CN118085607B - Modified silica micropowder and application thereof in external wall heat insulation coating - Google Patents
Modified silica micropowder and application thereof in external wall heat insulation coating Download PDFInfo
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- CN118085607B CN118085607B CN202410493961.4A CN202410493961A CN118085607B CN 118085607 B CN118085607 B CN 118085607B CN 202410493961 A CN202410493961 A CN 202410493961A CN 118085607 B CN118085607 B CN 118085607B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 238000009413 insulation Methods 0.000 title claims abstract description 37
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002071 nanotube Substances 0.000 claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims abstract 9
- 239000000839 emulsion Substances 0.000 claims description 47
- 229910052621 halloysite Inorganic materials 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 150000003376 silicon Chemical class 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000013530 defoamer Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 9
- 229960002887 deanol Drugs 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 7
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 7
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 7
- -1 isocyanato graphene Chemical compound 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910021487 silica fume Inorganic materials 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of exterior wall heat-insulating paint, and discloses modified silica micropowder and application thereof in exterior wall heat-insulating paint, wherein the preparation method comprises the following steps: taking graphene oxide and isophorone diisocyanate to react under the action of a catalyst to obtain isocyanated graphene oxide; according to the invention, the isocyanated graphene oxide is used as a silicon micropowder modifier, so that the heat insulation effect, the heat insulation effect in a corrosive environment and the impact resistance of the coating are improved, and in addition, the modified halloysite nanotube is added into the water-based acrylic coating, so that the coating has excellent flame retardant property, and meanwhile, the impact resistance of the coating is further improved.
Description
Technical Field
The invention belongs to the technical field of exterior wall heat-insulating coating, and particularly relates to modified silica micropowder and application thereof in exterior wall heat-insulating coating.
Background
The silicon micropowder is a silicon dioxide powder material obtained by taking natural quartz or fused quartz as a raw material and processing the raw material through the procedures of crushing, screening, grinding, magnetic separation, flotation, acid washing, high purity water treatment and the like, is taken as a typical inorganic filler, has excellent characteristics of three high (high insulativity, high heat conduction and high heat stability), three low (low thermal expansion coefficient, low dielectric constant and low raw material cost) and two resistances (acid and alkali resistance and wear resistance), and is taken as a high-performance filler to be widely applied to heat insulation coating.
The silicon micropowder is applied to the coating, has excellent heat insulation performance and high temperature resistance, and can effectively reflect and dissipate solar radiation energy due to higher solar reflectivity and emissivity, so that the temperature of the surface of the coating is reduced, heat transfer is reduced, and in addition, the silicon micropowder also has good cohesiveness and thickening property, and can provide better coating effect and adsorption performance for the coating. However, the silica micropowder belongs to polar and hydrophilic substances, has different interface properties with the polymer matrix, has poor compatibility and is difficult to disperse in the base material, so that the silica micropowder is usually required to be subjected to surface modification, and the physicochemical properties of the surface of the silica micropowder are purposefully changed according to the application requirements, so that the compatibility of the silica micropowder with the polymer matrix is improved, and the dispersibility and heat insulation requirements of the silica micropowder in the polymer matrix are met.
In addition, the common aqueous acrylic emulsion in the heat insulation coating for the outer wall uses water as a main solvent, is low in cost, safe and environment-friendly, has good stain resistance, washing resistance and light resistance, and is added with a large amount of flame retardants in order to realize the flame retardance of the aqueous acrylic emulsion in the prior art, but the migration and exudation phenomenon exists in the addition of the large amount of flame retardants, and meanwhile, the comprehensive performance of the coating, particularly the mechanical property of the coating after film formation, is also deteriorated.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide modified silicon micropowder and application thereof in external wall heat insulation coating, and the modified silicon micropowder is modified by using isocyanato graphene oxide as a modifier, so that the heat insulation effect, the heat insulation effect in corrosive environment and the impact resistance of the coating are improved, in addition, modified halloysite nanotubes are added in the aqueous acrylic external wall heat insulation coating, the coating is endowed with excellent flame retardant property, and meanwhile, the impact resistance of the coating is further improved.
The aim of the invention can be achieved by the following technical scheme:
The modified silicon micropowder comprises silicon micropowder and a modifier, wherein the modifier is isocyanated graphene oxide; the preparation method of the modified silicon micropowder comprises the following steps:
(1) Taking graphene oxide in N, N-dimethylformamide, performing ultrasonic dispersion to obtain graphene oxide dispersion liquid, adding isophorone diisocyanate and dibutyltin dilaurate into the graphene oxide dispersion liquid, heating to 70-85 ℃, continuously reacting for 6-8 hours under magnetic stirring in a nitrogen atmosphere, and centrifuging, washing and drying after the reaction is completed to obtain isocyanated graphene oxide;
(2) And (3) taking silicon micropowder in butyl acetate, ultrasonically dispersing at 25-40 ℃, transferring to a reactor, heating to 55-70 ℃, adding dibutyl tin dilaurate, uniformly mixing isocyanato graphene oxide and butyl acetate, adding into the reactor, reacting for 9-11 hours at the constant temperature of 55-70 ℃, and carrying out suction filtration, washing and drying after the reaction is completed to obtain the modified silicon micropowder.
Preferably, in the step (1), the mass ratio of graphene oxide, isophorone diisocyanate and dibutyltin dilaurate is 0.1: 8-12: 0.02 to 0.05.
Preferably, in the step (2), the mass ratio of the silicon micropowder, the dibutyl tin dilaurate and the isocyanated graphene oxide is 15-30: 0.02-0.05: 30-45.
The application of the modified silica micropowder in the external wall heat-insulating coating comprises the following raw materials in parts by weight: 40-60 parts of acrylic emulsion, 40-50 parts of modified silica micropowder, 5-15 parts of modified halloysite nanotube, 3-8 parts of pigment, 0.5-1 part of defoamer, 1-5 parts of thickener, 0.5-1 part of pH regulator and 20-43 parts of water; the acrylic emulsion is a copolymer emulsion prepared from 25-30 parts of acrylic acid, 5-12 parts of methacrylic acid, 15-30 parts of butyl acrylate and 5-15 parts of styrene.
Preferably, the pigment is one or a combination of more of rutile type titanium dioxide, zinc oxide and superfine mica powder; the defoaming agent is an organosilicon defoaming agent; the thickener is one or a combination of more of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose and polydimethylsiloxane; the pH regulator is dimethylaminoethanol.
Preferably, the preparation method of the modified halloysite nanotube comprises the following steps:
A. Adding halloysite nanotubes into an ethanol solvent, stirring to remove organic impurities, filtering, drying, grinding, adding the halloysite nanotubes into deionized water, mechanically stirring for 1-3 hours, adding sodium hexametaphosphate during stirring, removing lower impurity precipitates by using a filtering method after stirring, collecting solids in an upper suspension by using a centrifugal method, and drying and grinding the solids to obtain purified halloysite nanotubes;
B. Adding purified halloysite nanotubes into an acetone solvent, performing ultrasonic dispersion for 30-60 min, continuously adding 5-isocyanate isophthaloyl chloride and dibutyltin dilaurate, uniformly mixing, placing in a water bath kettle at 40-60 ℃ for stirring reaction for 12-24 h, centrifuging after the reaction is finished, collecting solid products, and performing vacuum drying to obtain chlorinated halloysite nanotubes;
C. Taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethanolamine and deionized water in a reactor, stirring and heating to 70-85 ℃, then dropwise adding paraformaldehyde, refluxing for 1-2 hours at constant temperature under the protection of nitrogen, cooling to room temperature, and then carrying out vacuum rotary evaporation, washing, purification, drying and grinding to obtain DOPO derivatives;
D. And adding N, N-dimethylacetamide into the DOPO derivative and the acyl chloride halloysite nanotube, ultrasonically oscillating at room temperature, then dropwise adding pyridine, heating to 105-130 ℃ for reflux reaction for 24-48 hours, cooling to room temperature, and then filtering, washing and drying to obtain the modified halloysite nanotube.
Preferably, the addition amount of the sodium hexametaphosphate in the step A is 1-3% of the mass of the halloysite nanotube, and the mass ratio of the purified halloysite nanotube, the 5-isocyanate isophthaloyl chloride and the dibutyl tin dilaurate in the step B is 1: 0.4-1: 0.01 to 0.03.
Preferably, in the step C, the mass ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethanolamine and paraformaldehyde is 10 to 25: 4-8: 1.5-2.
Preferably, the addition ratio of DOPO derivative, halloysite chloride nanotube and pyridine in step D is 10g: 1-5 g: 2-3 mL.
Preferably, the preparation method of the external wall heat insulation coating comprises the following steps:
s1, fully mixing acrylic acid, methacrylic acid, butyl acrylate and styrene, and then dripping the mixture into deionized water containing 1% of polyoxyethylene-4-phenolether ammonium sulfate, and preparing a pre-emulsion by high-speed dispersion;
S2, adding an ammonium persulfate initiator, a polyoxyethylene-4-phenol-based ether ammonium sulfate emulsifier and a pH buffer sodium bicarbonate into a reaction kettle, heating to 80-85 ℃, and dropwise adding 10% of pre-emulsion to prepare seed emulsion;
S3, carrying out heat preservation reaction on the seed emulsion for 10-30 min, then dropwise adding the rest pre-emulsion and an initiator, heating to 90-95 ℃ after the completion of dropwise adding, carrying out heat preservation reaction for 1-2 h, cooling to room temperature, regulating the pH value to 7-8 by using ammonia water, and discharging to obtain an acrylic emulsion base material;
And S4, adding the modified silica micropowder, the modified halloysite nanotube, the pigment and the defoamer into deionized water, stirring at a high speed, uniformly mixing to prepare slurry, then adding the acrylic emulsion base material, adding the pH regulator to adjust the pH value to 7-8, heating to 40-50 ℃ and stirring for 30-50 min, and finally adding the thickener, and continuing stirring for 10-20 min to prepare the external wall heat insulation coating.
The invention has the beneficial effects that:
According to the invention, isophorone diisocyanate is utilized to modify graphene oxide, wherein the reactivity of-NCO groups in isophorone diisocyanate, which are directly connected with cyclohexane rings, is higher, the isophorone diisocyanate is firstly reacted with carboxyl groups and hydroxyl groups on the surface of the graphene oxide, so that isocyanate groups are introduced on the surface of the graphene oxide, isocyanated graphene oxide is obtained, and then the isocyanated graphene oxide is used as a modifier of silicon micropowder, so that the-NCO groups on the surface of the isocyanated graphene oxide are reacted with the hydroxyl groups on the surface of the silicon micropowder, the silicon micropowder is grafted between graphene oxide layers, the grafted silicon micropowder improves the compatibility of the silicon micropowder in a polymer matrix, the dispersion of the silicon micropowder in the polymer matrix is facilitated, the heat insulation performance and the high temperature resistance performance of the silicon micropowder are fully exerted, meanwhile, the graphene oxide sheet layer presents a loose structure, the aggregation of the graphene oxide is avoided, the graphene oxide has higher heat stability, excellent barrier performance and low gas-liquid permeation performance, the modified graphene oxide forms a large-area protection layer in a sheet shape, the corrosion-resistant medium is immersed into the silicon micropowder, the corrosion-resistant coating is enhanced, and the corrosion-resistant performance of the heat-resistant coating is cooled, and the corrosion-resistant performance of the heat-resistant coating is improved.
According to the invention, organic matters in the halloysite nanotube are dissolved by using ethanol, organic matters are removed, the solution is redispersed in deionized water, a dispersing agent sodium hexametaphosphate is added in the stirring process, mineral matters with poor dispersibility can be settled, the settled matters are removed by filtration, the obtained halloysite nanotube in the upper suspension has higher purity, and the purified halloysite nanotube is separated by using a centrifugal separation mode, so that the further grafting reaction of the halloysite nanotube is facilitated, and hydroxyl groups on the surface of the purified halloysite nanotube are catalyzed and reacted with isocyanate groups in a 5-isocyanate isophthaloyl chloride structure to generate the acyl chloride halloysite nanotube.
According to the invention, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is reacted with diethanolamine to prepare the DOPO derivative as the flame retardant, and then the DOPO derivative is subjected to grafting reaction with the halloysite nanotube to obtain the modified halloysite nanotube, wherein the surface of the DOPO derivative contains dihydroxyl and is grafted to the surface of the halloysite nanotube through covalent bonds, so that the DOPO derivative flame retardant is modified on the surface of the halloysite nanotube, and the halloysite nanotube is in a tubular structure, so that the flame retardant can be slowly released, a good flame retardant effect can be achieved, the migration and exudation problem does not exist, the long-term flame retardant effect of the coating is ensured, the dispersion of the halloysite nanotube is facilitated, and the performance defect caused by the aggregation of the halloysite nanotube can be avoided to a certain extent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1a method for preparing modified silica micropowder comprises the following steps:
Taking 0.1g of graphene oxide, carrying out ultrasonic dispersion on the graphene oxide in 100mLN, N-dimethylformamide to obtain graphene oxide dispersion liquid, adding 8.2g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate into the graphene oxide dispersion liquid, heating to 75 ℃, continuously reacting for 6 hours under magnetic stirring in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is completed, and preparing isocyanated graphene oxide;
and (3) taking 25g of silicon micropowder in 170mL of butyl acetate, transferring to a reactor after ultrasonic dispersion at 30 ℃, heating to 55 ℃, adding 0.02g of dibutyltin dilaurate, uniformly mixing 30g of isocyanato graphene oxide and 70mL of butyl acetate, adding into the reactor, reacting for 9 hours at the constant temperature of 55 ℃, and carrying out suction filtration, washing and drying after the reaction is completed to obtain the modified silicon micropowder.
Example 2a method for preparing a modified halloysite nanotube comprises the steps of:
A. adding 5g halloysite nanotubes into 100mL ethanol solvent, stirring to remove organic impurities, filtering, drying, grinding, adding the halloysite nanotubes into 150mL deionized water, mechanically stirring for 1h, adding 0.05g sodium hexametaphosphate during stirring, removing lower impurity precipitate by using a filtering method after stirring, collecting solids in an upper suspension by using a centrifugal method, drying and grinding the solids to obtain purified halloysite nanotubes;
B. Adding 1g of purified halloysite nanotube into 40mL of acetone solvent, performing ultrasonic dispersion for 30min, continuously adding 0.4g of 5-isocyanate isophthaloyl chloride and 0.01g of dibutyltin dilaurate, uniformly mixing, placing into a water bath kettle at 40 ℃ for stirring reaction for 12h, centrifuging after the reaction is finished, collecting a solid product, and performing vacuum drying to obtain the chlorinated halloysite nanotube;
C. Taking 10g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4.5g of diethanolamine and 100mL of deionized water in a reactor, stirring and heating to 80 ℃, then dropwise adding 1.5g of paraformaldehyde, refluxing for 1h at constant temperature under the protection of nitrogen, cooling to room temperature, vacuum rotary evaporation, washing and purifying, drying and grinding to obtain DOPO derivatives;
D. adding 180mLN, N-dimethylacetamide into 10gDOPO derivatives and 1g of acyl chloride halloysite nanotube, ultrasonically oscillating at room temperature, dripping 2mL pyridine, heating to 120 ℃ for reflux reaction for 48h, cooling to room temperature, filtering, washing and drying to obtain the modified halloysite nanotube.
The embodiment 3 of the heat insulation coating for the outer wall comprises the following raw materials in parts by weight: 43 parts of acrylic emulsion, 40 parts of modified silica micropowder, 5 parts of modified halloysite nanotube, 3 parts of rutile type titanium dioxide, 0.5 part of organosilicon defoamer, 1 part of hydroxyethyl methyl cellulose, 0.5 part of dimethylaminoethanol and 20 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 25 parts of acrylic acid, 6 parts of methacrylic acid, 20 parts of butyl acrylate and 8 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating comprises the following steps:
S1, fully mixing 250g of acrylic acid, 60g of methacrylic acid, 200g of butyl acrylate and 80g of styrene, and then dripping into 4.5L of deionized water containing 1% polyoxyethylene-4-phenolether ammonium sulfate, and dispersing at a high speed to prepare a pre-emulsion;
S2, adding 1.2g of ammonium persulfate initiator, 4g of polyoxyethylene-4-phenol-based ether ammonium sulfate emulsifier and 12gpH buffer sodium bicarbonate into a reaction kettle, heating to 80 ℃, and dropwise adding 10% of pre-emulsion to prepare seed emulsion;
S3, carrying out heat preservation reaction on the seed emulsion for 20min, then dropwise adding the rest pre-emulsion and 3.6g of initiator, heating to 90 ℃ after the completion of dropwise adding, carrying out heat preservation reaction for 1h, cooling to room temperature, regulating the pH value to 7 by using ammonia water, and discharging to obtain an acrylic emulsion base material;
And S4, adding 450g of modified silica micropowder, 60g of modified halloysite nanotube, 40g of rutile type titanium dioxide and 10g of organic silicon defoamer into 300mL of deionized water, stirring at a high speed, uniformly mixing to prepare slurry, then adding 430g of acrylic emulsion base material, adding dimethylaminoethanol to adjust the pH value to 7, heating to 45 ℃, stirring for 30min, and finally adding 10g of hydroxyethyl methyl cellulose, and continuing stirring for 10-20 min to prepare the external wall heat insulation coating.
The embodiment 4 of the exterior wall heat insulation coating comprises the following raw materials in parts by weight: 50 parts of acrylic emulsion, 50 parts of modified silicon micropowder, 10 parts of modified halloysite nanotube, 4 parts of zinc oxide, 0.8 part of organosilicon defoamer, 1 part of hydroxypropyl methyl cellulose, 0.6 part of dimethylaminoethanol and 40 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 27 parts of acrylic acid, 8 parts of methacrylic acid, 20 parts of butyl acrylate and 10 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating is the same as that of example 3.
The embodiment 5 of the heat insulation coating for the outer wall comprises the following raw materials in parts by weight: 60 parts of acrylic emulsion, 50 parts of modified silicon micropowder, 15 parts of modified halloysite nanotube, 7 parts of rutile type titanium dioxide, 1 part of organosilicon defoamer, 4 parts of hydroxypropyl methyl cellulose, 0.5 part of dimethylaminoethanol and 43 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 27 parts of acrylic acid, 8 parts of methacrylic acid, 20 parts of butyl acrylate and 10 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating is the same as that of example 3.
Comparative example 1 an exterior wall heat insulation coating comprises the following raw materials in parts by weight: 46 parts of acrylic emulsion, 50 parts of silicon micropowder, 10 parts of modified halloysite nanotube, 3 parts of rutile type titanium dioxide, 1 part of organosilicon defoamer, 2 parts of hydroxypropyl methyl cellulose, 0.6 part of dimethylaminoethanol and 30 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 25 parts of acrylic acid, 8 parts of methacrylic acid, 20 parts of butyl acrylate and 8 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating is the same as that of example 3.
Comparative example 2 an exterior wall heat insulation coating comprises the following raw materials in parts by weight: 60 parts of acrylic emulsion, 27 parts of silicon micropowder, 23 parts of graphene oxide, 12 parts of modified halloysite nanotube, 7 parts of rutile type titanium dioxide, 1 part of organosilicon defoamer, 4 parts of hydroxypropyl methyl cellulose, 0.5 part of dimethylaminoethanol and 43 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 27 parts of acrylic acid, 8 parts of methacrylic acid, 20 parts of butyl acrylate and 10 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating is the same as that of example 3.
Comparative example 3 an exterior wall heat insulation coating comprises the following raw materials in parts by weight: 50 parts of acrylic emulsion, 45 parts of modified silicon micropowder, 15 parts of halloysite nanotube, 7 parts of rutile type titanium dioxide, 1 part of organosilicon defoamer, 2 parts of hydroxypropyl methyl cellulose, 0.6 part of dimethylaminoethanol and 40 parts of water; the acrylic emulsion is a copolymer emulsion prepared by taking 27 parts of acrylic acid, 8 parts of methacrylic acid, 20 parts of butyl acrylate and 10 parts of styrene as raw materials.
The preparation method of the external wall heat insulation coating is the same as that of example 3.
Performance detection
(1) Oil absorption value test: 1g of unmodified silica micropowder and the modified silica micropowder prepared in example 1 were weighed respectively, placed in a glass, dibutyl phthalate was added dropwise while stirring until the powder formed a dough, the mass of dibutyl phthalate (DBP) was recorded and measured three times, and the average value was taken, and the oil absorption value was calculated as follows: oil absorption value=m (DBP)/m (modified silica fume) ×100, and the measured oil absorption value of the unmodified silica fume is 33% and the oil absorption value of the modified silica fume is 22%, which indicates that the oil absorption value of the silica fume is reduced after modification, which means that the adsorption force between silica fume particles is reduced, the surface energy is reduced, and the agglomeration degree is reduced.
(2) Activation index test: 50mL of deionized water is taken in a beaker, 2g of the modified silica micropowder prepared in the example 1 is added and stirred for 5min, the mixture is left for 30min after stirring is finished until the solution is clear, a sample on the surface of the aqueous solution is scraped off, and the sample sunk into the bottom of the beaker is filtered, dried and weighed. The formula for the activation index H is as follows: h= (M 1/M2) x 100, where M 1 is the mass-g of the floating sample and M 2 is the mass-g of the sinking sample, the activation index was measured to be 78.9%.
(3) Wetting contact angle test: the surface wetting contact angles of the unmodified silica micropowder and the modified silica micropowder prepared in example 1 were respectively detected by a wetting contact angle measuring instrument, and the surface of the unmodified silica micropowder was 8.6 degrees, the surface was not hydrophobic, the contact angle of the modified silica micropowder was 117.2 degrees, and the surface was hydrophobic.
Performance test was performed on the exterior wall heat-insulating coating materials prepared in examples 3 to 5 and comparative examples 1 to 3:
a. And (3) heat insulation temperature difference test: coating a coating on the surface of the steel plate after sand blasting, drying and curing for 120 hours at 25 ℃, wherein the thickness of a dry film is 3mm, the temperature of a heat source is 250 ℃, and after 60min and 420 min heat insulation detection, measuring the temperature difference (heat insulation performance) between the heat source and the surface of a coating template to obtain data results shown in Table 1;
b. And (3) testing heat insulation temperature difference in a corrosion environment: performing corrosion soaking 420 h in 3.5% NaCl solution (50 ℃) to determine the temperature difference of the coating before and after corrosion, and obtaining the data result shown in Table 1;
c. impact resistance test: the impact resistance of the coating was measured with reference to GB/T1732-2020 and the data results are shown in Table 1;
d. Flame retardant performance test: the flame retardancy was passed through the limiting oxygen index test, and the data obtained are shown in Table 1.
TABLE 1 test sample Performance test results
As can be seen from the data in Table 1, the exterior wall heat-insulating coating prepared in examples 3 to 5 of the present invention has excellent heat-insulating effect, corrosion resistance, impact resistance and flame retardance. In comparative example 1, no modification treatment is performed on the silica micropowder, the heat insulation temperature difference and the impact strength of the silica micropowder are obviously reduced, the compatibility with a polymer matrix is poor, no graphene oxide is added, in comparative example 2, no grafting treatment is performed on the silica micropowder and the graphene oxide, the dispersion of the silica micropowder and the graphene oxide is unfavorable, the heat insulation temperature difference and the impact strength of the silica micropowder are slightly poorer than those of examples 3-5, wherein the heat insulation temperature difference and the impact strength of the silica micropowder in a corrosive environment in comparative example 1 are slightly lower than those of comparative example 2, the addition of the graphene oxide can enhance the cooling heat insulation performance and the impact resistance of the coating in the corrosive environment, in comparative example 3, the modification treatment is not performed on the halloysite nanotube, the flame retardant effect is poor, and the impact strength of the halloysite nanotube is slightly lower than those of examples 3-5 possibly caused by the phenomenon of the halloysite nanotube agglomeration.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The modified silicon micropowder is characterized by comprising silicon micropowder and a modifier, wherein the modifier is isocyanated graphene oxide; the preparation method of the modified silicon micropowder comprises the following steps:
(1) Taking graphene oxide in N, N-dimethylformamide, performing ultrasonic dispersion to obtain graphene oxide dispersion liquid, adding isophorone diisocyanate and dibutyltin dilaurate into the graphene oxide dispersion liquid, heating to 70-85 ℃, continuously reacting for 6-8 hours under magnetic stirring in a nitrogen atmosphere, and centrifuging, washing and drying after the reaction is completed to obtain isocyanated graphene oxide;
(2) And (3) taking silicon micropowder in butyl acetate, ultrasonically dispersing at 25-40 ℃, transferring to a reactor, heating to 55-70 ℃, adding dibutyl tin dilaurate, uniformly mixing isocyanato graphene oxide and butyl acetate, adding into the reactor, reacting for 9-11 hours at the constant temperature of 55-70 ℃, and carrying out suction filtration, washing and drying after the reaction is completed to obtain the modified silicon micropowder.
2. The modified silica micropowder according to claim 1, wherein the mass ratio of graphene oxide, isophorone diisocyanate and dibutyltin dilaurate in step (1) is 0.1: 8-12: 0.02 to 0.05.
3. The modified silica micropowder according to claim 1, wherein in the step (2), the mass ratio of the silica micropowder, dibutyltin dilaurate and isocyanato graphene oxide is 15-30: 0.02-0.05: 30-45.
4. The application of the modified silica micropowder in the external wall heat-insulating paint according to claim 1, wherein the external wall heat-insulating paint comprises the following raw materials in parts by weight: 40-60 parts of acrylic emulsion, 40-50 parts of modified silica micropowder, 5-15 parts of modified halloysite nanotube, 3-8 parts of pigment, 0.5-1 part of defoamer, 1-5 parts of thickener, 0.5-1 part of pH regulator and 20-43 parts of water; the acrylic emulsion is a copolymer emulsion prepared from 25-30 parts of acrylic acid, 5-12 parts of methacrylic acid, 15-30 parts of butyl acrylate and 5-15 parts of styrene.
5. The application of the modified silica micropowder in the external wall heat-insulating paint according to claim 4, wherein the pigment is one or a combination of more of rutile type titanium dioxide, zinc oxide and superfine mica powder; the defoaming agent is an organosilicon defoaming agent; the thickener is one or a combination of more of hydroxyethyl methylcellulose, hydroxypropyl methylcellulose and polydimethylsiloxane; the pH regulator is dimethylaminoethanol.
6. The application of the modified silica micropowder in the external wall heat-insulating coating according to claim 4, wherein the preparation method of the modified halloysite nanotube comprises the following steps:
A. Adding halloysite nanotubes into an ethanol solvent, stirring to remove organic impurities, filtering, drying, grinding, adding the halloysite nanotubes into deionized water, mechanically stirring for 1-3 hours, adding sodium hexametaphosphate during stirring, removing lower impurity precipitates by using a filtering method after stirring, collecting solids in an upper suspension by using a centrifugal method, and drying and grinding the solids to obtain purified halloysite nanotubes;
B. Adding purified halloysite nanotubes into an acetone solvent, performing ultrasonic dispersion for 30-60 min, continuously adding 5-isocyanate isophthaloyl chloride and dibutyltin dilaurate, uniformly mixing, placing in a water bath kettle at 40-60 ℃ for stirring reaction for 12-24 h, centrifuging after the reaction is finished, collecting solid products, and performing vacuum drying to obtain chlorinated halloysite nanotubes;
C. Taking 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethanolamine and deionized water in a reactor, stirring and heating to 70-85 ℃, then dropwise adding paraformaldehyde, refluxing for 1-2 hours at constant temperature under the protection of nitrogen, cooling to room temperature, and then carrying out vacuum rotary evaporation, washing, purification, drying and grinding to obtain DOPO derivatives;
D. And adding N, N-dimethylacetamide into the DOPO derivative and the acyl chloride halloysite nanotube, ultrasonically oscillating at room temperature, then dropwise adding pyridine, heating to 105-130 ℃ for reflux reaction for 24-48 hours, cooling to room temperature, and then filtering, washing and drying to obtain the modified halloysite nanotube.
7. The application of the modified silica micropowder in the exterior wall heat-insulating paint according to claim 6, wherein the addition amount of sodium hexametaphosphate in the step A is 1-3% of the mass of halloysite nanotubes, and the mass ratio of purified halloysite nanotubes, 5-isocyanate isophthaloyl chloride and dibutyltin dilaurate in the step B is 1: 0.4-1: 0.01 to 0.03.
8. The application of the modified silica micropowder in the exterior wall heat-insulating coating according to claim 6, wherein in the step C, the mass ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethanolamine and paraformaldehyde is 10-25: 4-8: 1.5-2.
9. The application of the modified silica micropowder in the external wall heat-insulating paint according to claim 6, wherein the addition ratio of DOPO derivative, halloysite chloride nanotube and pyridine in the step D is 10g: 1-5 g: 2-3 mL.
10. The application of the modified silica micropowder in the external wall heat-insulating paint according to claim 4, wherein the preparation method of the external wall heat-insulating paint comprises the following steps:
s1, fully mixing acrylic acid, methacrylic acid, butyl acrylate and styrene, and then dripping the mixture into deionized water containing 1% of polyoxyethylene-4-phenolether ammonium sulfate, and preparing a pre-emulsion by high-speed dispersion;
S2, adding an ammonium persulfate initiator, a polyoxyethylene-4-phenol-based ether ammonium sulfate emulsifier and a pH buffer sodium bicarbonate into a reaction kettle, heating to 80-85 ℃, and dropwise adding 10% of pre-emulsion to prepare seed emulsion;
S3, carrying out heat preservation reaction on the seed emulsion for 10-30 min, then dropwise adding the rest pre-emulsion and an initiator, heating to 90-95 ℃ after the completion of dropwise adding, carrying out heat preservation reaction for 1-2 h, cooling to room temperature, regulating the pH value to 7-8 by using ammonia water, and discharging to obtain an acrylic emulsion base material;
And S4, adding the modified silica micropowder, the modified halloysite nanotube, the pigment and the defoamer into deionized water, stirring at a high speed, uniformly mixing to prepare slurry, then adding the acrylic emulsion base material, adding the pH regulator to adjust the pH value to 7-8, heating to 40-50 ℃ and stirring for 30-50 min, and finally adding the thickener, and continuing stirring for 10-20 min to prepare the external wall heat insulation coating.
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