CN116855090A - High-water-repellency silicon-based micro-nano powder filler and preparation method thereof - Google Patents
High-water-repellency silicon-based micro-nano powder filler and preparation method thereof Download PDFInfo
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- 239000011858 nanopowder Substances 0.000 title claims abstract description 65
- 239000000945 filler Substances 0.000 title claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000005871 repellent Substances 0.000 claims abstract description 35
- 229920002050 silicone resin Polymers 0.000 claims abstract description 34
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- -1 ammonia hydrocarbon Chemical class 0.000 claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
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- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
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- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000002940 repellent Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 9
- 238000000593 microemulsion method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- FGZFESWHQXSPJU-UHFFFAOYSA-N 2-methyl-2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[Si]1(C)O[SiH2]O[SiH2]O1 FGZFESWHQXSPJU-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- XUKFPAQLGOOCNJ-UHFFFAOYSA-N dimethyl(trimethylsilyloxy)silicon Chemical compound C[Si](C)O[Si](C)(C)C XUKFPAQLGOOCNJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 24
- 238000001035 drying Methods 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 230000003068 static effect Effects 0.000 abstract description 6
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- 238000012703 microemulsion polymerization Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000007873 sieving Methods 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004844 aliphatic epoxy resin Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003075 superhydrophobic effect Effects 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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)
- Silicon Polymers (AREA)
Abstract
The invention relates to a high water-repellent silicon-based micro-nano powder filler and a preparation method thereof, comprising the following steps: firstly, respectively adding siloxane monomer components into a reactor; then adding the hydrolysis medium, the water carrying agent and the aqueous solution of the strong base catalyst in turn, and then uniformly stirring and heating for reaction. And after the reaction is finished, heating is continued, and the ammonia hydrocarbon modified silicone resin is obtained through reduced pressure distillation and purification. And then, fully and uniformly mixing the amino hydrocarbon modified silicone resin, the modified epoxy resin and the nano particles according to a certain weight ratio under a high-speed shearing mixer, adding an emulsifying agent, preparing a stable emulsion system through reverse microemulsion polymerization, curing at high temperature, and obtaining the micro-nano powder filler after suction filtration, separation, washing, drying, grinding and sieving. The powder filler has a static contact angle of more than 140 degrees, has excellent characteristics of micro-nano structure, low surface energy, stable performance and the like, and has mild reaction conditions, energy conservation and environmental protection.
Description
Technical Field
The invention relates to the field of chemical and organic silicon new materials, in particular to a high-water-repellency silicon-based micro-nano powder filler and a preparation method thereof.
Background
Water repellency is widely used in biological systems, such as self-cleaning mechanisms for lotus leaves and rice leaves. The water droplets can remove particles and pathogens from the leaves, thereby providing greater resilience to chemical and biological damage. This effect, also known as hydrophobicity, is of considerable advantage in many engineering applications. For example, a low cost water repellent coating that can be produced from clean building facades, is resistant to biological deterioration, algae growth and general contamination would be of significant advantage. Other important uses for hydrophobic coatings also include applications in anti-biofouling vessels and marine infrastructure, ice protection surfaces, and corrosion resistance. Meanwhile, the silicon resin material is widely applied to industrial fields and high and new technical fields of military industry, aerospace, petrochemical industry, machinery, construction, power and electrical appliances, automobile environmental protection, new energy and strategic emerging industry and the like due to the advantages of excellent oxidation resistance, temperature resistance, weather resistance, hydrophobicity, chemical corrosion resistance and the like, and is an important chemical environment-friendly new material. The side chain of the siloxane is connected with a functional group with low surface energy, the silicon resin with better water repellency can be synthesized, and the hydrophobic powder particles with special micro-nano structures and lower specific surface energy on the surface are further synthesized, so that the method has great application value in the field of surface protection of the outer wall of a wall body building and other objects. In recent years, researchers respectively construct micron nano coarse structures on the surfaces of objects through methods such as a template etching method, a chemical vapor deposition method, an electrochemical method and the like or modify low-surface-energy substances on the coarse solid surfaces to realize the surface hydrophobicity, but the technology still has a large technical barrier, such as incapability of being applied in a large scale and incapability of realizing large-area industrial application such as wall surfaces, building surfaces and the like. At present, the waterproof coating produced by compounding the water repellent powder filler with other materials is still the preferred mode of industry application. Therefore, the chemical synthesis of low-surface energy substances is directly carried out, and then a process design is adopted to form the micro-coarse structure on the required surface so as to realize the high-water-repellent micro-nano powder filler with a micro-nano structure and low specific surface energy.
Chinese patent (CN 104672962A) uses polymer nano particles such as polystyrene/polymethyl acrylate as a template, hydrosol obtained by hydrolysis of tetraethoxysilane hydrochloric acid as a mother solution, the mother solution is injected into the template to form gel, then polymer microspheres are removed by a calcining mode, and the obtained powder is ground and then modified with silane coupling agent containing hydrophobic groups to obtain super-hydrophobic powder with micro-nano structure and low surface energy group modification.
Chinese patent (CN 108384284A) utilizes the reaction of a nano microsphere template to prepare nano particle hydrogel, the nano particle hydrogel is dried and agglomerated in a constant temperature drying oven, finally, dry nano particle powder is obtained by grinding, then, the nano particle powder is reacted with a liquid-phase hydrophobic coupling agent in the presence of a catalyst for modification, and the super-hydrophobic inorganic material powder is obtained by filtering. The method simplifies the steps, has simple required equipment and can realize large-scale preparation, but actually carries out low surface energy substance modification on the nano particles through a coupling reaction, thereby endowing the powder material with super-hydrophobic property, and in the actual application scene, the stability of the powder material is still insufficient, and the surface modified low surface energy substance is easy to be broken. In addition, the silane coupling agent is selected to be perfluoro siloxane, and the raw material cost is high.
Chinese patent (CN 111777736A) uses isocyanate and hydroxy silicone oil to add into tetrahydrofuran, stir at certain temperature, condense and reflux in inert gas atmosphere; stopping heating, slowly adding tetrahydrofuran solution containing chain extender and catalyst after the system temperature is cooled, and continuously stirring and reacting in inert gas atmosphere; after the reaction is finished, pouring the reaction product into a precipitated phase, carrying out suction filtration and separation, drying the separated matter, grinding and sieving to obtain the super-hydrophobic powder material. Although the method simplifies the steps, the required equipment is simple, a large amount of organic solvents can be used in the whole reaction process, and the method does not accord with the green environmental protection concept in large-scale production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the preparation method which is simple, safe and efficient in industrialized flow, environment-friendly, and easy to realize mass production, and the material has the characteristics of micro-nano structure, low surface energy, stable structure and the like.
The technical scheme of the invention is as follows:
a high water-repellent silicon-based micro-nano powder filler and a preparation method thereof are provided, wherein the filler is prepared by the following steps: firstly, preparing and synthesizing colorless transparent amino hydrocarbon modified silicone resin under the action of a strong base catalyst through siloxane monomer components. And then, fully and uniformly mixing the amino hydrocarbon modified silicone resin, the modified epoxy resin and the nano particles according to a certain weight ratio under a high-speed emulsifying mixer, adding an emulsifying agent, and dropwise adding deionized water under high-speed shearing and dispersing. When the emulsion system is converted from liquid state to solid state oily body, pouring hot water to react for a certain time to make the reaction system present stable emulsion system in hot environment. After the reaction is finished, the emulsion system is heated to 120 ℃ and is stirred and cured for 2 hours under heat preservation, so as to ensure that the silicon resin is thoroughly solidified into powder particles, a powder crude product is obtained through suction filtration and separation, and then the powder crude product is washed by ethanol, dried by a vacuum oven, ground and sieved to obtain the high-water-repellent silicon-based micro-nano powder filler.
Further, the method comprises the following steps:
step S1, preparing amino alkyl modified silicone resin: adding 1-70g of siloxane, 1-20g of deionized water, 1-30g of hydrolysis medium, 1-10g of water carrying agent and 0.01-0.1g of potassium hydroxide into a reactor protected by inert atmosphere, stirring and reacting for 8-12 h at the temperature of 65-85 ℃ under alkaline condition, and carrying out reduced pressure distillation at the temperature of 130-140 ℃ to remove water and alcohol to obtain colorless and transparent amino alkyl modified silicone resin.
Step S2, preparing stable emulsion by an inverse microemulsion method: taking 1-50g of the amino hydrocarbon modified silicone resin prepared in the step S1, 1-40g of the modified epoxy resin and 0.01-0.5g of nano particles according to a certain mass ratio, shearing and dispersing at a high speed of 1200-2200r/min under 1-20g of an emulsifying agent, dripping deionized water at the same time for phase inversion, adding 20-500ml of hot water at 50-100 ℃ for emulsification self-assembly reaction for 4-8 hours, and obtaining a uniform and stable white emulsion system.
Step S3, after-treatment of an emulsion system: and (2) heating the white emulsion system in the step (S2) to 120 ℃, preserving heat, stirring and curing for 2-4 hours to ensure that the silicon resin is thoroughly solidified into micro-nano powder particles, standing, carrying out suction filtration on the obtained crude product, washing the crude product with absolute ethyl alcohol for three times, carrying out vacuum drying at 70 ℃ for 12 hours, and grinding the crude product and obtaining the high-water-repellency micro-nano powder particles through a 400-mesh screen.
Further, the siloxane monomers are of the following type: difunctional mer siloxanes: trifluoropropyl methyl cyclotrisiloxane (D3F), diphenyl dimethoxy (or ethoxy) silane, N-aminoethyl- γ -aminopropyl methyl dimethoxy silane (KH-602), octamethyltrisiloxane, and the like; trifunctional blocked siloxanes: perfluoroalkyl (C7-C12) trimethoxy (or ethoxy) silane, phenyltrimethoxy (or ethoxy) silane, and gamma-aminopropyl trimethoxy silane (KH-550), and the like; blocked siloxanes: pentamethyldisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, and the like; through three or more of the hydrolysis and condensation.
Further, the hydrolysis medium is a low boiling point organic solvent, and the boiling point is 50-140 ℃, such as acetone, cyclohexane, toluene or xylene, and other single or mixed organic solvents.
Further, the strong base catalyst may be one or more of sodium hydroxide, potassium hydroxide and other water soluble strong base catalysts.
Further, in the inverse microemulsion method, the ratio of the active hydrogen value of the amino hydrocarbon-based modified silicone resin to the epoxy value in the epoxy resin is 0.85 to 0.96:1 (mol/100 g), the content of nano particles is 0.1-0.5% (mass), the amount of dropwise adding deionized water is 30-45% of the total mass of the resin, the temperature of adding hot water is 50-100 ℃, and the mass of the hot water is 8-10 times of the total mass of the amino hydrocarbon modified silicone resin and the epoxy resin.
Further, the emulsifier is used in an amount of 5-20% of the mass of the reactant, and is any water-soluble nonionic emulsifier with a hydrophilic-lipophilic balance (HLB) value of 9-16.
Further, the nano particles in the reverse microemulsion method are single or combined nano particle size particles such as nano silicon dioxide, nano titanium dioxide, nano calcium carbonate and the like.
The invention also comprises the high-water-repellency silicon-based micro-nano powder filler prepared by the steps.
The invention has the following excellent characteristics:
1. the high-water-repellency silicon-based micro-nano powder filler and the preparation method thereof provided by the invention have the following characteristics: the preparation method has simple steps, safe and efficient industrialized flow and is environment-friendly;
2. the material has the advantages of micro-nano structure, low surface energy, stable structure, mild reaction condition, energy conservation and environmental protection, and the prepared silicon-based micro-nano powder filler has stable performance.
3. The introduction of the amino hydrocarbon modified silicon resin endows the nano powder filler with more excellent properties such as oxidation resistance, temperature resistance, weather resistance, hydrophobicity and chemical corrosion resistance, and the high-water-repellency silicon-based micro-nano powder filler prepared by the method can be applied to more engineering fields with hydrophobic requirements.
Drawings
FIG. 1 is a diagram of a silicone monomer hydrolytic condensation reaction mechanism and a polymerization mechanism of an epoxy resin and an amino hydrocarbon-based modified silicone resin;
FIG. 2 is a sample diagram of a high water repellent silicon-based micro-nano powder filler;
FIG. 3 is a graph showing apparent hydrophobic effects of a high water repellent silicon-based micro-nano powder filler;
FIG. 4 is an SEM microtopography of a high water repellent silicon-based micro-nano powder filler;
FIG. 5 is an infrared spectrum of an amino hydrocarbon-based modified silicone resin prepared by hydrolytic condensation of an organosilicon monomer and a high water repellent silicon-based micro-nano powder filler prepared by inverse microemulsion polymerization;
fig. 6 is a contact angle test chart of the high water repellent silicon based micro-nano powder filler of examples 1-4.
Detailed Description
The invention will now be described in detail with reference to the drawings and to specific embodiments.
Embodiment one:
step S1, preparing amino alkyl modified silicone resin: 27g of trifluoropropyl methyl cyclotrisiloxane (D3F) are added into the reactor under the protection of nitrogen; 11g of diphenyl diethoxy silane; 9g of dimethyl diethoxy silane; 3g of gamma-aminopropyl trimethoxysilane (KH-550); 13g of octamethyltrisiloxane; potassium hydroxide 0.01g; toluene 25g, xylene 5g. Then 0.01g of potassium hydroxide is dissolved in 15g of deionized water, stirred and added into a reactor, the temperature is raised to 70 ℃ for reaction for 12 hours, and then the system is slowly raised to 130 ℃ for reduced pressure distillation to remove low-boiling substances and moisture generated by hydrolytic condensation reaction, thus obtaining colorless and transparent amino hydrocarbon modified silicone resin.
Step S2, preparing uniform emulsion by an inverse microemulsion method: 20g of the amino hydrocarbon-based modified silicone resin prepared in the step S1, 10g of aliphatic epoxy resin and 0.1g of nano silicon dioxide (Hy-SiO 2) are taken and dispersed by high-speed shearing at 1500r/min under 6g of a nonionic emulsifier OS-15. When the drop amount of deionized water is 9g, the phase inversion phenomenon appears, namely, the emulsion system is converted from a liquid state to a solid oily body, and 280ml of hot water at 100 ℃ is added at the moment to carry out emulsification self-assembly reaction for 4 hours or more, so that a uniform and stable emulsion system is obtained.
Step S3, after-treatment of an emulsion system: and (3) heating the white emulsion system in the step (S2) to 120 ℃, preserving heat, stirring and curing for 2 hours, ensuring that the silicone resin is thoroughly solidified into micro-nano powder particles, standing, carrying out suction filtration on the obtained crude product, washing the crude product with absolute ethyl alcohol for three times, carrying out vacuum drying at 70 ℃ for 12 hours, and grinding the crude product and obtaining the high-water-repellent micro-nano powder particles through a 400-mesh screen.
The powder material is pressed into a plane block by a tablet press, then a contact angle of a water drop on the surface of the high-water-repellency silicon-based micro-nano powder filler is measured by a contact angle measuring instrument, the volume of the water drop is set to be 10 mu L, the contact angle is measured after the water drop is kept in a stable state for 30 seconds on the surface of the high-water-repellency silicon-based micro-nano powder filler, the contact angle is measured on three different positions of the same sample, and an average static contact angle value is obtained through calculation.
Embodiment two:
a high water-repellent silicon-based micro-nano powder filler and a preparation method thereof are provided, and the filler is prepared through the following steps:
step S1, preparing amino alkyl modified silicone resin: 27g of trifluoropropyl methyl cyclotrisiloxane (D3F) are added into the reactor under the protection of nitrogen; 8g of diphenyl diethoxysilane; 10g of dimethyl diethoxy silane; 5g of gamma-aminopropyl trimethoxysilane (KH-550); 13g of octamethyltrisiloxane; potassium hydroxide 0.01g; toluene 25g, xylene 5g. Then 0.01g of potassium hydroxide is dissolved in 15g of deionized water, stirred and added into a reactor, the temperature is raised to 70 ℃ for reaction for 12 hours, and then the system is slowly raised to 130 ℃ for reduced pressure distillation to remove low-boiling substances and moisture generated by hydrolytic condensation reaction, thus obtaining colorless and transparent amino hydrocarbon modified silicone resin.
Step S2, preparing uniform emulsion by an inverse microemulsion method: 25g of the aminoalkyl-modified silicone resin obtained in the step S1, 13g of aliphatic epoxy resin and 0.15g of nano silicon dioxide (Hy-SiO 2) are taken and dispersed by high-speed shearing at 1500r/min under the condition of 7.6g of non-ionic emulsifier OS-15. When the drop amount of deionized water is 11.5g, the phase inversion phenomenon occurs, namely, the emulsion system is converted from a liquid state to a solid oily body, and 360ml of hot water at 100 ℃ is added at the moment to carry out emulsification self-assembly reaction for 4 hours or more, so that a uniform and stable emulsion system is obtained.
Step S3, after-treatment of an emulsion system: and (3) heating the white emulsion system in the step (S2) to 120 ℃, preserving heat, stirring and curing for 2 hours, ensuring that the silicone resin is thoroughly solidified into micro-nano powder particles, standing, carrying out suction filtration on the obtained crude product, washing the crude product with absolute ethyl alcohol for three times, carrying out vacuum drying at 70 ℃ for 12 hours, and grinding the crude product and obtaining the high-water-repellent micro-nano powder particles through a 400-mesh screen.
The powder material is pressed into a plane block by a tablet press, then a contact angle of a water drop on the surface of the high-water-repellency silicon-based micro-nano powder filler is measured by a contact angle measuring instrument, the volume of the water drop is set to be 10 mu L, the contact angle is measured after the water drop is kept in a stable state for 30 seconds on the surface of the high-water-repellency silicon-based micro-nano powder filler, the contact angle is measured on three different positions of the same sample, and the average static contact angle value is calculated to be 141.4 degrees.
Embodiment III:
a high water-repellent silicon-based micro-nano powder filler and a preparation method thereof are provided, and the filler is prepared through the following steps:
step S1, preparing amino alkyl modified silicone resin: 27g of trifluoropropyl methyl cyclotrisiloxane (D3F) are added into the reactor under the protection of nitrogen; 9g of diphenyl diethoxy silane; 12g of dimethyl diethoxy silane; 3g of gamma-aminopropyl trimethoxysilane (KH-550); 12g of octamethyltrisiloxane; potassium hydroxide 0.01g; toluene 25g, xylene 5g. Then 0.01g of potassium hydroxide is dissolved in 15g of deionized water, stirred and added into a reactor, the temperature is raised to 70 ℃ for reaction for 12 hours, and then the system is slowly raised to 130 ℃ for reduced pressure distillation to remove low-boiling substances and moisture generated by hydrolytic condensation reaction, thus obtaining colorless and transparent amino hydrocarbon modified silicone resin.
Step S2, preparing uniform emulsion by an inverse microemulsion method: 19g of the aminoalkyl-modified silicone resin prepared in the step S1, 9g of aliphatic epoxy resin and 0.07g of nano silicon dioxide (Hy-SiO 2) are taken and dispersed by high-speed shearing at 1500r/min under 4.2g of a nonionic emulsifier OS-15. When the drop amount of deionized water is 8.6g, the phase inversion phenomenon appears, namely, the emulsion system is converted from a liquid state to a solid oily body, and 270ml of hot water at 100 ℃ is added at the moment to carry out emulsification self-assembly reaction for 4 hours or more, so that a uniform and stable emulsion system is obtained.
Step S3, after-treatment of an emulsion system: heating the white emulsion system in the step S2 to 120 ℃, preserving heat, stirring and curing for 2-4 hours to ensure that the silicone resin is thoroughly solidified into micro-nano powder particles, standing, washing a coarse product obtained by suction filtration with absolute ethyl alcohol for three times, drying in vacuum at 70 ℃ for 12 hours, and grinding the coarse product to obtain the high-water-repellent micro-nano powder particles through a 400-mesh screen.
The powder material is pressed into a plane block by a tablet press, then a contact angle of a water drop on the surface of the high-water-repellency silicon-based micro-nano powder filler is measured by a contact angle measuring instrument, the volume of the water drop is set to be 10 mu L, the contact angle is measured after the water drop is kept in a stable state for 30 seconds on the surface of the high-water-repellency silicon-based micro-nano powder filler, the contact angle is measured on three different positions of the same sample, and the average static contact angle value is calculated to be 140.8 degrees.
Embodiment four:
a high water-repellent silicon-based micro-nano powder filler and a preparation method thereof are provided, and the filler is prepared through the following steps:
step S1, preparing amino alkyl modified silicone resin: 27g of trifluoropropyl methyl cyclotrisiloxane (D3F) are added into the reactor under the protection of nitrogen; 7g of diphenyl diethoxy silane; 9g of dimethyl diethoxy silane; 7g of gamma-aminopropyl trimethoxysilane (KH-550); 12g of octamethyltrisiloxane; potassium hydroxide 0.01g; toluene 25g, xylene 5g. Then 0.01g of potassium hydroxide is dissolved in 15g of deionized water, stirred and added into a reactor, the temperature is raised to 70 ℃ for reaction for 12 hours, and then the system is slowly raised to 130 ℃ for reduced pressure distillation to remove low-boiling substances and moisture generated by hydrolytic condensation reaction, thus obtaining colorless and transparent amino hydrocarbon modified silicone resin.
Step S2, preparing uniform emulsion by an inverse microemulsion method: 24g of the amino hydrocarbon-based modified silicone resin prepared in the step S1, 11g of aliphatic epoxy resin and 0.14g of nano silicon dioxide (Hy-SiO 2) are taken and dispersed by high-speed shearing at 1500r/min under 6.5g of nonionic emulsifier OS-15. When the drop amount of deionized water is 10.8g, the phase inversion phenomenon occurs, namely, the emulsion system is converted from a liquid state to a solid oily body, and 320ml of hot water at 100 ℃ is added at the moment to carry out emulsification self-assembly reaction for 4 hours or more, so that a uniform and stable emulsion system is obtained.
Step S3, after-treatment of an emulsion system: heating the white emulsion system in the step S2 to 120 ℃, preserving heat, stirring and curing for 2-4 hours to ensure that the silicone resin is thoroughly solidified into micro-nano powder particles, standing, washing a coarse product obtained by suction filtration with absolute ethyl alcohol for three times, drying in vacuum at 70 ℃ for 12 hours, and grinding the coarse product to obtain the high-water-repellent micro-nano powder particles through a 400-mesh screen.
The powder material is pressed into a plane block by a tablet press, then the contact angle of a water drop on the surface of the high-water-repellency micro-nano powder particle is measured by using a contact angle measuring instrument, the volume of the water drop is set to be 10 mu L, the contact angle is measured after the water drop is kept in a stable state on the surface of the high-water-repellency micro-nano powder particle for 30s, the contact angle is measured on three different position points of the same sample, and the average static contact angle value is calculated to be 141.1 degrees. .
The high water repellency micro-nano powder particles prepared in examples 1-4 were subjected to a micro-morphology test, an infrared test, and a surface contact angle test:
1. microscopic topography testing
The microscopic dimensions of the high water repellent micro-nano powder particles were observed at the micrometer scale by a scanning electron microscope. The specific method comprises the following steps: dispersing the high-water-repellency micro-nano powder particles in ethanol, and keeping the concentration to be 0.5%. Then drop the glass sheet with a dropper, thoroughly dry in an oven, and observe the morphology under a scanning electron microscope after metal spraying treatment.
In the SEM image shown in fig. 4, the synthesized high water-repellent micro-nano powder particles are distributed uniformly. Because the size of the nano particles is in nano scale, the ratio of the surface to the volume is greatly increased, the surface energy of the particles is greatly increased, and a little aggregation phenomenon occurs between particles. Meanwhile, the synthesized powder particles have various forms, some of which have spherical shapes and some of which have polyhedral shapes, but most of which have irregular shapes. Under the nucleation of the nano-particles, the particle size of the powder particles synthesized by the silicon-based resin coating is obviously increased relative to the particle size of the nano-particles. Through observation of a scanning electron microscope, the particles with uneven particle size can be found, and the particles with micrometer size and nanometer size exist, so that the high water repellent micro-nano powder particles are successfully synthesized.
2. Infrared test
The testing method comprises the following steps: and fully drying the high-water-repellency silicon-based micro-nano powder filler, and taking 1mg of solid powder sample and 100mg of dry pure KBr solid particles by using a special sampling spoon for infrared test. Fully mixing and grinding the powder in an agate mortar to a plurality of micron granularity, baking the powder for 3min under an infrared baking lamp, adding the powder into a tabletting mold, maintaining the pressure for 30s by setting the pressure of the pressing machine to be 12-14 MPa, and finally removing the mold to obtain the light-transmitting thin sample piece. The sample was placed in a fourier transform infrared spectrometer (Nicolet-is model 5, sammer feishier technologies) to measure the outer pattern of the sample.
As shown in FIG. 5, the infrared spectrograms of the high-water-repellency micro-nano powder particles prepared by the hydrolysis and condensation of the siloxane monomer, the modified epoxy resin and the reverse microemulsion polymerization method are respectively obtained. In the infrared spectrogram of the amino hydrocarbon modified silicone resin, the infrared spectrogram is 3500cm in length -1 And 1206cm -1 There are respectively weaker and stronger-NH absorption vibration peaks at 1367cm -1 And 1062cm -1 The absorption vibration peaks of-CF, -Si-O-exist respectively, which shows that the synthesized product contains amino groups capable of reacting with epoxy and low-surface energy substances, so that the amino hydrocarbon-based modified silicone resin with the siloxane bond as a main body has water repellency. 1731cm in infrared spectrum of epoxy resin -1 And 910cm -1 The obvious absorption peak which appears at the position belongs to the absorption vibration peak of-C=O and the absorption vibration peak special for the epoxy group, which shows that the epoxy resin can further carry out polymerization reaction with the amino alkyl modified silicone resin. In an infrared spectrogram of the high-water-repellency micro-nano powder particles, the particle size is 3425cm -1 And 2937cm -1 where-OH and-CH occur 2 The broad absorption vibration peak also suggests that the high water repellent micro-nano powder particles have low surface energy groups and therefore high water repellency; at the same time, the amino groups and epoxy groups are weakened in peak position, which indicates that the reverse microemulsion polymerization method is successful.
3. Surface contact angle test
The testing method comprises the following steps: pressing the high-water-repellency silicon-based micro-nano powder filler into a plane block by a tablet press in a physical pressing manner, then measuring the contact angle of water drops on the high-water-repellency surface by using a contact angle measuring instrument, setting the volume of the water drops to be 10 mu L, measuring the contact angle after the water drops are kept in a stable state for 30 seconds on the surface of the high-water-repellency silicon-based micro-nano powder filler, measuring the contact of the same sample on three different position points, and taking the average value as the final hydrophobic angle of the sample.
In the surface contact angle diagram shown in fig. 6, the synthesized high-water-repellency micro-nano powder particles have better water-repellent characteristics. Wherein the static contact angles of the high water repellent micro-nano powder particles prepared in the embodiment cases 1-4 are all larger than 140 degrees.
The embodiments described above are only some, but not all, embodiments of the invention. 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.
Claims (10)
1. The preparation method of the high-water-repellency silicon-based micro-nano powder filler is characterized by comprising the following steps of:
step S1) preparing amino alkyl modified silicone resin: adding 1-70g of siloxane monomer, 1-20g of deionized water, 1-30g of hydrolysis medium, 1-10g of water carrying agent and 0.01-0.1g of strong base catalyst into a reactor protected by inert atmosphere, stirring and reacting for 8-12 h under the condition of alkaline heat preservation at 65-85 ℃, and then removing alcohol through reduced pressure distillation at 130-140 ℃ to obtain colorless transparent amino alkyl modified silicone resin;
step S2) preparing stable emulsion by an inverse microemulsion method: taking 1-50g of the amino hydrocarbon modified silicone resin prepared in the step S1), 1-40g of the modified epoxy resin and 0.01-0.5g of nano particles according to a certain mass ratio, shearing and dispersing at a high speed by 1200-2200r/min under 1-20g of an emulsifying agent, dripping deionized water at the same time for phase inversion, and adding 20-500ml of hot water with the temperature of 50-100 ℃ for emulsification self-assembly reaction for 4-8 hours when the emulsifying system is converted into solid oily body from liquid state, so as to obtain a uniform and stable white emulsion system.
Step S3) post-treatment of the emulsion system: heating the white emulsion system in the step S2) to 120 ℃, preserving heat, stirring and curing for 2-4 hours to ensure that the silicon resin is thoroughly solidified into micro-nano powder particles, standing, carrying out suction filtration on the obtained crude product, washing the crude product by absolute ethyl alcohol for three times, carrying out vacuum drying at 70 ℃ for 12 hours, and grinding the crude product by a 400-mesh screen to obtain the high-water-repellent micro-nano powder particles.
2. The method for preparing a high water repellent silicon based micro-nano powder filler according to claim 1, wherein the siloxane monomer is of the following type:
1) Difunctional mer siloxanes: trifluoropropyl methyl cyclotrisiloxane, diphenyl dimethoxy silane, diphenyl diethoxy silane, N-aminoethyl-gamma-aminopropyl methyl dimethoxy silane, and octamethyltrisiloxane;
2) Trifunctional blocked siloxanes: perfluoroalkyl trimethoxysilane, trifunctional building block siloxane perfluoroalkyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane and gamma-aminopropyl trimethoxysilane;
3) Blocked siloxanes: pentamethyldisiloxane, hexamethyldisiloxane and octamethyltrisiloxane; the siloxane monomer is formed by combining three or more than three random types.
3. The method for preparing a high water repellent silicon-based micro-nano powder filler according to claim 2, wherein the water-carrying agent is xylene.
4. The method for preparing the high water-repellent silicon-based micro-nano powder filler according to claim 3, wherein the hydrolysis medium is a low boiling point organic solvent, and the boiling point is 50-140 ℃.
5. The method for preparing the high water repellent silicon-based micro-nano powder filler according to claim 4, wherein the organic solvent is a single or mixed organic solvent of acetone, cyclohexane, toluene or xylene.
6. The method for preparing a high water repellent silicon based micro-nano powder filler according to claim 5, wherein the strong base catalyst is one or more of sodium hydroxide, potassium hydroxide and other water soluble strong base catalysts.
7. The method for preparing a high water repellent silicon-based micro-nano powder filler according to claim 6, wherein in step S2), the ratio of the active hydrogen value of the amino hydrocarbon-based modified silicone resin to the epoxy value in the modified epoxy resin is 0.85 to 0.96:1mol/100g, the content of nano particles is 0.1-0.5 percent (weight), the amount of dropwise adding deionized water is 30-45 percent of the total mass of the resin, and the mass of hot water is 8-10 times of the total mass of the resin.
8. The method for preparing the high water-repellent silicon-based micro-nano powder filler according to claim 7, wherein the emulsifier is any water-soluble nonionic emulsifier with a hydrophilic-lipophilic balance value of 9-16; the dosage of the emulsifier is 5-20% of the mass of the reactant.
9. The method for preparing a high water-repellent silicon-based micro-nano powder filler according to claim 8, wherein the nano particles in the reverse phase microemulsion method are single or combined nano particle size particles in nano silicon dioxide, nano titanium dioxide and nano calcium carbonate.
10. A high water repellent silicon-based micro-nano powder filler, characterized in that the high water repellent micro-nano powder filler is made by the preparation method of claim 1.
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