CN114773534B - Conductive PUA composite emulsion and preparation method thereof - Google Patents
Conductive PUA composite emulsion and preparation method thereof Download PDFInfo
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- CN114773534B CN114773534B CN202210298716.9A CN202210298716A CN114773534B CN 114773534 B CN114773534 B CN 114773534B CN 202210298716 A CN202210298716 A CN 202210298716A CN 114773534 B CN114773534 B CN 114773534B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 36
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 33
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000004970 Chain extender 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 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- -1 aliphatic isocyanate Chemical class 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000007865 diluting Methods 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
- 239000003999 initiator Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 239000000203 mixture Substances 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
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 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
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 238000000227 grinding Methods 0.000 claims description 2
- 238000007873 sieving 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 1
- 229920000921 polyethylene adipate Polymers 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 8
- 238000005485 electric heating Methods 0.000 abstract description 2
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 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
- 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
- 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 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- 150000002009 diols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- 238000000576 coating method Methods 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
- 230000032798 delamination Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 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
- 239000005543 nano-size silicon particle Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 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
- 238000013112 stability test Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 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
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- 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 modified nano carbon materials, and the preparation raw materials of the modified nano carbon materials comprise, by weight, 10 parts of graphene oxide, 20-30 parts of multi-wall carbon nanotubes, 1.5-2 parts of silane coupling agent, 3-4 parts of first polyester polyol and 5-10 parts of alcohol diluents. The conductive PUA composite emulsion has good stability and strong conductivity, and can be well applied to the fields of conductive paint, electric heating paint, electromagnetic shielding paint and the like.
Description
Technical Field
The invention relates to the technical field of aqueous polyurethane acrylate composite emulsion, in particular to conductive PUA composite emulsion and a preparation method thereof.
Background
The nano carbon material comprises nano carbon black, nano graphite, carbon nano tube, graphene and other materials, has excellent electric conductivity and thermal conductivity, is a common additive for preparing conductive polymer composite materials, and has wide application in various fields of nano electronic devices, thin film electrodes, flexible conductive materials, conductive adhesives and the like. However, the nano material is easy to agglomerate, has poor compatibility with the polymer, has poor dispersibility in the polymer resin, and directly influences the exertion of the conductivity of the nano carbon material.
The aqueous polyurethane acrylic ester (PUA) emulsion is a novel emulsion combining aqueous polyurethane and an aqueous acrylic ester synthesis method, has the advantages of good film forming property, high mechanical strength, high glossiness, strong weather resistance and the like, and has important application in the aspects of environment-friendly paint and adhesive. Sometimes, to enhance a certain performance of the PUA emulsion, an inorganic filler is often added to functionally modify it. For example, nano silicon dioxide is added into the PUA emulsion to improve the mechanical strength, heat resistance and chemical resistance of the PUA water-based paint. However, the current technical research on the conductivity of PUA emulsions is relatively small.
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, and the conductive PUA composite emulsion has good stability and strong conductivity.
In order to achieve the above 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 glycol adipate glycol (PEA), poly epsilon-caprolactone glycol (PCL), polycarbonate glycol (PCDL). Preferably, the first polyester polyol has a weight average molecular weight of 200 to 500, and the first polyester polyol has better transparency and smaller molecular weight, and is favorable for polymerization and coating. The weight average molecular weight of the first polyester polyol may be, but is not limited to, 200, 300, 400, 500.
Preferably, the oxidized Graphene (GO) adopts oxidized materials with the number of layers of 1-5 and the specific surface area of more than or equal to 350m 2 The powder graphene/g has stable performance, and can form infrared heating micro-areas around the graphene when current passes.
Preferably, the multiwall carbon nanotubes (MWCNTs) provide a one-dimensional conductive path, facilitating uniform distribution of the energy of the electrical heating. Further, the multi-walled carbon nanotube has a tube length of 1 to 10 μm and a tube diameter of 10 to 20nm.
Preferably, the silane coupling agent is selected from at least one of gamma-aminopropyl triethoxysilane (KH-550), gamma- (2, 3-glycidoxy) propyl trimethoxysilane (KH-560) and gamma-methacryloxypropyl trimethoxysilane (KH-570).
Preferably, the alcohol diluent is at least one selected from isopropanol, methanol, ethanol, benzyl alcohol and ethylene glycol. The alcohol diluent has similar polarity with the polyester polyol, is favorable for dispersion and is easy to volatilize, and after heating and volatilizing, the alcohol diluent is not in the modified nano carbon material powder, and only the polyester polyol and the silane coupling agent are left on the surface of the powder.
Preferably, the conductive PUA composite emulsion further comprises a second polyester polyol, an aliphatic isocyanate, a mixed chain extender, a catalyst, an initiator, an emulsifier, and an acrylic monomer. More preferably, the composition comprises, in parts by weight:
wherein the second polyester polyol is at least one selected from polyethylene glycol adipate glycol (PEA), poly epsilon-caprolactone glycol (PCL) and polycarbonate glycol (PCDL). The second polyester polyol may be the same as the first polyester polyol in terms of substance and molecular weight, and more preferably, the second polyester polyol has a weight average molecular weight of 500 to 1000, a higher molecular weight than the first polyester polyol, a higher soft segment content, and good flexibility of the synthetic resin. The weight average molecular weight of the second polyester polyol may be, but is not limited to 600, 700, 800, 900, 1000.
Preferably, the aliphatic isocyanate is Hexamethylene Diisocyanate (HDI) or isophorone diisocyanate (IPDI), and the yellowing resistance is better because the aliphatic diisocyanate does not contain benzene rings.
Preferably, the mixed chain extender comprises 5-7 parts of the first chain extender and 8-12 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). The second chain extender is introduced on the basis of the first chain extender, is hydrophilic and can be introduced into carboxylic acid, ready for subsequent reaction with acrylic monomers.
Preferably, the catalyst may be selected from dibutyltin dilaurate.
Preferably, the initiator is selected from aqueous solutions of potassium persulfate or ammonium persulfate with a 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 at least one selected from isooctyl acrylate (2-EHA), methyl Methacrylate (MMA), butyl Acrylate (BA).
Preferably, the neutralizing amine is triethylamine or ammonia water with the mass concentration of 20-25%.
Preferably, the solvent is selected from any one of acetone, butanone, 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 reaction kettle protected by nitrogen, vacuum dehydrating at 100-110 ℃ for 1-2 h, cooling to 60-80 ℃, adding a solvent with the formula amount of 1/3, 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 with the formula amount of 1/3, slowly dripping the diluted aliphatic isocyanate and the solvent into a reaction kettle, heating the mixture to 80-90 ℃ after dripping is completed within 20min, and stirring the mixture for 40-60 min for reaction;
(3) Cooling to 75-85 ℃, sequentially adding an initiator with the formula amount of 1/3 and an emulsifier with the formula amount of 1/2, increasing the stirring rotation speed to 240-600 rpm, diluting an acrylic acid monomer with a solvent with the formula amount of 1/3, slowly dripping the diluted acrylic acid monomer into a reaction kettle, adding deionized water with the formula amount of 1/2 after dripping 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, dripping the mixture into a reaction kettle for 20 to 40 minutes, and stirring the mixture for reaction for 40 to 60 minutes;
(5) And adding deionized water with the formula amount of 1/4, cooling to room temperature, closing a 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.
The preparation method of the modified nano carbon material comprises the following steps:
(1) Uniformly mixing polyester polyol and a silane coupling agent to obtain a mixed material;
(2) Immersing graphene oxide and multi-wall 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 obtain mixed slurry;
(3) Heating the mixed slurry to 60-90 ℃ for 30-40 min to solidify the mixed slurry into loose block-shaped objects;
(4) Grinding the blocky object into powder, sieving to obtain 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 firstly treated by adopting the silane coupling agent, so that the polyester polyol can be effectively attached to the surfaces of graphene oxide and multi-wall carbon nano tubes.
The invention has the beneficial effects that:
(1) The one-dimensional multiwall carbon nanotube and the two-dimensional graphene oxide are compounded to form a one-dimensional/two-dimensional hybridization system, so that a conductive path is easier to form in the prepared composite emulsion resin, and further conductive functions are realized;
(2) After the surface modification treatment is carried out on the nano carbon material, hydroxyl absorbed on the surface of the nano carbon material is easy to combine with polyester polyol when the conductive PUA composite emulsion is prepared, and the compatibility of the nano carbon material and an emulsifying agent is effectively improved due to the fact that 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, hydroxyl absorbed on the surface of the nano carbon material can participate in the polymerization reaction of aliphatic isocyanate when the conductive PUA composite emulsion is prepared, so that the stability of the conductive PUA composite emulsion is greatly improved, precipitation or sedimentation is not easy to occur, 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 recovered.
Detailed Description
In order to describe the technical content, the structural features, the achieved objects and effects of the present invention in detail, the following description will explain the embodiments in detail.
Wherein, partial raw material sources are as follows:
graphene oxide Shenzhen Huaen New Material Co., ltd;
multiwall carbon nanotubes Jiangsu Xianfeng nanomaterials technologies Inc.;
other raw materials or reagents are all commercially available or self-made.
Example 1
A preparation method of conductive PUA composite emulsion comprises the following steps:
(1) Adding 100 parts of polyethylene glycol adipate glycol (with molecular weight of 800), 5 parts of 1, 4-butanediol and 8 parts of trimethylolpropane into a nitrogen-protected reaction kettle, carrying out vacuum dehydration at 110 ℃ for 1h, cooling to 70 ℃, adding 50 parts of acetone solvent, stirring, opening a condensation reflux device, rotating at 120rpm for 15min until raw materials are dissolved, adding 15 parts of modified nano carbon material and 0.005 part of dibutyltin dilaurate catalyst, and stirring for 20min until the raw materials are uniformly dispersed;
(2) Slowly dripping 40 parts of hexamethylene diisocyanate and 50 parts of acetone solvent into a reaction kettle after dilution, heating to 85 ℃ after the dripping is completed within 20min, and stirring for 50min for reaction;
(3) Cooling to 78 ℃, sequentially adding 1 part of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate, lifting the stirring rotation speed to 400rpm, diluting 350 parts of methyl methacrylate with 50 parts of acetone solvent, slowly dripping into a reaction kettle, adding 500 parts of deionized water after the dripping is completed within 20min, and stirring for reacting for 60min;
(4) 2 parts of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate are diluted by 250 parts of deionized water and then are added into a reaction kettle in a dropwise manner, after the dropwise addition is completed for 20min, the mixture is stirred and reacts for 40min;
(5) And then 250 parts of deionized water is added, the temperature is reduced to room temperature, a condensing reflux device is closed, 8 parts of triethylamine is added for neutralization, and the PUA emulsion is prepared after the pH value is controlled to be 7.5-8.5.
The preparation method of the modified nano carbon material comprises the following steps:
(1) Uniformly mixing 4 parts of polyethylene glycol adipate glycol (with the molecular weight of 400) with 2 parts of gamma-aminopropyl triethoxysilane to obtain a mixed material;
(2) Immersing 10 parts of graphene oxide and 20 parts of multi-wall carbon nanotubes in the mixed material, adding 10 parts of isopropanol diluent, uniformly stirring at a stirring speed of 150rpm for 40min to obtain mixed slurry;
(3) Heating the mixed slurry to 80 ℃ for 30min to solidify the mixed slurry into loose block-shaped objects;
(4) The blocky 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 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 protected by nitrogen, carrying out vacuum dehydration 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 to a uniform dispersion state;
(2) Diluting 45 parts of isophorone diisocyanate with 60 parts of acetone solvent, slowly dripping the diluted isophorone diisocyanate into a reaction kettle, heating to 86 ℃ after dripping is completed within 20min, and stirring for 60min for reaction;
(3) Cooling to 79 ℃, sequentially adding 1 part of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate, lifting the stirring rotation speed to 400rpm, diluting 400 parts of butyl acrylate with 60 parts of acetone solvent, slowly dripping the diluted butyl acrylate into a reaction kettle, adding 500 parts of deionized water after the dripping is completed within 20min, and stirring for reacting for 40min;
(4) 2 parts of potassium persulfate with the mass concentration of 20% and 8 parts of sodium dodecyl sulfate are diluted by 250 parts of deionized water and then are added into a reaction kettle in a dropwise manner, after 20 minutes of adding is completed, stirring is carried out for 60 minutes;
(5) And adding 250 parts of deionized water, cooling to room temperature, closing a condensing 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) with 2 parts of gamma-aminopropyl triethoxysilane to obtain a mixed material;
(2) Immersing 10 parts of graphene oxide and 30 parts of multi-wall carbon nanotubes in the mixed material, adding 5 parts of isopropanol diluent, uniformly stirring at a stirring speed of 150rpm for 40min to obtain mixed slurry;
(3) Heating the mixed slurry to 80 ℃ for 30min to solidify the mixed slurry into loose block-shaped objects;
(4) The blocky object is ground into powder and filtered by a 1000-mesh screen to prepare the modified nano carbon material.
Comparative example 1
This comparative example is substantially identical to the preparation of the conductive PUA composite emulsion of example 1, except that: the modified nanocarbon material of this comparative example was prepared without using polyethylene glycol adipate diol, but the polyethylene glycol adipate diol of example 1 was used, and the remainder was the same, and is not described herein.
Comparative example 2
This comparative example is substantially identical to the preparation of the conductive PUA composite emulsion of example 1, except that: the modified nanocarbon material of this comparative example was prepared without using gamma-aminopropyl triethoxysilane, but example 1 contained gamma-aminopropyl triethoxysilane, the remainder being the same, and is not described herein.
The conductive PUA composite emulsions obtained in examples 1-2 and comparative examples 1-2 were tested for 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 residual substances by the mass of the initial emulsion;
viscosity: using a rotational viscometer to measure;
conductivity: directly measuring by using a liquid conductivity tester;
stability test: 300g of the emulsion was placed in a 500mL transparent reagent bottle, allowed to stand at room temperature for 1 month without moving, and visually inspected for delamination.
TABLE 1 Performance test results
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 paint, electric heating paint, electromagnetic shielding paint, etc.
The comparative example 1 does not contain polyethylene glycol adipate glycol, so that the emulsion has poor storage stability, the conductivity is obviously reduced under the condition of increasing the ratio of the nano carbon material, and the surface-coated polyester polyol is helpful for improving the compatibility of the nano carbon material and the emulsion, and the conductivity is greatly influenced when the compatibility is poor.
Wherein, the comparative example 2 does not contain gamma-aminopropyl triethoxy silane, the emulsion has poor storage stability and obviously reduced conductivity, which proves that the silane coupling agent is helpful for improving the compatibility of the nano carbon material and the emulsion, and the conductivity is also greatly influenced when the compatibility is poor.
The foregoing description of the preferred embodiments of the present invention is not intended to limit the scope of the claims, which follow, as defined in the claims.
Claims (6)
1. The conductive PUA composite emulsion is characterized by comprising the following components in parts by weight:
100 parts of a second polyester polyol;
35-45 parts of aliphatic isocyanate;
13-19 parts of mixed chain extender;
15-25 parts of modified nano carbon material;
0.005-0.01 part of catalyst;
2-3 parts of an initiator;
15-20 parts of an emulsifier;
350-450 parts of acrylic acid monomer;
8-12 parts of neutralizing amine;
150-180 parts of a solvent;
900-1500 parts of deionized water;
wherein, the preparation raw materials of the modified nano carbon material comprise the following components in parts by weight:
10 parts of graphene oxide;
20-30 parts of multi-wall carbon nanotubes;
1.5-2 parts of a silane coupling agent;
3-4 parts of first polyester polyol;
5-10 parts of alcohol diluent;
the preparation method of the conductive PUA composite emulsion comprises the following steps:
(1) Adding a second polyester polyol and a mixed chain extender into a nitrogen-protected reaction kettle, carrying out vacuum dehydration at 100-110 ℃ for 1-2 hours, cooling to 60-80 ℃, adding a solvent, stirring, opening a condensation reflux device, turning on the rotation 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 to a uniform dispersion state;
(2) Slowly dripping the diluted aliphatic isocyanate and the solvent into a reaction kettle, heating to 80-90 ℃ after the dripping is completed within 20min, and stirring for 40-60 min for reaction;
(3) Cooling to 75-85 ℃, sequentially adding an initiator with the formula amount of 1/3 and an emulsifier with the formula amount of 1/2, increasing the stirring rotation speed to 240-600 rpm, slowly dripping an acrylic acid monomer into a reaction kettle after diluting the acrylic acid monomer with a solvent, adding deionized water after the dripping 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, dropwise adding the mixture into a reaction kettle, after 20-40 min of dropwise adding, and stirring for reacting for 40-60 min;
(5) Adding the rest deionized water, cooling to room temperature, closing a 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;
the preparation method of the modified nano carbon material comprises the following steps:
(1) Uniformly mixing the first polyester polyol and the silane coupling agent to obtain a mixed material;
(2) Soaking the graphene oxide and the multiwall carbon nanotubes in the mixed material, adding the alcohol diluent, uniformly stirring at a stirring speed of 100-200 rpm for 30-60 min to obtain mixed slurry;
(3) Heating the mixed slurry to 60-90 ℃ for 30-40 min to solidify the mixed slurry into loose block-shaped objects;
(4) Grinding the block into powder, and sieving to obtain the modified nano carbon material.
2. The conductive PUA composite emulsion according to claim 1 wherein said first polyester polyol is selected from at least one of polyethylene adipate glycol, polyepsilon caprolactone glycol, polycarbonate glycol.
3. The conductive PUA composite emulsion according to claim 1 wherein said alcohol diluent is selected from at least one of isopropanol, methanol, ethanol, benzyl alcohol, and ethylene glycol.
4. The conductive PUA composite emulsion according to claim 1 wherein said silane coupling agent is selected from at least one of gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane and gamma-methacryloxypropyl trimethoxysilane.
5. The electrically conductive PUA composite emulsion of claim 1, wherein the 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.
6. The conductive PUA composite emulsion according to claim 1 wherein said emulsifier is anionic.
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