CN110449094B - Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating - Google Patents
Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating Download PDFInfo
- Publication number
- CN110449094B CN110449094B CN201910788461.2A CN201910788461A CN110449094B CN 110449094 B CN110449094 B CN 110449094B CN 201910788461 A CN201910788461 A CN 201910788461A CN 110449094 B CN110449094 B CN 110449094B
- Authority
- CN
- China
- Prior art keywords
- self
- porous
- stirring
- mixed solution
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 56
- 239000003094 microcapsule Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002105 nanoparticle Substances 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 37
- 239000002775 capsule Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 230000002209 hydrophobic effect Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- -1 polydimethylsiloxane Polymers 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 9
- 229920002643 polyglutamic acid Polymers 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000008055 phosphate buffer solution Substances 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 229910021426 porous silicon Inorganic materials 0.000 claims description 6
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 239000003755 preservative agent Substances 0.000 claims description 5
- 230000002335 preservative effect Effects 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000008363 phosphate buffer Substances 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical group CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a preparation method of a self-repairing microcapsule and application of the self-repairing microcapsule in a super-hydrophobic coating. The self-repairing microcapsule provided by the invention adopts the porous nanoparticles wrapped with low surface energy as the capsule core, the nano-scale porous particle structure can enable the nanoparticles to fill cracks when the microcapsule is damaged by acid and alkali, so as to play a self-repairing role, the porous structure can increase the specific surface area of the capsule core, increase the surface energy and further have stronger surface adsorption capacity, so that a low-surface-energy substance can be more easily adsorbed on the surface of the capsule core, and the microcapsule has a better self-repairing effect when the pH value is 5-9; the capsule wall of the microcapsule is selected from high molecular polymers, and through the synergistic action of the capsule wall and the capsule wall, when the structure of the capsule wall is damaged, the surface of the capsule still has high roughness, and through the synergistic action of the capsule wall and the capsule wall, the damaged superhydrophobic surface can be automatically repaired.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a preparation method of a self-repairing microcapsule and application of the self-repairing microcapsule in a super-hydrophobic coating.
Background
The super-hydrophobic surface (the contact angle is more than 150 degrees and the rolling angle is less than 10 degrees) has excellent performance, so the super-hydrophobic surface has wide application prospect in a plurality of fields, such as self-cleaning, corrosion resistance, ice coating prevention, drag reduction, antifouling and the like. However, the artificial super-hydrophobic surface has poor durability in the actual use process, easily loses super-hydrophobic performance due to physical damage such as scraping and abrasion and the like, and greatly limits the application of the super-hydrophobic material.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a self-repairing microcapsule and application of the self-repairing microcapsule in a super-hydrophobic coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a self-repairing microcapsule comprises the following steps:
(1) firstly, preparing porous nano particles;
(2) adding the prepared porous nanoparticles into a mixture with a volume ratio of 2: 1, stirring and dissolving the mixed solution of deionized water and ethanol, adding a low-surface-energy substance into the mixed solution, and stirring for 2-3 hours to form a mixed solution A to obtain a capsule;
(3) respectively dissolving polyglutamic acid and acrylic acid in 0.1mol/L phosphate buffer solution, adding initiator ammonium sulfate under the condition of stirring, stirring for 25-35min, then adding tetramethylethylenediamine, stirring for 1.8-2.2h to form mixed solution B, dropwise adding the mixed solution A into the mixed solution B, stirring for 2-3h, cleaning, drying at 50-60 ℃, and grinding to obtain the self-repairing microcapsule.
Further, the porous nanoparticles in the step (1) are one or more of porous titanium dioxide nanoparticles, porous zinc oxide nanoparticles and porous silicon dioxide nanoparticles.
Further, the porous titanium dioxide nano particle is prepared by the following method: sequentially adding ethanol, tetrabutyl orthotitanate, diethanolamine and glacial acetic acid into a beaker according to the volume ratio of 1:0.5:0.05:0.8, stirring for 2-3h to form milky suspension, aging for 12h, pouring out supernatant, centrifugally cleaning for 3 times by using acetone to remove impurity ions, drying for 12h at 60 ℃, grinding to obtain powdery titanium dioxide, and calcining the powdery titanium dioxide at 400 ℃ for 3-4h to obtain porous titanium dioxide nanoparticles;
further, the porous zinc oxide nanoparticles are prepared by the following method: dissolving 2.2g of zinc acetate in 15-25ml of ethanolamine, adding a mixed solution of deionized water and ethanol with a volume ratio of 1:1-3, stirring for 25-35min, reacting at 180 ℃ for 4-8h at 170-;
further, the porous silica nanoparticles are prepared by the following method: dissolving 0.5g of polyvinylpyrrolidone in a mixed solution of 40ml of ethanol and 60ml of deionized water, dissolving 1g of dodecylamine in 5ml of anhydrous ethanol, adding the mixture, stirring for 50-70min, adding 5ml of ethyl orthosilicate, stirring for 5-7h at 30-50 ℃ to form white colloid, centrifugally cleaning, drying for 12h at 100 ℃, grinding, and calcining for 3.5-4.5h at 550-650 ℃ to obtain the porous silica nanoparticles.
Further, in the step (2), according to parts by weight, 15-30 parts of porous nano particles, 20-30 parts of a mixed solution of deionized water and ethanol and 1-4 parts of a low surface energy substance.
Further, the low surface energy substance in the step (2) is one or more of zinc tridecafluoro-based triethoxysilane, 1H,2H, 2H-perfluorooctyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane and octadecyltrimethoxysilane.
Further, in the step (3), the mass ratio of the polyglutamic acid to the acrylic acid to the ammonium sulfate to the tetramethylethylenediamine is 3:7:0.55:0.043, and the mass-to-volume ratio of the polyglutamic acid to the phosphate buffer solution is 0.03 g: 5 ml.
The self-repairing microcapsule prepared by the method is applied to a super-hydrophobic coating.
Further, the sensitive range of the pH value of the super-hydrophobic coating is 5-9.
Namely, the pH value is between 5 and 9, the super-hydrophobic coating prepared by the invention has a good self-repairing effect, and the hydrophobic property and the durability are durable and stable.
Further, the super-hydrophobic coating comprises the following raw materials in parts by weight: 15-20 parts of acrylic resin, 15-30 parts of solvent, 5-20 parts of microcapsule, 1-3 parts of surfactant, 10-20 parts of hydrophobic substance, 1-5 parts of defoaming agent, 1-5 parts of flatting agent and 2-8 parts of curing agent.
Further, the solvent is one or more of toluene, xylene, acetone, polyamide and tetrahydrofuran, the surfactant is polyvinylpyrrolidone or hexadecyl trimethyl ammonium bromide, the hydrophobic substance is one or more of paraffin, talcum powder, bentonite, tridecafluoro zinc-based triethoxysilane, 1H,2H, 2H-perfluoro octyl trimethoxysilane, dodecyl trimethoxysilane, hexadecyl trimethoxysilane and octadecyl trimethoxysilane, the defoaming agent is polydimethylsiloxane or polypropylene glycol-alkylene oxide polymer, the leveling agent is polyether modified polysiloxane, the curing agent is one or more of benzoyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide and cyclohexanone peroxide.
Further, the preparation method of the super-hydrophobic coating comprises the following steps:
(a) pretreatment of a base material: selecting silicon dioxide glass as a substrate, immersing the substrate in ethanol, ultrasonically cleaning for 15-20min, cleaning with ultrapure water for three times, drying, and wrapping with a preservative film for later use;
(b) the super-hydrophobic coating is prepared by the following method: according to the weight of each raw material, dissolving acrylic resin in a solvent, sequentially adding microcapsules, a surfactant, a hydrophobic substance, a defoaming agent, a flatting agent and a curing agent, uniformly stirring by ultrasonic waves, coating on a standby base material, and curing at the temperature of 100-110 ℃.
The prepared super-hydrophobic coating can be used in the fields of outdoor buildings, glass, metal, textiles and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the self-repairing microcapsule provided by the invention adopts the porous nanoparticles wrapped with low surface energy as the capsule core, the nano-scale porous particle structure can enable the nanoparticles to fill cracks when the microcapsule is damaged by acid and alkali, so as to play a self-repairing role, the porous structure can increase the specific surface area of the capsule core, increase the surface energy and further have stronger surface adsorption capacity, so that a low-surface-energy substance can be more easily adsorbed on the surface of the capsule core, and the microcapsule has a better self-repairing effect when the pH value is 5-9; the capsule wall of the microcapsule is made of high molecular polymer, the high molecular polymer contains a group with pH response characteristics of weak acid or weak base, such as carboxyl, amino and the like, the weak acid or weak base group can be ionized along with the change of pH value and ionic strength, hydrogen bond dissociation can be carried out, polymerization swelling is caused, the surface of the capsule core still has high roughness through the synergistic action of the capsule core and the capsule wall when the structure of the capsule wall is damaged, and the damaged superhydrophobic surface can be automatically repaired through the synergistic action of the capsule wall and the capsule core;
(2) the prepared super-hydrophobic coating can timely release low surface energy substances in a pH sensitive range and the porous nanoparticles can fill cracks to achieve a self-repairing effect, so that the hydrophobic property and the durability of the super-hydrophobic coating are durable and stable.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a transmission electron micrograph of porous titania nanoparticles prepared in example 1;
FIG. 2 is the contact angle of the superhydrophobic coating prepared in example 4;
FIG. 3 is a contact angle of the superhydrophobic coating prepared in example 4 after treatment with an acid solution having a pH of 5;
fig. 4 is a contact angle of the superhydrophobic coating prepared in example 4 after treatment with an alkali solution having a pH of 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The preparation method of the self-repairing microcapsule of the embodiment includes the following steps:
(1) firstly, preparing porous titanium dioxide nano particles: the porous titanium dioxide nano particle is prepared by the following method: sequentially adding ethanol, tetrabutyl orthotitanate, diethanolamine and glacial acetic acid into a beaker according to the volume ratio of 1:0.5:0.05:0.8, stirring for 2h to form a milky suspension, aging for 12h, pouring out a supernatant, centrifugally cleaning for 3 times by using acetone to remove impurity ions, drying for 12h at 60 ℃, grinding to obtain powdery titanium dioxide, and calcining the powdery titanium dioxide for 3h at 300 ℃ to obtain porous titanium dioxide nanoparticles;
(2) adding the prepared porous titanium dioxide nano particles into a reactor with the volume ratio of 2: 1, adding a low-surface-energy substance into the mixed solution of deionized water and ethanol, and stirring for 2.5 hours to form a mixed solution A to obtain a capsule, wherein the capsule comprises 15g of porous titanium dioxide nanoparticles, 20g of the mixed solution of deionized water and ethanol, 1g of the low-surface-energy substance, and the low-surface-energy substance is tridecafluoro zinc-based triethoxysilane;
(3) respectively dissolving 3g of polyglutamic acid and 7g of acrylic acid in 500ml of 0.1mol/L phosphate buffer solution, adding 0.55g of ammonium sulfate serving as an initiator under the stirring condition, stirring for 30min, then adding 0.043g of tetramethylethylenediamine, stirring for 2h to form a mixed solution B, dropwise adding the mixed solution A into the mixed solution B, stirring for 2.5h, washing with deionized water, drying at 55 ℃, and grinding to obtain the self-repairing microcapsule.
The transmission electron microscope image of the porous titania nanoparticles prepared in this example is shown in fig. 1.
The pore diameter of the micropores of the porous titanium dioxide nanoparticles is reduced with the increase of the calcination temperature, the specific surface area is reduced, the crystallinity of the crystal grains is increased, and the average particle diameter of the nanoparticles is increased, as shown in fig. 1, the pores formed by the porous titanium dioxide nanoparticles prepared in the embodiment at the calcination temperature of 300 ℃ have smaller pore diameter, the pore diameter is 1-2nm, the particle diameter is 10-12nm, and the pore diameter change is not obvious. The applicant has carried out a number of experiments and has found that when the calcination temperature is increased to 400 c, titanium dioxide in anatase form is formed. However, when the calcination temperature is too high, the porous structure is shrunk or collapsed, the specific surface area is greatly reduced, the specific surface energy is reduced, the adsorption quantity of low-surface substances is further influenced, and the hydrophobic effect of the coating is poor.
Example 2
The preparation method of the self-repairing microcapsule of the embodiment includes the following steps:
(1) firstly, preparing porous zinc oxide nano particles: the porous zinc oxide nano-particles are prepared by the following method: dissolving 2.2g of zinc acetate in 20ml of ethanolamine, adding 10ml of a mixed solution of deionized water and ethanol in a volume ratio of 1:2, stirring for 30min, then reacting at 175 ℃ for 6h at constant temperature, centrifugally cleaning to neutrality, drying at 60 ℃ for 12h, grinding, and calcining at 350 ℃ for 3.5h to obtain porous zinc oxide nanoparticles;
(2) adding the prepared porous zinc oxide nano particles into a mixture with the volume ratio of 2: 1, stirring and dissolving in a mixed solution of deionized water and ethanol, adding a low surface energy substance into the mixed solution, and stirring for 2 hours to form a mixed solution A, thereby obtaining a capsule core, wherein the porous zinc oxide nanoparticles are 22g, the mixed solution of deionized water and ethanol is 25g, the low surface energy substance is 2.5g, and the low surface energy substance is dodecyl trimethoxy silane;
(3) respectively dissolving 3g of polyglutamic acid and 7g of acrylic acid in 500ml of 0.1mol/L phosphate buffer solution, adding 0.55g of ammonium sulfate serving as an initiator under the stirring condition, stirring for 30min, then adding 0.043g of tetramethylethylenediamine, stirring for 1.8h to form a mixed solution B, dropwise adding the mixed solution A into the mixed solution B, stirring for 2h, washing with deionized water, drying at 50 ℃, and grinding to obtain the self-repairing microcapsule.
Example 3
The preparation method of the self-repairing microcapsule of the embodiment includes the following steps:
(1) firstly, preparing porous silicon dioxide nano particles: the porous silicon dioxide nano particle is prepared by the following method: dissolving 0.5g of polyvinylpyrrolidone in a mixed solution of 40ml of ethanol and 60ml of deionized water, dissolving 1g of dodecylamine in 5ml of absolute ethanol, adding the solution, stirring for 60min, adding 5ml of ethyl orthosilicate, stirring for 6 hours at 40 ℃ to form a white colloid, centrifugally cleaning, drying for 12 hours at 100 ℃, grinding, and calcining for 4 hours at 600 ℃ to obtain porous silica nanoparticles;
(2) adding the prepared porous silica nano particles into a mixture with the volume ratio of 2: 1, stirring and dissolving in a mixed solution of deionized water and ethanol, and adding a low-surface-energy substance into the mixed solution for stirring for 2 hours to form a mixed solution A, thereby obtaining a capsule, wherein the capsule comprises 30g of porous silicon dioxide nanoparticles, 30g of a mixed solution of deionized water and ethanol, 4g of a low-surface-energy substance, and the low-surface-energy substance is 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane;
(3) respectively dissolving 1.5g of polyglutamic acid and 3.5g of acrylic acid in 250ml of 0.1mol/L phosphate buffer solution, adding 0.275g of ammonium sulfate serving as an initiator under the stirring condition, stirring for 30min, then adding 0.0215g of tetramethylethylenediamine, stirring for 2.2h to form a mixed solution B, dropwise adding the mixed solution A into the mixed solution B, stirring for 3h, washing with deionized water, drying at 60 ℃, and grinding to obtain the self-repairing microcapsule.
Example 4
In this embodiment, for the application of the self-repairing microcapsule prepared in embodiment 1 in the superhydrophobic coating, the raw materials for preparing the superhydrophobic coating include: 15g of acrylic resin, 15g of solvent, 5g of microcapsule prepared in example 1, 1g of surfactant, 10g of hydrophobic substance, 1g of defoaming agent, 1g of leveling agent and 2g of curing agent; wherein, the solvent is toluene, the surfactant is polyvinylpyrrolidone, the hydrophobic substance is tridecafluoro zinc-based triethoxysilane, the defoamer is polydimethylsiloxane, the leveling agent is polyether modified polysiloxane (the manufacturer Hubei New Sihai chemical industry Co., Ltd.), and the curing agent is benzoyl peroxide;
the preparation method of the super-hydrophobic coating comprises the following steps:
(a) pretreatment of a base material: selecting silicon dioxide glass as a substrate, immersing the substrate in ethanol, ultrasonically cleaning for 15min, cleaning with ultrapure water for three times, drying, and wrapping with a preservative film for later use;
(b) the super-hydrophobic coating is prepared by the following method: dissolving acrylic resin in a solvent, sequentially adding microcapsules, a surfactant, a hydrophobic substance, a defoaming agent, a flatting agent and a curing agent, uniformly stirring by ultrasonic waves, coating the mixture on a standby base material, and curing at 100 ℃.
Example 5
This example is an application of the self-repairing microcapsule prepared in example 2 in a superhydrophobic coating, and the raw materials for preparing the superhydrophobic coating include the following: 17.5g of acrylic resin, 22.5g of solvent, 12.5g of microcapsule prepared in example 2, 2g of surfactant, 15g of hydrophobic substance, 3g of defoaming agent, 3g of flatting agent and 5g of curing agent; wherein, the solvent is tetrahydrofuran, the surfactant is cetyl trimethyl ammonium bromide, the hydrophobic substance is dodecyl trimethoxy silane, the antifoaming agent is a polypropylene glycol-alkylene oxide polymer, the flatting agent is polyether modified polysiloxane (chemical industry Co., Ltd., New four seas, Hubei of manufacturers), and the curing agent is cumene hydroperoxide;
the preparation method of the super-hydrophobic coating comprises the following steps:
(a) pretreatment of a base material: selecting silicon dioxide glass as a substrate, immersing the substrate in ethanol, ultrasonically cleaning for 17.5min, cleaning with ultrapure water for three times, drying, and wrapping with a preservative film for later use;
(b) the super-hydrophobic coating is prepared by the following method: dissolving acrylic resin in a solvent, sequentially adding microcapsules, a surfactant, a hydrophobic substance, a defoaming agent, a flatting agent and a curing agent, uniformly stirring by ultrasonic waves, coating on a standby base material, and curing at 105 ℃.
Example 6
This example is an application of the self-repairing microcapsule prepared in example 3 in a superhydrophobic coating, and the raw materials for preparing the superhydrophobic coating include the following: 20g of acrylic resin, 30g of solvent, 20g of microcapsule prepared in example 3, 3g of surfactant, 20g of hydrophobic substance, 5g of defoaming agent, 5g of flatting agent and 8g of curing agent; wherein, the solvent is acetone, the surfactant is cetyl trimethyl ammonium bromide, the hydrophobic substance is 1H,1H,2H, 2H-perfluorooctyl trimethoxy silane, the defoaming agent is a polypropylene glycol-alkylene oxide polymer, the flatting agent is polyether modified polysiloxane (the manufacturer Hubei New Sihai chemical industry Co., Ltd.), and the curing agent is benzoyl peroxide;
the preparation method of the super-hydrophobic coating comprises the following steps:
(a) pretreatment of a base material: selecting silicon dioxide glass as a substrate, immersing the substrate in ethanol, ultrasonically cleaning for 20min, cleaning with ultrapure water for three times, drying, and wrapping with a preservative film for later use;
(b) the super-hydrophobic coating is prepared by the following method: dissolving acrylic resin in a solvent, sequentially adding microcapsules, a surfactant, a hydrophobic substance, a defoaming agent, a flatting agent and a curing agent, uniformly stirring by ultrasonic waves, coating on a standby base material, and curing at 110 ℃.
Comparative example 1
The superhydrophobic coating prepared by the comparative example is the same as that prepared in example 4, except that the porous titanium dioxide nanoparticles are directly ground and crushed without calcining in the preparation process.
Test example 1
The self-healing performance of the superhydrophobic coating prepared by the method of example 4 under acid-base conditions was tested.
Hydrophobicity test method: the contact angle of a water drop on the surface of the film layer is measured by a contact angle tester, the contact angle value is obtained by averaging 5 random position measurement values, the static contact angle is measured by a lying drop method (sessile drop), and when a super-hydrophobic surface (namely a surface with the static contact angle larger than 150 degrees) is measured, 5 mu L of water drop is uniformly used during measurement.
1. The contact angle of the superhydrophobic coating prepared in test example 4 was 159.12 ° according to the hydrophobicity test method described above, and is shown in fig. 2.
2. Acid solutions with pH 4, 5 and 6 were prepared with hydrochloric acid, and base solutions with pH 8, 9 and 10 were prepared with sodium hydroxide, respectively.
6 groups of sample coatings are respectively prepared according to the method of the embodiment 4 to test the self-repairing performance of the super-hydrophobic coatings under different acid and alkali conditions, and the test method is as follows: respectively immersing the sample coating in solutions with different pH values for 24h, then removing the coating, removing acid-base solution on the surface, measuring the contact angle, then placing the coating in an environment with the temperature of 80 ℃ for repairing for 2h, and measuring the contact angle of the coating, wherein the results are shown in table 1.
TABLE 1
pH of the treated solution | Contact angle (°) after treatment with acid or alkali solution | Contact Angle after restoration (°) |
4 | 132.14 | 138.95 |
5 | 153.26 | 158.16 |
6 | 154.49 | 158.87 |
8 | 153.62 | 158.71 |
9 | 154.03 | 158.83 |
10 | 134.62 | 139.82 |
As can be seen from Table 1, the repairing performance of the coating is better when the pH is 5-9, and the repairing effect is poorer when the pH is less than 5 or more than 9, which shows that the super-hydrophobic coating of the invention has better self-repairing effect when the pH is 5-9, and when the super-hydrophobic coating of the invention is damaged by a solution with the pH of 5-9, the stable hydrophobic performance can be maintained.
Wherein, the contact angle of the super-hydrophobic coating after the treatment of the acid solution with pH 5 is shown in FIG. 3, and the contact angle of the super-hydrophobic coating after the treatment of the alkali solution with pH 9 is shown in FIG. 4.
The inventors also conducted the above tests on the superhydrophobic coatings prepared in other examples, and the results were substantially consistent and are not listed due to limited space.
Test example 2
In the test example, the super-hydrophobic coating prepared in comparative example 1 was tested for self-repairing performance under acid and alkali conditions, the test method was the same as in test example 1, and the measurement results are shown in table 2.
1. The contact angle of the superhydrophobic coating prepared in comparative example 1 was 153.12 °.
TABLE 2
pH of the treated solution | Contact angle (°) after treatment with acid or alkali solution | Contact Angle after restoration (°) |
4 | 123.45 | 127.56 |
5 | 146.32 | 148.28 |
6 | 147.56 | 147.98 |
8 | 145.85 | 146.13 |
9 | 146.38 | 148.23 |
10 | 114.62 | 123.87 |
It can be seen from tables 1 and 2 that the self-repairing performance of the hydrophobic coating of the nano titanium dioxide without calcination treatment is poorer than that of the hydrophobic coating with calcination treatment, and the contact angle is small, i.e. the hydrophobicity is also reduced, because the calcination treatment increases the holes on the surface of the porous nano particles to increase the surface area, the adsorption performance of the low surface energy substance is stronger, the self-repairing effect is better, and the hydrophobic performance is better.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A preparation method of a self-repairing microcapsule is characterized by comprising the following steps:
(1) firstly, preparing porous nano particles;
(2) adding the prepared porous nanoparticles into a mixture with a volume ratio of 2: 1, stirring and dissolving the mixed solution of deionized water and ethanol, adding a low-surface-energy substance into the mixed solution, and stirring for 2-3 hours to form a mixed solution A to obtain a capsule;
(3) respectively dissolving polyglutamic acid and acrylic acid in 0.1mol/L phosphate buffer solution, adding an initiator ammonium sulfate under the stirring condition, stirring for 25-35min, then adding tetramethylethylenediamine, stirring for 1.8-2.2h to form a mixed solution B, dropwise adding the mixed solution A into the mixed solution B, stirring for 2-3h, cleaning, drying at 50-60 ℃, and grinding to obtain the self-repairing microcapsule;
wherein the porous nanoparticles in the step (1) are one or more of porous titanium dioxide nanoparticles, porous zinc oxide nanoparticles and porous silicon dioxide nanoparticles;
the porous titanium dioxide nano particle is prepared by the following method: sequentially adding ethanol, tetrabutyl orthotitanate, diethanolamine and glacial acetic acid into a beaker according to the volume ratio of 1:0.5:0.05:0.8, stirring for 2-3h to form milky suspension, aging for 12h, pouring out supernatant, centrifugally cleaning for 3 times by using acetone to remove impurity ions, drying for 12h at 60 ℃, grinding to obtain powdery titanium dioxide, and calcining the powdery titanium dioxide at 400 ℃ for 3-4h to obtain porous titanium dioxide nanoparticles;
the porous zinc oxide nano particles are prepared by the following method: dissolving 2.2g of zinc acetate in 15-25ml of ethanolamine, adding a mixed solution of deionized water and ethanol with a volume ratio of 1:1-3, stirring for 25-35min, reacting at 180 ℃ for 4-8h at 170-;
the porous silicon dioxide nano particle is prepared by the following method: dissolving 0.5g of polyvinylpyrrolidone in a mixed solution of 40ml of ethanol and 60ml of deionized water, dissolving 1g of dodecylamine in 5ml of anhydrous ethanol, adding the mixture, stirring for 50-70min, adding 5ml of ethyl orthosilicate, stirring for 5-7h at 30-50 ℃ to form white colloid, centrifugally cleaning, drying for 12h at 100 ℃, grinding, and calcining for 3.5-4.5h at 550-650 ℃ to obtain the porous silica nanoparticles.
2. The preparation method of the self-repairing microcapsule according to claim 1, wherein in the step (2), the porous nanoparticles are 15-30 parts by weight, the mixed solution of deionized water and ethanol is 20-30 parts by weight, and the low surface energy substance is 1-4 parts by weight.
3. The method for preparing the self-repairing microcapsule according to claim 1 or 2, wherein the low surface energy substance in the step (2) is one or more of tridecafluoro zinc-based triethoxysilane, 1H,2H, 2H-perfluorooctyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane and octadecyltrimethoxysilane.
4. The preparation method of the self-repairing microcapsule according to claim 1, wherein the mass ratio of the polyglutamic acid, the acrylic acid, the ammonium sulfate and the tetramethylethylenediamine in the step (3) is 3:7:0.55:0.043, and the mass-volume ratio of the polyglutamic acid to the phosphate buffer is 0.03 g: 5 ml.
5. Use of self-healing microcapsules prepared according to the process of any one of claims 1 to 4 in superhydrophobic coatings.
6. The application of the self-repairing microcapsule to the super-hydrophobic coating, which is characterized in that the super-hydrophobic coating comprises the following raw materials in parts by weight: 15-20 parts of acrylic resin, 15-30 parts of solvent, 5-20 parts of microcapsule, 1-3 parts of surfactant, 10-20 parts of hydrophobic substance, 1-5 parts of defoaming agent, 1-5 parts of flatting agent and 2-8 parts of curing agent.
7. The use of the self-repairing microcapsule of claim 6 in a superhydrophobic coating, wherein the solvent is one or more of toluene, xylene, acetone, polyamide, tetrahydrofuran, the surfactant is polyvinylpyrrolidone or cetyltrimethylammonium bromide, the hydrophobic material is one or more of paraffin, talc, bentonite, tridecafluoro-zinc-based triethoxysilane, 1H,2H, 2H-perfluorooctyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, the antifoaming agent is polydimethylsiloxane or polypropylene glycol-alkylene oxide polymer, the leveling agent is polyether-modified polysiloxane, and the curing agent is benzoyl peroxide, cumene hydroperoxide, or octadecyl trimethoxysilane, One or more of tert-butyl hydroperoxide, benzoyl peroxide and cyclohexanone peroxide.
8. The application of the self-repairing microcapsule to the super-hydrophobic coating, which is characterized in that the preparation method of the super-hydrophobic coating comprises the following steps:
(a) pretreatment of a base material: selecting silicon dioxide glass as a substrate, immersing the substrate in ethanol, ultrasonically cleaning for 15-20min, cleaning with ultrapure water for three times, drying, and wrapping with a preservative film for later use;
(b) the super-hydrophobic coating is prepared by the following method: according to the weight of each raw material, dissolving acrylic resin in a solvent, sequentially adding microcapsules, a surfactant, a hydrophobic substance, a defoaming agent, a flatting agent and a curing agent, uniformly stirring by ultrasonic waves, coating on a standby base material, and curing at the temperature of 100-110 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910788461.2A CN110449094B (en) | 2019-08-26 | 2019-08-26 | Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910788461.2A CN110449094B (en) | 2019-08-26 | 2019-08-26 | Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110449094A CN110449094A (en) | 2019-11-15 |
CN110449094B true CN110449094B (en) | 2021-09-17 |
Family
ID=68488969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910788461.2A Active CN110449094B (en) | 2019-08-26 | 2019-08-26 | Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110449094B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111364249B (en) * | 2020-03-25 | 2021-07-20 | 东华大学 | Preparation method of self-repairing super-hydrophobic fabric |
CN111423785B (en) * | 2020-04-09 | 2021-12-14 | 青岛理工大学 | Super-hydrophobic coating with self-repairing function and preparation method thereof |
CN116558327A (en) * | 2022-01-27 | 2023-08-08 | 浙江三花智能控制股份有限公司 | Heat exchanger and composite material for heat exchanger |
CN115651533A (en) * | 2022-11-02 | 2023-01-31 | 佛山科学技术学院 | Super-hydrophobic self-repairing silane coating and preparation method thereof |
CN117165135B (en) * | 2023-11-02 | 2024-01-02 | 江苏新福乐威涂料有限公司 | Preparation method of anti-corrosion and anti-scale fluorocarbon coating material |
CN117603621B (en) * | 2023-12-01 | 2024-04-23 | 胜利油田金岛实业有限责任公司 | Anti-scale and anti-corrosion coating for oil pipe and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104028184A (en) * | 2014-06-21 | 2014-09-10 | 电子科技大学 | Conductive polymer microcapsule of reactive liquid core material and preparation method thereof |
CN104624132A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院化学研究所 | Epoxy resin self-repairing microcapsule and preparation method thereof |
CN105885679A (en) * | 2016-06-07 | 2016-08-24 | 江南大学 | Self-repairing water-based super-hydrophobic coating based on microcapsule type and preparing method thereof |
CN107201140A (en) * | 2017-06-17 | 2017-09-26 | 常州福隆工控设备有限公司 | A kind of self-healing coatings and preparation method thereof |
CN107474615A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院过程工程研究所 | A kind of anti-corrosion self-healing coatings |
CN108659602A (en) * | 2018-06-08 | 2018-10-16 | 河北麦森钛白粉有限公司 | Nanometer titanium dioxide composite material microcapsules and its preparation process for selfreparing |
CN109971331A (en) * | 2019-03-21 | 2019-07-05 | 湖北大学 | A kind of microcapsule-type self-repairing super hydrophobic coating and preparation method thereof |
CN110079140A (en) * | 2019-04-30 | 2019-08-02 | 中山大学 | A kind of intelligent response selfreparing anticorrosion coating material and preparation method |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201620609A (en) * | 2014-02-18 | 2016-06-16 | 羅門哈斯公司 | Microcapsules |
-
2019
- 2019-08-26 CN CN201910788461.2A patent/CN110449094B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104624132A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院化学研究所 | Epoxy resin self-repairing microcapsule and preparation method thereof |
CN104028184A (en) * | 2014-06-21 | 2014-09-10 | 电子科技大学 | Conductive polymer microcapsule of reactive liquid core material and preparation method thereof |
CN105885679A (en) * | 2016-06-07 | 2016-08-24 | 江南大学 | Self-repairing water-based super-hydrophobic coating based on microcapsule type and preparing method thereof |
CN107201140A (en) * | 2017-06-17 | 2017-09-26 | 常州福隆工控设备有限公司 | A kind of self-healing coatings and preparation method thereof |
CN107474615A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院过程工程研究所 | A kind of anti-corrosion self-healing coatings |
CN108659602A (en) * | 2018-06-08 | 2018-10-16 | 河北麦森钛白粉有限公司 | Nanometer titanium dioxide composite material microcapsules and its preparation process for selfreparing |
CN109971331A (en) * | 2019-03-21 | 2019-07-05 | 湖北大学 | A kind of microcapsule-type self-repairing super hydrophobic coating and preparation method thereof |
CN110079140A (en) * | 2019-04-30 | 2019-08-02 | 中山大学 | A kind of intelligent response selfreparing anticorrosion coating material and preparation method |
Also Published As
Publication number | Publication date |
---|---|
CN110449094A (en) | 2019-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110449094B (en) | Preparation method of self-repairing microcapsule and application of self-repairing microcapsule in super-hydrophobic coating | |
US11149152B2 (en) | Durable hydrophilic-super-hydrophobic bipolar self-cleaning composite film, and preparation method therefor | |
Jannatun et al. | A facile cross-linking approach to fabricate durable and self-healing superhydrophobic coatings of SiO2-PVA@ PDMS on cotton textile | |
CN112226155B (en) | Bionic fouling release type organic silicon marine antifouling paint and preparation method thereof | |
CN111534162B (en) | Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof | |
CN107150020B (en) | High-adhesion wear-resistant temperature-resistant super-amphiphobic self-cleaning surface coating and preparation method thereof | |
CN111270514B (en) | Preparation method of stable superhydrophobic antibacterial cotton fabric based on glutaraldehyde crosslinking | |
CN108912754A (en) | A kind of super-hydrophobic SiO2The preparation method and application of nano functional liquid | |
CN115960496B (en) | Weather-resistant corrosion-resistant metal fluorocarbon coating and preparation method thereof | |
CN114106416B (en) | Preparation method and application of double-response halloysite nano container | |
CN108755111A (en) | A method of deposition silver nano-grain processability stablizes antibacterial superhydrophobic fabric | |
CN113292902A (en) | Modified graphene oxide anticorrosive paint and preparation method thereof | |
CN110407482A (en) | In SiO2Method for preparing super-hydrophobic coating on glass surface | |
CN115074007A (en) | Inorganic-organic composite super-hydrophilic coating and preparation method and application thereof | |
CN110922865A (en) | Steel surface composite coating and preparation method thereof | |
Xu et al. | Preparation of robust and self-healing superamphiphobic cotton fabrics based on modified silica aerogel particles | |
CN107629657B (en) | Attapulgite/aqueous polyurethane coating and its application | |
CN114106694A (en) | Super-hydrophobic agent, preparation method of super-hydrophobic agent and self-repairing super-hydrophobic structure | |
CN113321985A (en) | PH stimulus response intelligent repair coating and preparation method thereof | |
CN106785937B (en) | A kind of lightning rod for substation | |
CN110408316B (en) | Preparation method of photocatalytic super-hydrophobic coating | |
CN115478449B (en) | Preparation method of self-cleaning paper-based super-hydrophobic coating, coating and application | |
CN112408789A (en) | Preparation method of hydrophobic antifouling ground coat slurry | |
CN104672480A (en) | Surface treatment method for anti-pollution self-cleaning PVC (polyvinyl chloride) film structure material | |
CN115304942A (en) | Water-based long-acting antifogging self-cleaning coating and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |