CN111196866A - Preparation method of transparent conductive small ball, transparent conductive small ball and application - Google Patents
Preparation method of transparent conductive small ball, transparent conductive small ball and application Download PDFInfo
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- CN111196866A CN111196866A CN202010001489.XA CN202010001489A CN111196866A CN 111196866 A CN111196866 A CN 111196866A CN 202010001489 A CN202010001489 A CN 202010001489A CN 111196866 A CN111196866 A CN 111196866A
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- transparent conductive
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- eutectic solvent
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- photoinitiator
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000008188 pellet Substances 0.000 claims abstract description 33
- 230000005496 eutectics Effects 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 238000001746 injection moulding Methods 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 239000011324 bead Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000005693 optoelectronics Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
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- 238000004528 spin coating Methods 0.000 claims description 3
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- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000370 acceptor Substances 0.000 description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 101150085511 PEDS1 gene Proteins 0.000 description 5
- 102100037592 Plasmanylethanolamine desaturase Human genes 0.000 description 5
- 244000028419 Styrax benzoin Species 0.000 description 5
- 235000000126 Styrax benzoin Nutrition 0.000 description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 description 5
- 229960002130 benzoin Drugs 0.000 description 5
- 235000019382 gum benzoic Nutrition 0.000 description 5
- 229920003199 poly(diethylsiloxane) Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 4
- 235000019743 Choline chloride Nutrition 0.000 description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 4
- 229960003178 choline chloride Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRSYWPMGIIAQIW-UHFFFAOYSA-N 5-bromo-2,3-dihydro-1,4-benzodioxine-7-carbaldehyde Chemical compound O1CCOC2=C1C=C(C=O)C=C2Br HRSYWPMGIIAQIW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000005563 spheronization Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- 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 1
- VSYDLUXFKAXBBY-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O VSYDLUXFKAXBBY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- -1 alkyl benzophenone Chemical compound 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- PRTXHLNVNLADCY-UHFFFAOYSA-N azanium;prop-2-enoic acid;chloride Chemical compound [NH4+].[Cl-].OC(=O)C=C PRTXHLNVNLADCY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229950010582 betaine anhydrous Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0016—Processes relating to electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of a transparent conductive small ball, the transparent conductive small ball and application thereof, wherein the preparation method comprises the following steps: (1) uniformly mixing a polymerizable eutectic solvent, a photoinitiator and a crosslinking agent to form a mixed solution, wherein the dosage of the photoinitiator is 1-3% of the polymerizable eutectic solvent, and the dosage of the crosslinking agent is 1-3% of the polymerizable eutectic solvent; (2) and (3) adopting a continuous controllable fluid method injection molding technology to make the formed liquid drops into transparent conductive pellets under the irradiation of ultraviolet light. The preparation method is rapid, simple and convenient, the equipment is easy to obtain, the cost is low, and no surfactant is needed, so that the preparation method is completely green and environment-friendly.
Description
Technical Field
The invention relates to the field of electronics, in particular to a preparation method of a transparent conductive small ball, the transparent conductive small ball and application.
Background
The conductive pellets can be used in electronic devices, such as flexible pressure sensing devices, human-computer interfaces, optoelectronic devices, and conductive films. At present, the conductive pellets are usually prepared by conductive materials (carbon materials, metal nanoparticles, nanowires or conductive polymers, etc.) to impart conductivity thereto, and are prepared by various methods such as spraying, solvent evaporation or microfluidics, for example, chinese patent CN104342646A discloses that conductive gold pellets are prepared by a cyanide-free gold plating method. However, the above conductive beads are complicated, time-consuming and expensive in preparation process, and the method of coating the above dark color conductive material may limit the prepared conductive beads to optical transparency, which is not favorable for the development of photoelectric devices.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a preparation method of a transparent conductive small ball, which is quick, simple and convenient, has easily obtained equipment and low cost, does not need to use a surfactant, is completely green and environment-friendly to the environment and can prepare spherical particles of 50 um-4 mm.
Another object of the present invention is to provide a transparent conductive pellet prepared by the above method, which has excellent mechanical properties, high sensitivity and stable electrical signal.
The invention also provides application of the transparent conductive small ball in an electroluminescent device, a pressure sensor or an optoelectronic device.
The technical scheme adopted by the invention is as follows:
(1) uniformly mixing a polymerizable eutectic solvent, a photoinitiator and a crosslinking agent to form a mixed solution, wherein the dosage of the photoinitiator is 1-3% of the polymerizable eutectic solvent, and the dosage of the crosslinking agent is 1-3% of the polymerizable eutectic solvent; preferably, the amount of the photoinitiator is 1-2% of the polymerizable eutectic solvent, and the amount of the cross-linking agent is 1.5-2.5% of the polymerizable eutectic solvent.
(2) Under the irradiation of ultraviolet light, the transparent conductive small balls are manufactured by adopting a continuous controllable fluid method injection molding technology.
The technical scheme develops a continuous controllable fluid injection molding technology and realizes the rapid preparation of conductive transparent pellets of 50 um-4 mm. The green polymerizable eutectic solvent (PDES) adopted by the main material component of the transparent conductive pellet is one of key composition factors of the transparent conductive pellet with excellent performance, the mixed solution of the PDES, the initiator and the cross-linking agent has excellent transparency and good elasticity after being cured under the irradiation of ultraviolet light, and a hydrogen bond acceptor in a PDES system transmits ions in the mixed solution, so that the transparent conductive pellet also has excellent conductivity, and in addition, the polymerizable PDES system does not contain volatile organic compounds in the preparation and polymerization processes. The invention further prepares the PDES into the transparent conductive small ball by a continuous controllable fluid method, and the transparent conductive small ball has excellent mechanical property and high sensitivity and stable electric signals. The preparation method has the advantages of no need of expensive preparation, low preparation cost, simple and quick preparation process, capability of obtaining 50-4 mm spherical small particles by injection molding within 2-3 s, no need of any surfactant (the surfactant can damage the environment and change the interfacial property of the spherical particles), and complete environmental protection.
In the experimental process, the dosage of the photoinitiator and the cross-linking agent has great influence on whether the transparent gel with the small ball structure can be prepared.
Preferably, step S2 is:
a: preparation of injection: sucking the mixed liquid into an injector, wherein an ultraviolet light source is arranged on one side of the injector;
b: polymerizing and forming: and (3) spraying the mixed solution from the injection head at a constant speed, irradiating the sprayed liquid by ultraviolet light, and polymerizing and forming to obtain the transparent conductive pellets.
Preferably, the preparation method further comprises the step of pulling out the transparent conductive small balls prepared and molded by polymerization reaction by using the carrying object.
Preferably, the preparation method comprises the following steps:
s1: preparation of polymerizable eutectic solvent: mixing a hydrogen bond acceptor and a hydrogen bond donor to form a polymerizable eutectic solvent;
s2: preparing a mixed solution: adding a photoinitiator and a cross-linking agent into a polymerizable eutectic solvent, and uniformly mixing to obtain a mixed solution; preferably, the photoinitiator is a mixture of Irgacure1173 and TPO;
s3: preparation of injection: sucking the mixed liquid into an injector, wherein an ultraviolet light source is arranged on one side of the injector, the horizontal distance between the ultraviolet light source and the injector is 16-20 cm, the vertical distance is 15-17 cm, and the power is 2800-3500 w;
s4: polymerizing and forming: spraying the mixed liquid from the injection head at a constant speed, and simultaneously, receiving the materials at a speed of 15-17 cm s-1The mixture is drawn out at the speed, and is polymerized and molded by the ultraviolet light irradiation to obtain the transparent conductive pellets. Preferably, the speed of the mixed liquid sprayed from the injection head is 0.3-0.35 mL s-1。
The preparation method of the invention adopts UV irradiation to lead the hydrogen bond donor containing double bonds in the polymerizable eutectic solvent to be rapidly polymerized into spheres, and the external force and the surface tension determine the balanced shape of the liquid drop, and the result shows that the surface tension (making the polymerizable eutectic solvent into spheres) of the polymerizable eutectic solvent is far greater than the external force in the polymerization process; the surface properties of the pellets are not affected during the preparation process.
The transparent conductive small ball prepared by the preparation method.
The radius of the transparent conductive small ball is adjustable and is 50 um-4 mm. More preferably, the radius of the transparent conductive small ball is 2 mm.
The transparent conductive small ball is applied to electroluminescent devices, pressure sensors or optoelectronic devices. The transparent conductive small ball not only has excellent mechanical property, but also has high sensitivity and stable electric signals, and can be applied to electroluminescent devices, pressure sensors or optoelectronic devices.
An electroluminescent device comprises a conductive glass layer, a luminescent layer, a transparent conductive bead layer consisting of a plurality of transparent conductive beads and a non-conductive glass layer which are sequentially laminated.
The light-emitting layer is a ZnS Cu/Dow Corning SYLGARD 184 light-emitting layer.
The preparation method of the luminescent layer comprises the following steps: the electroluminescent powder ZnS with certain mass: adding Cu into the uniformly mixed Dow Corning SYLGARD 184, and uniformly stirring to obtain a light-emitting layer opaque solution, wherein the weight ratio of the Dow Corning SYLGARD 184 to the ZnS: Cu particles is (1-2): (1-2), spin-coating at a speed of 800-1200 r/s for 45-80 s, and curing at 75-85 ℃ for 1.5-2.5 h.
The polymerizable eutectic solvent is obtained by mixing a hydrogen bond acceptor and a hydrogen bond donor at 60-100 ℃, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1:3, and the hydrogen bond donor is acrylic acid or methacrylic acid.
Preferably, the hydrogen bond acceptor is one or more of choline chloride, ammonium chloride, betaine anhydrous and betaine monohydrate.
Preferably, the hydrogen bond acceptor is choline chloride, the hydrogen bond donor is acrylic acid and methacrylic acid, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is not less than 1: 1.
More preferably, the hydrogen bond acceptor is choline chloride, the hydrogen bond donor is acrylic acid, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 2.
The photoinitiator may be two or more of benzoin and derivatives photoinitiator, benzoin-based photoinitiator, alkyl benzophenone photoinitiator, and acylphosphorus oxide photoinitiator, specifically, the benzoin and derivatives photoinitiator may be benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, etc. the benzil-based initiator may be diphenylethanone, α -dimethoxy- α -phenylacetophenone, etc. the alkyl phenone may be α -diethoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylphenone, etc. the acylphosphorus oxide may be aroylphosphine oxide, bisbenzoylphenylphosphine oxide, etc. more specifically, the photoinitiator may be two or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine (TPO), 1173 (2-hydroxy-2-methyl-1-phenylpropanone), 1-hydroxycyclohexylphenylketone (1-hydroxycyclohexylphenylketone), etc. the ratio of the mass ratio of the TPO 3 to the gacure (Irgacure) is preferably: (1172-gacure-1).
Preferably, the cross-linking agent is one or more of polyethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts a continuous controllable fluid method to prepare transparent gel pellets with regular spherical structure and excellent conductivity, the pellets not only show excellent mechanical property, but also have high sensitivity and stable electric signals, and an electroluminescent device is successfully constructed, thereby providing a new visual field for the development of transparent high-performance electronic devices;
(2) the continuous controllable fluid method developed by the invention does not need to use a surfactant or expensive experimental equipment, the time consumption of the preparation process is short, the rapid preparation of the conductive pellets of 50 um-4 mm is realized, and the preparation process is completely green and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing transparent conductive pellets.
Fig. 2 is an external view of the transparent conductive pellet prepared in example 1.
FIG. 3 is a graph of compression sensor performance.
FIG. 4 is a graph showing the formation process and emission performance of an electroluminescent device according to example 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The transparent conductive pellets are prepared by the polymerizable eutectic solvent through a continuous controllable fluid method injection molding technology, so that the excellent performance of the polymerizable eutectic solvent can be kept, the Young modulus and the bearing capacity of the polymerizable eutectic solvent are further improved, and the transparent conductive pellets have high sensitivity and stable electric signals.
Examples 1 to 7
A transparent conductive pellet is prepared by the following steps:
s1: preparation of polymerizable eutectic solvent: hydrogen bond acceptor choline chloride and hydrogen bond donor acrylic acid are mixed in a molar ratio of 1:2, heating and stirring at 90 ℃ for about 3 hours to form a uniform colorless polymerizable eutectic solvent;
s2: preparing a mixed solution: adding a photoinitiator (1173 and TPO which are mixed according to the mass ratio of 1:1) and a crosslinking agent polyethylene glycol diacrylate into a polymerizable eutectic solvent, and uniformly mixing to obtain a mixed solution, wherein the mass fractions of the photoinitiator and the crosslinking agent relative to the polymerizable eutectic solvent are respectively shown in table 1;
s3: preparation of injection: sucking the mixed solution into a 1 ml injector, wherein an ultraviolet light source is arranged on one side of the injector, the horizontal distance between the ultraviolet light source and the injector is 17cm, the vertical distance is 16cm, and the power is 3000 w;
s4: polymerizing and forming: the mixed solution is treated with 0.33mL s-1Is ejected from a 20G equipped injection head at a constant rate, while the receiving material is ejected at 16cm s-1The mixture is drawn out at the speed, and is polymerized and molded by the ultraviolet light irradiation to obtain the transparent conductive pellets.
TABLE 1
Examples 8 to 9
A transparent conductive pellet was prepared in substantially the same manner as in example 1 except that the polymerizable eutectic solvent used was different in composition, as shown in table 2.
TABLE 2
| Examples | Hydrogen bond acceptors | Hydrogen bond donors | Molar ratio (hydrogen bond acceptor: hydrogen bond donor) |
| Example 8 | Betaine monohydrate | Acrylic acid | 1:2 |
| Example 9 | Ammonium chloride | Acrylic acid | 1:2 |
Examples 10 to 14
A transparent conductive pellet was prepared in substantially the same manner as in example 1, except that the injection preparation and polymerization process were different in process parameters, as shown in Table 3.
TABLE 3
The diameter of the transparent conductive pellets prepared in examples 1 to 14 was about 2 mm.
Example 15
As shown in fig. 4, an electroluminescent device includes a conductive glass, a light emitting layer, a transparent conductive bead layer composed of a plurality of transparent conductive beads, and a non-conductive glass layer, which are sequentially stacked. Specifically, in this embodiment, the light-emitting layer is a ZnS: Cu/Dow Corning SYLGARD 184 light-emitting layer.
The preparation process of the luminescent layer comprises the following steps: the electroluminescent powder ZnS with certain mass: adding Cu into uniformly mixed Dow Corning SYLGARD 184, and uniformly stirring to obtain a light-emitting layer opaque solution, wherein the weight ratio of the Dow Corning SYLGARD 184 to ZnS: Cu particles is 1:1, spin coating at 1000r/s for 60s, and curing at 80 ℃ for 2 h.
The preparation process of the electroluminescent device comprises the following steps: the light-emitting diode comprises conductive glass, a light-emitting layer, a transparent conductive small ball layer and a non-conductive glass layer, wherein the transparent conductive small ball layer is formed by a plurality of transparent conductive small balls which are sequentially laminated from bottom to top.
Comparative example 1
The preparation process was substantially the same as in example 1 except that the photoinitiator in comparative example 1 was used in an amount of 4% by mass based on the total mass of the polymerizable eutectic solvent.
Comparative example 2
The preparation process was substantially the same as in example 5 except that the amount of the crosslinking agent used in comparative example 2 was 0.5% by mass of the total mass of the polymerizable eutectic solvent, and no spheronization occurred.
Comparative example 3
The procedure was substantially the same as in example 4 except that the photoinitiator 2959 was used instead of the photoinitiator in example 4 (1173 to TPO mass ratio 1:1), and no spheronization occurred.
Comparative example 4
The procedure was substantially the same as in example 4 except that in the preparation for injection in this comparative example 4, the ultraviolet light source was spaced 25cm horizontally from the injector and was not allowed to form a sphere.
The products of examples 1 to 14, comparative example 1, comparative example 2, comparative example 3 and comparative example 4 were subjected to performance tests, and the specific test items and test results are shown in table 4.
TABLE 4
| Test items | Conductivity S m-1 | Balling property | Appearance of the product |
| Example 1 | 0.025 | Ball forming | Is transparent |
| Example 2 | 0.024 | Ball forming | Is transparent |
| Example 3 | 0.021 | Ball forming | Is transparent |
| Example 4 | 0.011 | Ball forming | Is transparent |
| Example 5 | 0.023 | Ball forming | Is transparent |
| Example 6 | 0.017 | Ball forming | Is transparent |
| Example 7 | 0.015 | Ball forming | Is transparent |
| Example 8 | 0.023 | Ball forming | Is transparent |
| Example 9 | 0.025 | Ball forming | Is transparent |
| Example 10 | 0.020 | Ball forming | Is transparent |
| Example 11 | 0.027 | Ball forming | Is transparent |
| Example 12 | 0.025 | Ball forming | Is transparent |
| Example 13 | 0.025 | Ball forming | Is transparent |
| Example 14 | 0.022 | Ball forming | Is transparent |
| Comparative example 1 | 0.015 | Ball forming | Is not transparent |
| Comparative example 2 | - | Does not form balls | - |
| Comparative example 3 | - | Does not form balls | - |
| Comparative example 4 | - | Does not form balls | - |
Fig. 4 shows the forming process and the light emitting performance of the electroluminescent device according to example 15. It was also found during the experiments that the brightness of the electroluminescent device increased with increasing pressure. The transparent conductive pellets may be arranged in different patterns, and thus the light emitting shape may be patterned.
Fig. 3 is a graph showing the resistance response stability of 500 turns of the transparent conductive pellets prepared in example 1 under a compressive strain of 80%. As can be seen from fig. 3, the resistance change during the cyclic compression process has good repeatability, which indicates that the transparent conductive pellet of the present invention is a reliable and stable compression sensor.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a transparent conductive small ball is characterized by comprising the following steps:
(1) uniformly mixing a polymerizable eutectic solvent, a photoinitiator and a crosslinking agent to form a mixed solution, wherein the dosage of the photoinitiator is 1-3% of the polymerizable eutectic solvent, and the dosage of the crosslinking agent is 1-3% of the polymerizable eutectic solvent;
(2) under the irradiation of ultraviolet light, the transparent conductive small balls are manufactured by adopting a continuous controllable fluid method injection molding technology.
2. The method according to claim 1, wherein step S2 is:
a: preparation of injection: sucking the mixed liquid into an injector, wherein an ultraviolet light source is arranged on one side of the injector;
b: polymerizing and forming: and (3) spraying the mixed solution from the injection head at a constant speed, irradiating the sprayed liquid by ultraviolet light, and polymerizing and forming to obtain the transparent conductive pellets.
3. The method of claim 1, further comprising the step of drawing the transparent conductive pellets molded by polymerization out by using a receiving material.
4. The method of claim 1, comprising the steps of:
s1: preparation of polymerizable eutectic solvent: mixing a hydrogen bond acceptor and a hydrogen bond donor to form a polymerizable eutectic solvent;
s2: preparing a mixed solution: adding a photoinitiator and a cross-linking agent into a polymerizable eutectic solvent, and uniformly mixing to obtain a mixed solution;
s3: preparation of injection: sucking the mixed liquid into an injector, wherein an ultraviolet light source is arranged on one side of the injector, the horizontal distance between the ultraviolet light source and the injector is 16-20 cm, the vertical distance is 15-17 cm, and the power is 2800-3500 w;
s4: polymerizing and forming: spraying the mixed liquid from the injection head at a constant speed, and simultaneously, receiving the materials at a speed of 15-17 cm s-1The mixture is drawn out at the speed, and is polymerized and molded by the ultraviolet light irradiation to obtain the transparent conductive pellets.
5. The transparent conductive pellets prepared by the preparation method according to any one of claims 1 to 4.
6. The transparent conductive pellet of claim 5, wherein the radius of the transparent conductive pellet is adjustable and is 50um to 4 mm.
7. Use of the transparent conductive pellets of claim 5 in an electroluminescent device, a pressure sensor or an optoelectronic device.
8. The use according to claim 7, wherein the electroluminescent device comprises a conductive glass, a light-emitting layer, a layer of transparent conductive beads comprising a plurality of transparent conductive beads, and a layer of non-conductive glass, which are laminated in this order.
9. Use according to claim 7, wherein the light-emitting layer is a ZnS: Cu/Dow Corning SYLGARD 184 light-emitting layer.
10. The use according to claim 7, wherein the light-emitting layer is prepared by a method comprising: the electroluminescent powder ZnS with certain mass: adding Cu into uniformly mixed Dow Corning SYLGARD 184, and uniformly stirring to obtain a light-emitting layer opaque solution, wherein the weight ratio of the Dow Corning SYLGARD 184 to ZnS: Cu particles is (1-2): (1-2), spin-coating at a speed of 800-1200 r/s for 45-80 s, and curing at 75-85 ℃ for 1.5-2.5 h.
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