method of intrinsic photo-cured anti-static resin |
| CN104629611A (en) * | 2013-11-14 | 2015-05-20 | 江南大学 | Method for preparing light-curing conductive coating |
| CN104927029A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Preparation method of UV-curable branched polythiophene derivative conductive polymer material |
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| CN104629611A (en) * | 2013-11-14 | 2015-05-20 | 江南大学 | Method for preparing light-curing conductive coating |
| CN103642383A (en) * | 2013-12-04 | 2014-03-19 | 江南大学 | Preparation method of intrinsic photo-cured anti-static resin |
| CN104927029A (en) * | 2014-03-20 | 2015-09-23 | 江南大学 | Preparation method of UV-curable branched polythiophene derivative conductive polymer material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160908A (en) * | 2022-07-06 | 2022-10-11 | 海利得新材料研究(上海)有限公司 | Solvent-free UV (ultraviolet) matte coating and preparation method thereof |
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