CN114773534A - Conductive PUA composite emulsion and preparation method thereof - Google Patents
Conductive PUA composite emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN114773534A CN114773534A CN202210298716.9A CN202210298716A CN114773534A CN 114773534 A CN114773534 A CN 114773534A CN 202210298716 A CN202210298716 A CN 202210298716A CN 114773534 A CN114773534 A CN 114773534A
- Authority
- CN
- China
- Prior art keywords
- conductive
- composite emulsion
- parts
- pua
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000004945 emulsification Methods 0.000 title description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 37
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000004970 Chain extender Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- -1 polyethylene adipate Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000921 polyethylene adipate Polymers 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000005485 electric heating Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a conductive PUA composite emulsion and a preparation method thereof, wherein the raw materials of the conductive PUA composite emulsion comprise a modified nano carbon material, and the raw materials for preparing the modified nano carbon material comprise, by weight, 10 parts of graphene oxide, 20-30 parts of multi-walled carbon nanotubes, 1.5-2 parts of a silane coupling agent, 3-4 parts of a first polyester polyol and 5-10 parts of an alcohol diluent. The conductive PUA composite emulsion has good stability and strong conductivity, and can be well applied to the fields of conductive coatings, electric heating coatings, electromagnetic shielding coatings and the like.
Description
Technical Field
The invention relates to the technical field of aqueous poly-amino-acid-acrylate composite emulsion, and more particularly relates to conductive PUA composite emulsion and a preparation method thereof.
Background
The nano carbon material comprises materials such as nano carbon black, nano graphite, carbon nano tubes, graphene and the like, has excellent electrical conductivity and thermal conductivity, is a common additive for preparing a conductive polymer composite material, and is widely applied to various fields such as nano electronic devices, film electrodes, flexible conductive materials, conductive adhesives and the like. However, the nano material is very easy to agglomerate, has poor compatibility with a high polymer, has poor dispersibility in a high polymer resin, and directly influences the exertion of the conductivity of the nano carbon material.
The aqueous polyurethane acrylate (PUA) emulsion is a novel emulsion combining aqueous polyurethane and an aqueous acrylate synthesis method, has the advantages of good film forming property, high mechanical strength, high gloss, strong weather resistance and the like, and has important application in the aspects of environment-friendly coatings and adhesives. In some cases, inorganic fillers are added to functionally modify the PUA emulsion in order to enhance one of its properties. For example, the nano silicon dioxide is added into the PUA emulsion, so that the mechanical strength, heat resistance and chemical resistance of the PUA water-based paint are improved. However, the conductivity of the PUA emulsion has been studied less.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the conductive PUA composite emulsion and the preparation method thereof.
In order to achieve the purpose, the invention discloses a conductive PUA composite emulsion, which comprises a modified nano carbon material, wherein the modified nano carbon material comprises the following raw materials in parts by weight:
preferably, the first polyester polyol is selected from at least one of polyethylene adipate diol (PEA), poly epsilon-caprolactone diol (PCL), polycarbonate diol (PCDL). Preferably, the weight average molecular weight of the first polyester polyol is 200-500, and the first polyester polyol has better transparency and smaller molecular weight, and is beneficial to polymerization and coating. The weight average molecular weight of the first polyester polyol can be, but is not limited to, 200, 300, 400, 500.
Preferably, the Graphene Oxide (GO) is subjected to oxidation treatment, the number of material layers is 1-5, and the specific surface area is more than or equal to 350m2The powder graphene has stable performance, and an infrared heating micro-area can be formed around the graphene when current passes through the graphene.
Preferably, the multi-walled carbon nanotubes (MWCNTs) provide a one-dimensional conductive path, facilitating uniform distribution of energy for electrical heating. Furthermore, the multi-walled carbon nanotube has a tube length of 1 to 10 μm and a tube diameter of 10 to 20 nm.
Preferably, the silane coupling agent is at least one selected from the group consisting of gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and gamma-methacryloxypropyltrimethoxysilane (KH-570).
Preferably, the alcohol diluent is at least one selected from the group consisting of isopropyl alcohol, methanol, ethanol, benzyl alcohol, and ethylene glycol. The alcohol diluent and the polyester polyol have similar polarity, are favorable for dispersion and are volatile, and are not in the modified nano carbon material powder after being heated and volatilized, and only the polyester polyol and the silane coupling agent are remained on the surface of the powder.
Preferably, the conductive PUA composite emulsion further comprises a second polyester polyol, aliphatic isocyanate, a mixed chain extender, a catalyst, an initiator, an emulsifier and an acrylic monomer. More preferably, the paint comprises the following components in parts by weight:
wherein the second polyester polyol is at least one selected from polyethylene adipate diol (PEA), poly epsilon-caprolactone diol (PCL) and polycarbonate diol (PCDL). The second polyester polyol can be the same as the first polyester polyol in material and molecular weight, and more preferably, the second polyester polyol has a weight average molecular weight of 500-1000, which is higher than that of the first polyester polyol in content of soft segment, and the synthesized resin has good flexibility. The second polyester polyol may have a weight average molecular weight of, but not limited to, 600, 700, 800, 900, 1000.
Preferably, the aliphatic isocyanate is Hexamethylene Diisocyanate (HDI) or isophorone diisocyanate (IPDI), and since the aliphatic diisocyanate does not contain a benzene ring, yellowing resistance is better.
Preferably, the mixed chain extender comprises 5 to 7 parts of the first chain extender and 8 to 12 parts of the second chain extender,
the first chain extender comprises one of 1, 4-Butanediol (BDO) or 1, 6-Hexanediol (HDO);
the second chain extender comprises at least one of Trimethylolpropane (TMP), dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA). And introducing a second chain extender on the basis of the first chain extender, wherein the second chain extender has hydrophilicity and can introduce carboxylic acid to prepare for the subsequent reaction with an acrylic monomer.
Preferably, the catalyst may be selected from dibutyltin dilaurate.
Preferably, the initiator is selected from a potassium persulfate or ammonium persulfate aqueous solution with the mass concentration of 15-20%.
Preferably, the emulsifier is anionic, in particular, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate is used.
Preferably, the acrylic monomer is selected from at least one of isooctyl acrylate (2-EHA), Methyl Methacrylate (MMA), Butyl Acrylate (BA).
Preferably, the neutralized amine is triethylamine or ammonia water with mass concentration of 20-25%.
Preferably, the solvent is any one selected from the group consisting of acetone, methyl ethyl ketone, and N-methylpyrrolidone (NMP).
The invention also provides a preparation method of the conductive PUA composite emulsion, which comprises the following steps:
(1) adding polyester polyol and a mixed chain extender into a nitrogen-protected reaction kettle, performing vacuum dehydration for 1-2 hours at the temperature of 100-110 ℃, cooling to 60-80 ℃, adding a solvent with the formula amount of 1/3, stirring, opening a condensation reflux device, rotating at the speed of 120-180 rpm for 10-15 min until the raw materials are dissolved, adding a modified nano carbon material and a catalyst, and stirring for 20-30 min until the raw materials are uniformly dispersed;
(2) diluting aliphatic isocyanate and a solvent with the formula amount of 1/3, slowly adding the diluted aliphatic isocyanate and the solvent into a reaction kettle in a dropwise manner, heating to 80-90 ℃ after the dropwise addition is finished within 20min, and stirring for 40-60 min for reaction;
(3) cooling to 75-85 ℃, adding an initiator with the formula amount of 1/3 and an emulsifier with the formula amount of 1/2 in sequence, increasing the stirring rotation speed to 240-600 rpm, diluting an acrylic monomer with a solvent with the formula amount of 1/3, slowly adding the diluted acrylic monomer into a reaction kettle in a dropwise manner, adding deionized water with the formula amount of 1/2 after the dropwise addition is completed within 10-30 min, and stirring for reacting for 40-60 min;
(4) diluting an initiator with the formula amount of 2/3 and an emulsifier with the formula amount of 1/2 with deionized water with the formula amount of 1/4, dropwise adding into a reaction kettle, stirring and reacting for 40-60 min after dropwise adding is completed within 20-40 min;
(5) and adding 1/4 parts of deionized water, cooling to room temperature, closing a condensation reflux device, adding neutralized amine for neutralization, controlling the pH value to be 7.5-8.5, and discharging to obtain the PUA emulsion.
The preparation method of the modified nano carbon material comprises the following steps:
(1) uniformly mixing polyester polyol with a silane coupling agent to obtain a mixed material;
(2) soaking graphene oxide and multi-walled carbon nanotubes in the mixed material, adding an alcohol diluent, uniformly stirring at a stirring speed of 100-200 rpm for 30-60 min to prepare a mixed slurry;
(3) heating the mixed slurry to 60-90 ℃ for 30-40 min to solidify the mixed slurry into loose massive objects;
(4) grinding the massive object into powder, sieving to prepare a modified nano carbon material, and preparing the conductive PUA composite emulsion by using the modified nano carbon material.
In the preparation method of the modified nano carbon material, the polyester polyol is treated by adopting the silane coupling agent firstly, so that the polyester polyol can be effectively attached to the surfaces of the graphene oxide and the multi-walled carbon nano tube.
The invention has the following beneficial effects:
(1) the one-dimensional multi-walled carbon nanotube and the two-dimensional graphene oxide are compounded to form a one-dimensional/two-dimensional hybrid system, so that a conductive path is easier to form in the prepared composite emulsion resin, and the further conductive function is facilitated to be realized;
(2) after the surface modification treatment is carried out on the nano-carbon material, when the conductive PUA composite emulsion is prepared, hydroxyl adsorbed on the surface of the nano-carbon material is easily combined with polyester polyol, and the compatibility of the nano-carbon material and an emulsifier is effectively improved because the surface of the nano-carbon material is coated with the silane coupling agent and the polyester polyol.
(3) After the surface modification treatment is carried out on the nano carbon material, when the conductive PUA composite emulsion is prepared, hydroxyl adsorbed on the surface of the nano carbon material can participate in the polymerization reaction of aliphatic isocyanate, so that the stability of the conductive PUA composite emulsion is greatly improved, the conductive PUA composite emulsion is not easy to precipitate or settle, the addition amount of the nano carbon material can be increased, and the conductivity is improved.
(4) The conductive PUA composite emulsion has the advantages of simple production process, high production efficiency and low cost, and the solvent is kept in the emulsion and is not recycled.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the present invention in detail, the following description is given in detail with reference to the embodiments.
Wherein, part of raw materials are as follows:
graphene oxide Shenzhen Huaen New Material Co., Ltd;
multi-walled carbon nanotubes Jiangsu Xiancheng nanomaterial science and technology Co., Ltd;
other raw materials or reagents are all sold or made by self.
Example 1
A preparation method of a conductive PUA composite emulsion comprises the following steps:
(1) adding 100 parts of polyethylene glycol adipate glycol (with the molecular weight of 800), 5 parts of 1, 4-butanediol and 8 parts of trimethylolpropane into a reaction kettle under the protection of nitrogen, dehydrating in vacuum at 110 ℃ for 1 hour, cooling to 70 ℃, adding 50 parts of acetone solvent, stirring, opening a condensation reflux device, rotating at the speed of 120rpm for 15min until the raw materials are dissolved, adding 15 parts of modified nanocarbon material and 0.005 part of dibutyltin dilaurate catalyst, and stirring for 20min until the mixture is in a uniformly dispersed state;
(2) diluting 40 parts of hexamethylene diisocyanate and 50 parts of acetone solvent, slowly dripping into a reaction kettle, heating to 85 ℃ within 20min, and stirring for 50min for reaction;
(3) cooling to 78 ℃, adding 1 part of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate in sequence, increasing the stirring rotation speed to 400rpm, diluting 350 parts of methyl methacrylate with 50 parts of acetone solvent, slowly adding the diluted methyl methacrylate into the reaction kettle in a dropwise manner, adding 500 parts of deionized water after the dropwise addition is finished within 20min, and stirring and reacting for 60 min;
(4) diluting 2 parts of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate by 250 parts of deionized water, dropwise adding into the reaction kettle, and stirring and reacting for 40min after 20min of dropwise adding is finished;
(5) and adding 250 parts of deionized water, cooling to room temperature, closing a condensation reflux device, adding 8 parts of triethylamine for neutralization, controlling the pH value to be 7.5-8.5, and discharging to obtain the PUA emulsion.
The preparation method of the modified nano carbon material comprises the following steps:
(1) uniformly mixing 4 parts of polyethylene glycol adipate (molecular weight is 400) and 2 parts of gamma-aminopropyltriethoxysilane to obtain a mixed material;
(2) soaking 10 parts of graphene oxide and 20 parts of multi-walled carbon nanotubes in the mixed material, adding 10 parts of isopropanol diluent, uniformly stirring at a stirring speed of 150rpm for 40min to prepare mixed slurry;
(3) heating the mixed slurry to 80 ℃ for 30min to solidify the mixed slurry into loose block-shaped objects;
(4) the block-shaped object is ground into powder and filtered by a 1000-mesh screen to prepare the modified nano carbon material.
Example 2
A preparation method of a conductive PUA composite emulsion comprises the following steps:
(1) adding 100 parts of polycarbonate diol (with the molecular weight of 1000), 7 parts of 1, 6-hexanediol and 10 parts of dimethylolbutyric acid into a reaction kettle under the protection of nitrogen, dehydrating in vacuum at 110 ℃ for 1h, cooling to 70 ℃, adding 60 parts of acetone solvent, stirring, opening a condensation reflux device, rotating at 120rpm for 15min until the raw materials are dissolved, adding 20 parts of modified nano carbon material and 0.005 part of dibutyltin dilaurate catalyst, and stirring for 25min until the raw materials are uniformly dispersed;
(2) diluting 45 parts of isophorone diisocyanate and 60 parts of acetone solvent, slowly dripping into a reaction kettle, heating to 86 ℃ within 20min after dripping is finished, and stirring for 60min to react;
(3) cooling to 79 ℃, sequentially adding 1 part of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate, increasing the stirring rotation speed to 400rpm, diluting 400 parts of butyl acrylate with 60 parts of acetone solvent, slowly adding the diluted butyl acrylate into the reaction kettle in a dropwise manner, adding 500 parts of deionized water after dropwise addition is completed within 20min, and stirring and reacting for 40 min;
(4) diluting 2 parts of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate by 250 parts of deionized water, dropwise adding into a reaction kettle, stirring and reacting for 60min after dropwise adding is finished for 20 min;
(5) and adding 250 parts of deionized water, cooling to room temperature, closing a condensation reflux device, adding 8 parts of triethylamine for neutralization, controlling the pH value to be 7.5-8.5, and discharging to obtain the PUA emulsion.
The preparation method of the modified nano carbon material comprises the following steps:
(1) uniformly mixing 3 parts of polycarbonate diol (with the molecular weight of 500) and 2 parts of gamma-aminopropyltriethoxysilane to obtain a mixed material;
(2) soaking 10 parts of graphene oxide and 30 parts of multi-walled carbon nanotubes in the mixed material, adding 5 parts of isopropanol diluent, uniformly stirring at the stirring speed of 150rpm for 40min to prepare mixed slurry;
(3) heating the mixed slurry to 80 ℃ for 30min to solidify the mixed slurry into loose massive objects;
(4) grinding the block into powder, and filtering with a 1000-mesh screen to obtain the modified nano carbon material.
Comparative example 1
This comparative example is essentially the same as the preparation of the conductive PUA composite emulsion of example 1, except that: in this comparative example, no polyethylene glycol adipate glycol was used in the preparation of the modified nanocarbon material, and in example 1, polyethylene glycol adipate glycol was used, and the rest is the same, and will not be described.
Comparative example 2
This comparative example is essentially the same as the preparation of the conductive PUA composite emulsion of example 1, except that: in this comparative example, the modified nanocarbon material was prepared without using gamma-aminopropyltriethoxysilane, and example 1 contained gamma-aminopropyltriethoxysilane, and the rest was the same, and thus, no description will be made.
The conductive PUA composite emulsions obtained in examples 1 to 2 and comparative examples 1 to 2 were tested for their properties, and the results are shown in Table 1.
The test items and the method are as follows:
solid content: weighing 2-5 g of emulsion by adopting a drying and weighing differential method, baking for 1h in a baking oven at 120 ℃, and dividing the mass of the initial emulsion by the mass of the residual substances;
viscosity: measured using a rotational viscometer;
conductivity: directly measuring by using a liquid conductivity tester;
and (3) testing the stability: and (3) taking 300g of emulsion, placing the emulsion in a 500mL transparent reagent bottle, standing the emulsion for 1 month at normal temperature without moving, and observing whether the emulsion is layered by naked eyes.
TABLE 1 Performance test results
As can be seen from the data in Table 1, the conductive PUA composite emulsion of the present invention has good stability and conductivity, and can be well applied to the fields of conductive coatings, electrical heating coatings, electromagnetic shielding coatings, etc.
The comparative example 1 has poor storage stability of the emulsion because no glycol adipate exists, and the conductivity is obviously reduced under the condition that the proportion of the nano carbon material is increased, which shows that the polyester polyol coated on the surface is beneficial to improving the compatibility of the nano carbon material and the emulsion, and has great influence on the conductivity when the compatibility is poor.
Wherein, comparative example 2 does not contain gamma-aminopropyltriethoxysilane, the emulsion storage stability is not good, the conductivity is obviously reduced, show that the silane coupling agent helps to improve the compatibility of the nanocarbon material and the emulsion, and when the compatibility is poor, the conductivity is also greatly influenced.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (10)
1. The conductive PUA composite emulsion is characterized by comprising a modified nano carbon material, wherein the modified nano carbon material comprises the following raw materials in parts by weight:
2. the electrically conductive PUA composite emulsion of claim 1, wherein the first polyester polyol is selected from at least one of polyethylene adipate glycol, poly-epsilon-caprolactone glycol, and polycarbonate glycol.
3. The conductive PUA composite emulsion of claim 1, wherein said alcoholic diluent is selected from at least one of isopropyl alcohol, methanol, ethanol, benzyl alcohol, ethylene glycol.
4. The electrically conductive PUA composite emulsion according to claim 1, wherein the silane coupling agent is at least one selected from the group consisting of γ -aminopropyltriethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane.
5. The conductive PUA composite emulsion of claim 1, further comprising a second polyester polyol, an aliphatic isocyanate, a mixed chain extender, a catalyst, an initiator, an emulsifier, and an acrylic monomer.
6. The conductive PUA composite emulsion according to claim 5, which comprises, in parts by weight:
7. the conductive PUA composite emulsion according to claim 6, wherein said mixed chain extender comprises 5 to 7 parts of a first chain extender and 8 to 12 parts of a second chain extender,
the first chain extender comprises one of 1, 4-butanediol or 1, 6-hexanediol;
the second chain extender comprises at least one of trimethylolpropane, dimethylolpropionic acid and dimethylolbutyric acid.
8. The electrically conductive PUA composite emulsion of claim 6, wherein the emulsifier is anionic.
9. The conductive PUA composite emulsion according to claim 1, wherein the method for preparing the modified nanocarbon material comprises the steps of:
(1) uniformly mixing the first polyester polyol with the silane coupling agent to obtain a mixed material;
(2) soaking the graphene oxide and the multi-walled carbon nanotubes in the mixed material, adding the alcohol diluent, and uniformly stirring at a stirring speed of 100-200 rpm for 30-60 min to prepare mixed slurry;
(3) heating the mixed slurry to 60-90 ℃ for 30-40 min to solidify the mixed slurry into loose massive objects;
(4) grinding the massive object into powder, sieving to prepare a modified nano carbon material, and preparing the conductive PUA composite emulsion by using the modified nano carbon material.
10. A method for preparing the conductive PUA composite emulsion according to claim 6, comprising the steps of:
(1) adding a second polyester polyol and a mixed chain extender into a nitrogen-protected reaction kettle, carrying out vacuum dehydration for 1-2 h at 100-110 ℃, cooling to 60-80 ℃, adding a solvent, stirring, opening a condensation reflux device, rotating at 120-180 rpm for 10-15 min until the raw materials are dissolved, adding a modified nano carbon material and a catalyst, and stirring for 20-30 min until the raw materials are uniformly dispersed;
(2) diluting aliphatic isocyanate and a solvent, slowly adding the diluted aliphatic isocyanate and the solvent into a reaction kettle in a dropwise manner, heating to 80-90 ℃ within 20min after the dropwise addition is finished, and stirring for 40-60 min for reaction;
(3) cooling to 75-85 ℃, adding 1/3 formula amount of initiator and 1/2 formula amount of emulsifier, increasing the stirring speed to 240-600 rpm, diluting the acrylic monomer with solvent, slowly adding the diluted acrylic monomer into the reaction kettle, adding deionized water after dropwise addition is completed within 10-30 min, and stirring for reaction for 40-60 min;
(4) diluting an initiator with the formula amount of 2/3 and an emulsifier with the formula amount of 1/2 with deionized water, dropwise adding the diluted initiator and the emulsifier into a reaction kettle, and stirring for reacting for 40-60 min after dropwise adding is finished for 20-40 min;
(5) and adding the rest deionized water, cooling to room temperature, closing the condensation reflux device, adding neutralizing amine for neutralization, controlling the pH value to be 7.5-8.5, and discharging to obtain the PUA emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210298716.9A CN114773534B (en) | 2022-03-24 | 2022-03-24 | Conductive PUA composite emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210298716.9A CN114773534B (en) | 2022-03-24 | 2022-03-24 | Conductive PUA composite emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114773534A true CN114773534A (en) | 2022-07-22 |
| CN114773534B CN114773534B (en) | 2023-11-07 |
Family
ID=82425740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210298716.9A Active CN114773534B (en) | 2022-03-24 | 2022-03-24 | Conductive PUA composite emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773534B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007182546A (en) * | 2005-12-06 | 2007-07-19 | Mitsubishi Rayon Co Ltd | Carbon nanotube-containing composition, composite and manufacturing process of those |
| CN101333280A (en) * | 2007-06-26 | 2008-12-31 | 同济大学 | Method for preparing modified urethane elastomer |
| CN102942810A (en) * | 2012-11-21 | 2013-02-27 | 太原理工大学 | Surface modification method for carbon nano tube |
| US20150275016A1 (en) * | 2012-10-29 | 2015-10-01 | 3M Innovative Properties Company | Conductive inks and conductive polymeric coatings |
| CN106752878A (en) * | 2017-01-20 | 2017-05-31 | 苏州碳丰石墨烯科技有限公司 | A kind of Graphene low-voltage heating coating and preparation method thereof |
| CN106978128A (en) * | 2017-05-09 | 2017-07-25 | 东莞市普力达光学材料科技有限公司 | Polyurethane adhesive and preparation method thereof and heat-conducting glue band |
| CN107312440A (en) * | 2017-07-14 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | High-termal conductivity aqueous polyurethane coating and preparation method thereof |
| CN107629179A (en) * | 2017-09-26 | 2018-01-26 | 广东省石油与精细化工研究院 | A kind of electrically conductive ink modified acrylic acid emulsion and preparation method thereof |
| CN107903692A (en) * | 2017-11-30 | 2018-04-13 | 宁波诗宏千禧贸易有限公司 | A kind of modified graphene electrically-conducting paint and preparation method thereof |
| CN110396220A (en) * | 2019-06-21 | 2019-11-01 | 福建师范大学 | A kind of carbon nanotube polylol and carbon nano-tube/poly urethane composite material and preparation method |
| CN111410905A (en) * | 2020-04-26 | 2020-07-14 | 朱建程 | Functional graphene modified polyurethane conductive anticorrosive coating and preparation method thereof |
| CN112662268A (en) * | 2019-10-15 | 2021-04-16 | 中车唐山机车车辆有限公司 | Electromagnetic shielding coating and preparation method thereof |
| CN112777590A (en) * | 2019-11-08 | 2021-05-11 | 宁波锋成先进能源材料研究院 | Preparation method of amphiphilic graphene oxide and surfactant containing amphiphilic graphene oxide |
| CN114213902A (en) * | 2021-12-14 | 2022-03-22 | 湖南金阳烯碳新材料有限公司 | Water-based graphene conductive ink for battery and preparation method and application thereof |
-
2022
- 2022-03-24 CN CN202210298716.9A patent/CN114773534B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007182546A (en) * | 2005-12-06 | 2007-07-19 | Mitsubishi Rayon Co Ltd | Carbon nanotube-containing composition, composite and manufacturing process of those |
| CN101333280A (en) * | 2007-06-26 | 2008-12-31 | 同济大学 | Method for preparing modified urethane elastomer |
| US20150275016A1 (en) * | 2012-10-29 | 2015-10-01 | 3M Innovative Properties Company | Conductive inks and conductive polymeric coatings |
| CN102942810A (en) * | 2012-11-21 | 2013-02-27 | 太原理工大学 | Surface modification method for carbon nano tube |
| CN106752878A (en) * | 2017-01-20 | 2017-05-31 | 苏州碳丰石墨烯科技有限公司 | A kind of Graphene low-voltage heating coating and preparation method thereof |
| CN106978128A (en) * | 2017-05-09 | 2017-07-25 | 东莞市普力达光学材料科技有限公司 | Polyurethane adhesive and preparation method thereof and heat-conducting glue band |
| CN107312440A (en) * | 2017-07-14 | 2017-11-03 | 合肥思敬齐化工材料有限责任公司 | High-termal conductivity aqueous polyurethane coating and preparation method thereof |
| CN107629179A (en) * | 2017-09-26 | 2018-01-26 | 广东省石油与精细化工研究院 | A kind of electrically conductive ink modified acrylic acid emulsion and preparation method thereof |
| CN107903692A (en) * | 2017-11-30 | 2018-04-13 | 宁波诗宏千禧贸易有限公司 | A kind of modified graphene electrically-conducting paint and preparation method thereof |
| CN110396220A (en) * | 2019-06-21 | 2019-11-01 | 福建师范大学 | A kind of carbon nanotube polylol and carbon nano-tube/poly urethane composite material and preparation method |
| CN112662268A (en) * | 2019-10-15 | 2021-04-16 | 中车唐山机车车辆有限公司 | Electromagnetic shielding coating and preparation method thereof |
| CN112777590A (en) * | 2019-11-08 | 2021-05-11 | 宁波锋成先进能源材料研究院 | Preparation method of amphiphilic graphene oxide and surfactant containing amphiphilic graphene oxide |
| CN111410905A (en) * | 2020-04-26 | 2020-07-14 | 朱建程 | Functional graphene modified polyurethane conductive anticorrosive coating and preparation method thereof |
| CN114213902A (en) * | 2021-12-14 | 2022-03-22 | 湖南金阳烯碳新材料有限公司 | Water-based graphene conductive ink for battery and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 肖能君;李强军;姜其斌;: "UV固化聚氨酯丙烯酸酯涂料的研究进展", 绝缘材料, no. 01 * |
| 赖双权;金勇;祝晨耀;何文顺;: "氧化石墨烯的共价键功能化修饰研究进展(续)", 中国皮革, no. 02 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773534B (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845217B (en) | Preparation method of water-based polyurethane/nano-silicon dioxide composite emulsion | |
| CN104403548B (en) | Containing polyether polyol/nano-TiO2the aqueous polyurethane coating of hybrid material | |
| CN108467467A (en) | Plant oil base Anionic Water-borne Polyurethane Emulsion and its preparation method and application | |
| CN108264755B (en) | Preparation method of graphene-carbon nanotube/waterborne polyurethane composite material | |
| CN108395485B (en) | Modified nanocellulose, filler and water-based coating containing same | |
| CN110643016B (en) | Preparation method of carbon nanotube-loaded nano silver wire modified polyurethane antistatic emulsion | |
| CN109575782B (en) | Graphene oxide modified polyurethane electrophoretic resin, polyurethane electrophoretic paint and preparation method thereof | |
| CN111925642B (en) | Preparation method of self-repairing carbon nano tube-cationic waterborne polyurethane electromagnetic shielding composite material | |
| CN108424502B (en) | Multifunctional monomer and low-sheet-resistance flexible transparent conductive film based on same | |
| CN109384936B (en) | Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin, cathode polyurethane electrophoretic paint and preparation methods thereof | |
| Xu et al. | Effect of polydopamine-modified multi-walled carbon nanotubes on the thermal stability and conductivity of UV-curable polyurethane/polysiloxane pressure-sensitive adhesives | |
| CN110294989A (en) | A kind of composite nano-coating and preparation method thereof | |
| Chen et al. | Synthesis and properties of novel UV–curable hyperbranched waterborne polyurethane/Fe 3 O 4 nanocomposite films with excellent magnetic properties | |
| CN115011175A (en) | Rare earth pigment photocuring color paste and preparation method thereof | |
| CN113801271A (en) | Silica sol modified waterborne polyurethane acrylate composite emulsion and preparation thereof | |
| CN117362581A (en) | Modified graphene oxide in-situ polymerization waterborne polyurethane and preparation method thereof | |
| CN114773534A (en) | Conductive PUA composite emulsion and preparation method thereof | |
| CN111040474B (en) | Conductive titanium dioxide and preparation method thereof | |
| KR101102867B1 (en) | Composition of Water-dispersive Re-emulsifiable Polyurethane/Arcrylate Copolymer Hybrid and Method of Producing the Same | |
| CN115403980B (en) | Water-based quick-drying antibacterial coating for electronic device, and preparation method and application thereof | |
| CN103923498A (en) | Composition for forming black matrix, black matrix, display substrate and modification method | |
| CN114437595B (en) | Flexible transparent electric heating composite coating and preparation method thereof | |
| CN114574062A (en) | Preparation method of modified fluorine-containing polyacrylate coating | |
| CN114479583B (en) | Preparation method of coating composition | |
| CN114410171B (en) | Water-based paint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |