CN116515349A - Tara adhesive conductive coating and preparation method thereof - Google Patents
Tara adhesive conductive coating and preparation method thereof Download PDFInfo
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- CN116515349A CN116515349A CN202211579590.9A CN202211579590A CN116515349A CN 116515349 A CN116515349 A CN 116515349A CN 202211579590 A CN202211579590 A CN 202211579590A CN 116515349 A CN116515349 A CN 116515349A
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- conductive coating
- solution
- tara gum
- tara
- silver
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- 238000000576 coating method Methods 0.000 title claims abstract description 105
- 239000011248 coating agent Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 title claims abstract description 21
- 241000388430 Tara Species 0.000 title claims abstract description 21
- 239000000853 adhesive Substances 0.000 title claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 18
- 239000000213 tara gum Substances 0.000 claims abstract description 92
- 235000010491 tara gum Nutrition 0.000 claims abstract description 92
- -1 silver amide Chemical class 0.000 claims abstract description 46
- 239000002070 nanowire Substances 0.000 claims abstract description 45
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- 239000003755 preservative agent Substances 0.000 claims abstract description 39
- 230000002335 preservative effect Effects 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002562 thickening agent Substances 0.000 claims abstract description 38
- XHWHHMNORMIBBB-UHFFFAOYSA-N 2,2,3,3-tetrahydroxybutanedioic acid Chemical compound OC(=O)C(O)(O)C(O)(O)C(O)=O XHWHHMNORMIBBB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 91
- 238000003756 stirring Methods 0.000 claims description 52
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 36
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 27
- 101710134784 Agnoprotein Proteins 0.000 claims description 23
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 13
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 12
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- WJHHIVYNOVTVGY-UHFFFAOYSA-N methyl 3h-benzimidazole-5-carboxylate Chemical group COC(=O)C1=CC=C2N=CNC2=C1 WJHHIVYNOVTVGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000003431 cross linking reagent Substances 0.000 abstract description 10
- 239000002042 Silver nanowire Substances 0.000 abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011231 conductive filler Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- UXLRAFSUPRUBFW-UHFFFAOYSA-N silver;azanide Chemical compound [Ag]N UXLRAFSUPRUBFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 239000011120 plywood Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004026 adhesive bonding Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000013101 initial test Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a tara adhesive conductive coating and a preparation method thereof. The tara gum conductive coating comprises an amino silver nanowire, tara gum, water, dihydroxytartaric acid, a thickener and a preservative; according to the tara gum conductive coating, the silver amide nanowire is used as a conductive material, the tara gum is used as a matrix, and the construction of a polymer network system with double acting forces of ester bonds and hydrogen bonds in the conductive coating is realized through a dihydroxytartaric acid cross-linking agent; silver nanowires are traditional one-dimensional conductive fillers, and have high length-diameter ratio and high conductivity, so that the material has good conductivity; meanwhile, the surface of the silver amide nanowire is provided with rich amino active groups, and an ester bond and hydrogen bond polymer network is formed by crosslinking dihydroxyl tartaric acid and tara gum. The conductive coating disclosed by the invention has better self-healing performance, can prolong the service life of the conductive coating, and has better mechanical properties.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a tara adhesive conductive coating and a preparation method thereof.
Background
The development of the conductive coating is half century so far, and the conductive coating is a functional coating which is rapidly developed along with the modern science and technology. Currently, conductive coatings play a significant role in a variety of military and civil industrial fields such as electronics, electrical appliances, aviation, printing, and the like. Silver nanowires (Ag NWs) are one-dimensional conductive materials, have the characteristics of excellent conductivity, high length-diameter ratio, large specific surface area and the like, can be coated with the same coating area as other metal fillers by only a very small amount of silver nanowires in the coating, and improve the conductivity of the coating. The prior art discloses a flexible transparent conductive coating doped with silver nanowires and graphene, wherein the conductive filler used by the flexible transparent conductive coating is silver nanowires and graphene, the dispersing agent is butyl acetate, ethylene glycol butyl ether or modified hydroxyl-containing polymer, the solvent is water, ethanol or isopropanol, and the binder is siloxane polymer, polyurethane or polyacrylic acid; but the conductive coating does not have self-healing properties. The prior art also discloses an anti-lightning conductive coating, but the mass fraction of the used metal silver powder is as high as 35-70%, and the cost is high.
Based on the defects existing in the current conductive coating, improvement is needed.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention provides a tara gum conductive coating and a preparation method thereof.
In a first aspect, the invention provides a tara gum conductive coating, which comprises the following raw materials in parts by weight: 1 to 15 parts of silver amide nanowire, 30 to 40 parts of tara gum, 80 to 100 parts of water, 1 to 10 parts of dihydroxytartaric acid, 0.2 to 0.5 part of thickener and 0.2 to 0.5 part of preservative.
Preferably, the tara gum conductive coating comprises at least one of carboxymethyl cellulose and sodium carboxymethyl cellulose.
Preferably, the tara gum conductive coating and the preservative is benzimidazole-5-methyl formate.
Preferably, the preparation method of the tara gum conductive coating and the silver amide nanowire comprises the following steps:
CuCl is added 2 Dissolving in water to obtain CuCl 2 A solution;
dissolving NaBr in water to obtain NaBr solution;
dissolving polyvinylpyrrolidone in ethylene glycol to obtain polyvinylpyrrolidone solution;
AgNO is to be carried out 3 Dissolving in glycol to obtain AgNO 3 A solution;
placing ethylene glycol into a container, heating to 145-155 ℃ for reaction for 0.5-1.5 h, and then adding CuCl 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature;
and (3) centrifugally separating a product obtained by the reaction to obtain a precipitate, and centrifugally washing the precipitate with acetone to finally obtain the silver amide nanowire.
Preferably, the Tara adhesive conductive coating, cuCl 2 The concentration of the solution is 2-6 mM;
the concentration of NaBr solution is 0.5-2 mM;
dissolving 1-3 g of polyvinylpyrrolidone in 5-15 mL of ethylene glycol to obtain polyvinylpyrrolidone solution;
0.5 g to 3g AgNO 3 Dissolving in 5-15 mL glycol to obtain AgNO 3 A solution.
Preferably, the tara gum conductive paint is prepared by placing glycol into a container, heating to 145-155 ℃ for reaction for 0.5-1.5 h, and then adding CuCl 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature; wherein, glycol, cuCl 2 Solution, naBr solution, polyvinylpyrrolidone solution, agNO 3 The volume ratio of the solution to the ethylenediamine is (60-100) mL (400-600) mu L (50-150) mu L (5-15) mL (3-7) mL.
In a second aspect, the invention also provides a preparation method of the tara gum conductive coating, which comprises the following steps:
adding the tara gum into water for stirring, adding the silver amide nanowires and the dihydroxytartaric acid, stirring, performing a crosslinking reaction, and adding a thickener and a preservative to obtain the tara gum conductive coating.
Preferably, in the preparation method of the Tara adhesive conductive coating, the reaction temperature of the crosslinking reaction is 35-45 ℃ and the reaction time is 0.5-2 h.
Preferably, in the preparation method of the tara gum conductive coating, the tara gum is added into water for stirring for 20-60 min.
Compared with the prior art, the tara adhesive conductive coating and the preparation method thereof have the following beneficial effects:
the tara gum conductive coating comprises an amino silver nanowire, tara gum, water, dihydroxytartaric acid, a thickener and a preservative; according to the tara gum conductive coating, the silver amide nanowire is used as a conductive material, the tara gum is used as a matrix, and the construction of a polymer network system with double acting forces of ester bonds and hydrogen bonds in the conductive coating is realized through a dihydroxytartaric acid cross-linking agent; silver nanowires are traditional one-dimensional conductive fillers, and have high length-diameter ratio and high conductivity, so that the material has good conductivity; meanwhile, the surface of the silver amide nanowire is provided with rich amino active groups, and an ester bond and hydrogen bond polymer network is formed by crosslinking dihydroxyl tartaric acid and tara gum. The conductive coating disclosed by the invention has better self-healing performance, can prolong the service life of the conductive coating, and has better mechanical properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 shows the bonding strength of the conductive coating materials prepared in examples 1 to 8 and comparative example 1 of the present invention;
fig. 2 shows the bonding strength of the repaired conductive paint in examples 1 to 8 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials in parts by weight: 1 to 15 parts of silver amide nanowire, 30 to 40 parts of tara gum, 80 to 100 parts of water, 1 to 10 parts of dihydroxytartaric acid, 0.2 to 0.5 part of thickener and 0.2 to 0.5 part of preservative.
According to the tara gum conductive coating, the silver amide nanowire is used as a conductive material, the tara gum is used as a matrix, and the construction of a polymer network system with double acting forces of ester bonds and hydrogen bonds in the conductive coating is realized through a dihydroxytartaric acid cross-linking agent; silver nanowires are traditional one-dimensional conductive fillers, and have high length-diameter ratio and high conductivity, so that the material has good conductivity; meanwhile, the surface of the silver amide nanowire is provided with rich amino active groups, and an ester bond and hydrogen bond polymer network is formed by crosslinking dihydroxyl tartaric acid and tara gum. The conductive coating disclosed by the invention has better self-healing performance, can prolong the service life of the conductive coating, and has better mechanical properties.
Specifically, the Tara gum of the application is also called Tara gum (Tara gum), tara bean gum (Peruvian carob), tara gum and Tara gum, which is prepared by grinding endosperm of Tara (C aesalpin iaspinosa) seeds of the leguminous family as a raw material, and the processing mode is similar to other bean gums.
Specifically, the preparation method of the silver amide nanowire adopted by the application comprises the following steps:
s1, cuCl 2 Dissolving in water to obtain CuCl 2 A solution;
s2, dissolving NaBr in water to obtain NaBr solution;
s3, dissolving polyvinylpyrrolidone (PVP) in Ethylene Glycol (EG) to obtain a polyvinylpyrrolidone solution;
s4, agNO 3 Dissolved in glycolAgNO obtained in (EG) 3 A solution;
s5, placing Ethylene Glycol (EG) into a container, heating to 145-155 ℃, reacting for 0.5-1.5 h, and then adding CuCl 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature;
and S6, centrifugally separating the product obtained by the reaction to obtain a precipitate, and centrifugally washing the precipitate with acetone to finally obtain the silver amide nanowire.
Specifically, in the above embodiment, cuCl 2 The concentration of the solution is 2-6 mM; the concentration of NaBr solution is 0.5-2 mM; dissolving 1-3 g of polyvinylpyrrolidone (PVP) in 5-15 mL of Ethylene Glycol (EG) to obtain a polyvinylpyrrolidone solution; 0.5 g to 3g AgNO 3 Dissolving in 5-15 mL of Ethylene Glycol (EG) to obtain AgNO 3 A solution.
Concretely, glycol (EG) is placed in a container, heated to 145-155 ℃ and reacted for 0.5-1.5 h, and then CuCl is added 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature; wherein Ethylene Glycol (EG), cuCl 2 Solution, naBr solution, polyvinylpyrrolidone solution, agNO 3 The volume ratio of the solution to the ethylenediamine is (60-100) mL (400-600) mu L (50-150) mu L (5-15) mL (3-7) mL.
Specifically, the dihydroxytartaric acid is used as a cross-linking agent, and the action principle is as follows:
(1) Dihydroxytartaric acid cross-linking agent and ortho-hydroxyl on tara to form polymer with ester bond
(2) OH in polymer having ester bond and NH on surface of silver amide nanowire (Ag NWs) 2 Forming intermolecular hydrogen bonds
In some embodiments, the thickener comprises at least one of carboxymethyl cellulose, sodium carboxymethyl cellulose.
In some embodiments, the preservative is methyl benzimidazole-5-carboxylate.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the tara gum conductive coating, which comprises the following steps:
adding the tara gum into water for stirring, adding the silver amide nanowires and the dihydroxytartaric acid, stirring, performing a crosslinking reaction, and adding a thickener and a preservative to obtain the tara gum conductive coating.
In some embodiments, the reaction temperature of the crosslinking reaction is 35 to 45 ℃ and the reaction time is 0.5 to 2 hours.
In some embodiments, the step of adding the tara gum to the water for agitation is performed for a period of 20 to 60 minutes.
In some embodiments, the tara gum is added into water for stirring, then the silver amide nanowire and the dihydroxytartaric acid are added, the stirring is carried out for 0.5 to 2 hours for crosslinking reaction, and then the thickener and the preservative are added, thus obtaining the tara gum conductive coating.
The conductive coating prepared by the method can realize better self-healing repair performance and can increase the mechanical property of the material by constructing a high polymer network system with double acting forces of ester bonds and hydrogen bonds in the conductive coating; the Tara adhesive has low cost and no toxicity, can be degraded, and can be recycled after being coated or sprayed on a base material; the preparation method of the tara gum conductive coating has the advantages of simple preparation process, short time consumption and wide raw material sources, is carried out under normal temperature conditions, can obtain the conductive coating with multiple functions of good adhesion performance, good conductivity, excellent self-healing performance, degradability and the like, and has good development prospect compared with the conductive coating with the same type.
The tara gum conductive coating of the present application and a method of preparing the same are further described in the following specific examples. This section further illustrates the summary of the invention in connection with specific embodiments, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The tara gum used in the following examples was purchased from wuhan Hua Xiangke biotechnology limited.
The preparation method of the silver amide nanowire used in the following examples specifically comprises the following steps:
s1, cuCl 2 Dissolving in water to obtain 4mM CuCl 2 A solution;
s2, dissolving NaBr in water to obtain a 1mM NaBr solution;
s3, dissolving 2g of polyvinylpyrrolidone (PVP, weight average molecular weight Mw=58000) in 10mL of Ethylene Glycol (EG) to obtain a polyvinylpyrrolidone solution;
S4、1g AgNO 3 dissolving in 10mL Ethylene Glycol (EG) to obtain AgNO 3 A solution;
s5, placing 80mL of Ethylene Glycol (EG) in a container, heating to 150 ℃, reacting for 1h, and then adding 500 mu L of 4mM CuCl 2 The solution and 100 mu L of 1mM NaBr solution are continuously reacted for 15min under stirring, and the polyvinylpyrrolidone solution obtained in the step S3 and the AgNO obtained in the step S4 are continuously added 3 Continuously reacting the solution with 5mL of ethylenediamine for 1.5h, stopping the reaction and cooling to room temperature;
s6, centrifugally separating the product obtained by the reaction at the speed of 6500rpm/min to obtain a precipitate, and centrifugally washing the precipitate with acetone to finally obtain the silver amide nanowire.
Example 1
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 2g of silver amide nanowires, 40g of tara gum, 100g of water, 3g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 2
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 4g of silver amide nanowires, 40g of tara gum, 100g of water, 3g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 3
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 6g of silver amide nanowires, 40g of tara gum, 100g of water, 3g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 4
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 8g of silver amide nanowires, 40g of tara gum, 100g of water, 3g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 5
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 10g of silver amide nanowires, 40g of tara gum, 100g of water, 3g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 6
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 10g of silver amide nanowires, 40g of tara gum, 100g of water, 5g of dihydroxytartaric acid, 0.25g of thickening agent and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 7
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 6g of silver amide nanowires, 40g of tara gum, 100g of water, 7g of dihydroxytartaric acid, 0.25g of thickener and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Example 8
The embodiment of the application provides a tara adhesive conductive coating, which comprises the following raw materials: 6g of silver amide nanowires, 40g of tara gum, 100g of water, 10g of dihydroxytartaric acid, 0.25g of thickener and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding dihydroxytartaric acid, stirring for 30min at 40 ℃ to perform a crosslinking reaction, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Comparative example 1
The comparative example provides a tara gum conductive coating, comprising the following raw materials: 10g of silver amide nanowires, 40g of tara gum, 100g of water, 0.25g of thickener and 0.25g of preservative;
wherein the thickener is carboxymethyl cellulose, and the preservative is benzimidazole-5-methyl formate.
The preparation method of the tara gum conductive coating comprises the following steps:
adding the tara gum into water, stirring for 25min, adding the silver amide nanowire, continuously stirring for 30min, adding the thickener and the preservative, and continuously stirring for 30min to obtain the tara gum conductive coating.
Performance testing
The conductive paints prepared in examples 1 to 8 and comparative example 1 were coated on a natural rubber of 2cm×1cm, and the prepared materials were subjected to resistance test at room temperature using a multimeter, and the thickness of the materials was measured. And the conductivity is calculated by a formula. The formula is as follows:
wherein σ represents conductivity, R represents resistance, L represents length, b represents width, and d represents thickness.
The conductive coatings prepared in examples 1 to 8 and comparative example 1 were poured into a polytetrafluoroethylene rectangular mold, dried at 50℃to form a film, and the prepared conductive coatings were subjected to a tensile test at room temperature using a universal tester to detect the tensile strength and elongation at break of the samples, wherein the sample size was 60X 10mm (length X width), the initial test distance between the two jigs was 20mm, and the samples were tested at a loading speed of 5 mm/min. The test results are shown in table 1 below.
TABLE 1 mechanical Properties and conductivities of conductive coatings prepared in different examples
Examples | Tensile Strength (MPa) | Elongation at break (%) | Conductivity (S/m) |
Example 1 | 3.65 | 63.5 | 3.16×10 -3 |
Example 2 | 4.13 | 50.3 | 2.08×10 -2 |
Example 3 | 4.88 | 41.6 | 1.00×10 -1 |
Example 4 | 5.76 | 32.1 | 3.12 |
Example 5 | 6.56 | 26.8 | 6.45 |
Example 6 | 7.53 | 28.6 | 6.50 |
Example 7 | 8.43 | 29.7 | 6.53 |
Example 8 | 9.55 | 31.2 | 6.58 |
Comparative example 1 | 1.35 | 22.3 | 6.43 |
As can be seen from table 1, with the gradual increase of the silver amide nanowires, the conductivity of the conductive coating is continuously increased, the elongation at break is gradually reduced, the influence of the crosslinking agent on the conductivity of the coating is very small, the dihydroxytartaric acid crosslinking agent is continuously added, a compact ester bond and hydrogen bond dual acting force crosslinking network is formed between the silver amide nanowires and the tara gum, and the tensile strength of the coating is greatly increased; this demonstrates that the addition of the dihydroxytartaric acid cross-linking agent can enhance the interfacial force between the silver amide nanowires and the tara gum, forming a conductive coating with excellent mechanical properties.
Referring to the specification of class II plywood in China national Standard (general plywood) (GB/T9846-2015), the plywood prepared from the conductive paint prepared in examples 1 to 8 and comparative example 1 was subjected to a bonding strength test. Each three-layer plywood is sawn into 9 test pieces with the size of 100 multiplied by 25mm and the gluing area of the test pieces of 25 multiplied by 25mm 2 . The test results are shown in FIG. 1.
As can be seen from fig. 1, the addition of the dihydroxytartaric acid crosslinking agent can effectively increase the bonding strength of the conductive coating. From examples 1 to 5, the bonding strength of the conductive coating slowly increases with increasing amount of the silver amide nanowires, and from examples 5 to 8, the addition of the dihydroxytartaric acid can significantly enhance the bonding strength of the conductive coating, because a polymer network system with compact ester bonds and hydrogen bond acting forces can be formed between the silver amide nanowires and the tara gum; whereas example 1 without the crosslinking agent failed to form a network of ester bonds, hydrogen bonds, the bond strength of the conductive coating was significantly reduced.
Self-healing performance test
The conductive coatings prepared in examples 1 to 8 were poured into a rectangular mold, dried at 50℃to form a film, and left to stand for 24 hours after being scratched on the material with a blade (self-repairing stage), the repaired material was subjected to a tensile test at room temperature using a universal tester to detect the tensile strength and elongation at break of the sample, wherein the sample size was 60X 10mm (length X width), the initial test distance between the two jigs was 20mm, and the sample was tested at a loading speed of 5 mm/min. The test results are shown in Table 2.
TABLE 2 mechanical Properties and conductivity of the self-healing conductive coatings in examples 1-8
Examples | Tensile Strength (MPa) | Elongation at break (%) | Conductivity (S/m) |
Example 1 | 3.53 | 61.2 | 3.08×10 -3 |
Example 2 | 4.03 | 48.6 | 2.05×10 -2 |
Example 3 | 4.80 | 39.5 | 0.95×10 -1 |
Example 4 | 5.68 | 30.8 | 3.06 |
Example 5 | 6.49 | 26.0 | 6.37 |
Example 6 | 7.51 | 28.0 | 6.43 |
Example 7 | 8.40 | 29.2 | 6.48 |
Example 8 | 9.53 | 30.7 | 6.50 |
As can be seen from Table 2, the tensile strength, conductivity and elongation at break of the repaired conductive coatings in examples 1 to 8 were all reduced, but the reduction was small, which is due to the interaction of the hydrogen bond and the ester bond forces in the materials.
The repaired guide in examples 1-8 was conducted with reference to the specification of class II plywood in the national Standard of China (general plywood) (GB/T9846-2015)And (5) preparing the plywood by using the electric paint for gluing strength test. Each three-layer plywood is sawn into 9 test pieces with the size of 100 multiplied by 25mm and the gluing area of the test pieces of 25 multiplied by 25mm 2 . The results are shown in FIG. 2.
The comparison of fig. 1-2 shows that the bonding strength change value of the repaired conductive coating in examples 1-8 is smaller, which shows that the conductive coating has good self-healing repair effect and benefits from an ester bond and hydrogen bond crosslinking network system of the material.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. The tara adhesive conductive coating is characterized by comprising the following raw materials in parts by weight: 1 to 15 parts of silver amide nanowire, 30 to 40 parts of tara gum, 80 to 100 parts of water, 1 to 10 parts of dihydroxytartaric acid, 0.2 to 0.5 part of thickener and 0.2 to 0.5 part of preservative.
2. The tara gum conductive coating of claim 1, wherein the thickener comprises at least one of carboxymethyl cellulose, sodium carboxymethyl cellulose.
3. The tara gum conductive coating of claim 1, wherein the preservative is methyl benzimidazole-5-carboxylate.
4. The tara gum conductive coating of claim 1, wherein the preparation method of the silver amide nanowires comprises:
CuCl is added 2 Dissolving in water to obtain CuCl 2 A solution;
dissolving NaBr in water to obtain NaBr solution;
dissolving polyvinylpyrrolidone in ethylene glycol to obtain polyvinylpyrrolidone solution;
AgNO is to be carried out 3 Dissolving in glycol to obtain AgNO 3 A solution;
placing ethylene glycol into a container, heating to 145-155 ℃ for reaction for 0.5-1.5 h, and then adding CuCl 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature;
and (3) centrifugally separating a product obtained by the reaction to obtain a precipitate, and centrifugally washing the precipitate with acetone to finally obtain the silver amide nanowire.
5. The tara gum conductive coating of claim 4, wherein cuci 2 The concentration of the solution is 2-6 mM;
the concentration of NaBr solution is 0.5-2 mM;
dissolving 1-3 g of polyvinylpyrrolidone in 5-15 mL of ethylene glycol to obtain polyvinylpyrrolidone solution;
0.5 g to 3g AgNO 3 Dissolving in 5-15 mL glycol to obtain AgNO 3 A solution.
6. The tara gum conductive paint of claim 4, wherein the ethylene glycol is placed in a container, heated to 145-155 ℃ and reacted for 0.5-1.5 hours, then CuCl is added 2 The solution and NaBr solution are continuously reacted for 10 to 20 minutes under stirring, and the polyvinylpyrrolidone solution and AgNO are continuously added 3 Continuously reacting the solution with ethylenediamine for 1-2 h, stopping the reaction and cooling to room temperature; wherein, glycol, cuCl 2 Solution, naBr solution, polyvinylpyrrolidone solution, agNO 3 The volume ratio of the solution to the ethylenediamine is (60-100) mL (400-600) mu L (50-150) mu L (5-15) mL (3-7) mL.
7. A method for preparing the tara gum conductive coating according to any one of claims 1 to 6, comprising the steps of:
adding the tara gum into water for stirring, adding the silver amide nanowires and the dihydroxytartaric acid, stirring, performing a crosslinking reaction, and adding a thickener and a preservative to obtain the tara gum conductive coating.
8. The method for preparing a conductive coating of tara gum according to claim 7, wherein the reaction temperature of the crosslinking reaction is 35-45 ℃ and the reaction time is 0.5-2 h.
9. The method for preparing a conductive coating of tara gum according to claim 7, wherein the step of adding the tara gum to water and stirring is performed for 20 to 60 minutes.
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