CN115232508A - Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating - Google Patents
Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating Download PDFInfo
- Publication number
- CN115232508A CN115232508A CN202110444166.2A CN202110444166A CN115232508A CN 115232508 A CN115232508 A CN 115232508A CN 202110444166 A CN202110444166 A CN 202110444166A CN 115232508 A CN115232508 A CN 115232508A
- Authority
- CN
- China
- Prior art keywords
- self
- isocyanate
- microcapsule
- derivative
- capsule
- 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.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 106
- 238000000576 coating method Methods 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002775 capsule Substances 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims description 43
- 229920002635 polyurethane Polymers 0.000 claims description 43
- 239000012948 isocyanate Substances 0.000 claims description 41
- 150000002513 isocyanates Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910021389 graphene Inorganic materials 0.000 claims description 30
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 20
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- 238000005260 corrosion Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 15
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyoxypropylene Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010406 interfacial reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- MGOLNIXAPIAKFM-UHFFFAOYSA-N 2-isocyanato-2-methylpropane Chemical compound CC(C)(C)N=C=O MGOLNIXAPIAKFM-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 229950008882 polysorbate Drugs 0.000 claims description 5
- 229920000136 polysorbate Polymers 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000013638 trimer Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical group CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 3
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 claims description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 2
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 claims description 2
- 235000001014 amino acid Nutrition 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000787 lecithin Substances 0.000 claims description 2
- 235000010445 lecithin Nutrition 0.000 claims description 2
- 229940067606 lecithin Drugs 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229960004274 stearic acid Drugs 0.000 claims description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 230000002035 prolonged effect Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 229940075507 glyceryl monostearate Drugs 0.000 description 9
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008439 repair process Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 6
- 239000010695 polyglycol Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229940093476 ethylene glycol Drugs 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
Images
Classifications
-
- 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
- C09D7/65—Additives macromolecular
-
- 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
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to the technical field of intelligent anticorrosive coatings, in particular to a self-repairing microcapsule, a preparation method and application thereof, an anticorrosive coating and an anticorrosive coating. The self-repairing microcapsule comprises a capsule wall and a capsule core, wherein the load strength of the capsule wall is 0.1-50mN, and the capsule core has fluidity and can generate polymerization reaction when meeting water. The capsule wall of the self-repairing microcapsule provided by the invention is easy to damage under the action of external force, the capsule core wrapped by the capsule wall can flow out, and the polymerization reaction is generated when the capsule wall meets water, so that the coating cracks can be automatically filled, and the quick repairing of the coating cracks is realized; meanwhile, the self-repairing microcapsule provided by the invention can make up for the crack width of a coating in a larger range, such as 100nm-1 mm.
Description
Technical Field
The invention relates to the technical field of intelligent anticorrosive coatings, in particular to a self-repairing microcapsule, a preparation method and application thereof, an anticorrosive coating and an anticorrosive coating.
Background
In the preparation process of the coating, factors such as crosslinking, condensation polymerization and solvent volatilization of organic molecules are accompanied in the coating forming process, so that the internal density of the coating is uneven, and micro defects such as micropores, crack gaps and the like are formed. And then, because the solvent volatilizes, the coating surface can leave the micropore passageway, become the transmission channel of external electrolyte solution infiltration. Therefore, the organic coating itself has drawbacks of gas permeability and porosity, allowing water, dissolved oxygen, and electrolyte ions to permeate to the metal surface, thereby causing corrosion of the interface between the metal and the coating, resulting in failure of the coating.
The traditional corrosion-resistant coating material can generate cracks due to collision and other reasons in the using process, corrosion starts from the microcracks, and the corrosion-resistant coating material can finally fail if the corrosion-resistant coating material is not repaired in time.
To solve the problem, researchers at home and abroad put forward a self-repairing concept, and microcapsules with a self-repairing function are added into the anticorrosive coating, wherein the size of the microcapsules is 20-200 mu m. Firstly, dispersing 1-5% of microcapsules in an active diluent, such as methacrylic acid-beta-hydroxyethyl ester, 1, 6-hexanediol diacrylate and the like, by mass percent, adopting a high-speed stirrer at a speed of not less than 100r/min, stirring for a time of not less than 1h, after stirring is finished, quickly transferring the microcapsules into a resin (such as epoxy resin) system, and then fully stirring the microcapsules to be uniform, wherein the prepared coating can effectively repair cracks, prolong the service life of the material and play a good anti-corrosion role.
However, some microcapsule wall failures require the addition of an external catalyst to the effluent liquid, which in combination with the external catalyst cures to repair the failure of the coating. In addition, although some microcapsules can repair damaged parts, the corrosion resistance of the repaired parts is poor, the corrosion resistance of the repairing agent wrapped by the microcapsules is relatively poor, and even if the damaged parts can be temporarily compensated, the compensated damaged parts cannot resist the corrosion and the erosion of the outside for a long time.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, an external catalyst needs to be added to a self-repairing microcapsule, the repairing effect is poor, or the time for resisting external corrosion of a repaired damaged part is short and the like, and provides the self-repairing microcapsule, a preparation method and application thereof, an anticorrosive coating and an anticorrosive coating. The self-repairing microcapsule can generate polymerization reaction when meeting water, and an external catalyst is not required to be added, so that the coating cracks can be quickly repaired.
In order to achieve the above object, a first aspect of the present invention provides a self-healing microcapsule comprising: the capsule comprises a capsule wall and a capsule core, wherein the load strength of the capsule wall is 0.1-50mN, and the capsule core has fluidity and can generate polymerization reaction when meeting water.
Preferably, the capsule wall comprises polyurethane; the core comprises isocyanate and/or derivatives thereof, optionally graphene and/or derivatives thereof.
The second aspect of the invention provides a preparation method of a self-repairing microcapsule, which comprises the following steps:
(1) Mixing water, an emulsifier and an optional surfactant to obtain emulsion A;
(2) Mixing isocyanate and/or derivatives thereof and optional graphene and/or derivatives thereof to obtain a mixed solution B;
(3) Under the condition of interfacial reaction, contacting the emulsion A and the mixed solution B with polyurethane;
wherein the weight average molecular weight of the polyurethane is 5000-15000g/mol.
In a third aspect, the present invention provides a self-repairing microcapsule provided in the first aspect and/or a self-repairing microcapsule prepared by the method provided in the second aspect, and the application of the self-repairing microcapsule in a coating.
In a fourth aspect, the invention provides an anticorrosive coating, which comprises the self-repairing microcapsules provided by the first aspect and/or the self-repairing microcapsules prepared by the method provided by the second aspect.
In a fifth aspect, the invention provides an anticorrosive coating comprising the self-repairing microcapsules provided in the first aspect and/or the self-repairing microcapsules prepared by the method provided in the second aspect.
Through the technical scheme, the capsule wall of the self-repairing microcapsule provided by the invention is easy to damage under the action of external force, and the capsule core wrapped by the capsule wall can flow out and generate polymerization reaction when meeting water, so that the coating cracks can be automatically filled, and the coating cracks can be quickly repaired; in particular, the core comprises isocyanates and/or derivatives thereof capable of achieving curing in water without the addition of an external catalyst; particularly, the coating contains graphene and/or derivatives thereof, so that the corrosion resistance duration of the capsule core after curing is further effectively prolonged, the service life of the repaired coating is prolonged, and the corrosion resistance duration of the whole coating is prolonged. The self-repairing microcapsule provided by the invention can make up the crack width of a coating in a large range, such as 100nm-1 mm.
Drawings
Fig. 1 is an SEM image of the self-healing microcapsule S1 made in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a self-healing microcapsule comprising: the capsule wall has the load strength of 0.1-50mN, and the capsule core has fluidity and can generate polymerization reaction when meeting water.
In the present invention, the load strength of the capsule wall is measured using a NanoIndenter tester (Agilent G200NanoIndenter (Agilent Technologies, inc., chandler, AZ)); the test conditions included: a triangular cone Berkovich pressure head is adopted, before testing, the microcapsules are dispersed and washed for 2-3 times by alcohol, then filtered and moved to a drying oven for drying for 24 hours, and the dried microcapsules are moved to a glass slide and fixed by strong glue. The microcapsule test process adopts a continuous rigidity matrix method, and the speed of pressing the probe into the microcapsule is 0.05s -1 The penetration depth was 3 μm and 8 μm. And after the probe is pressed in, the probe stays for 10s and then is lifted, and finally the stress curve of the microcapsule is obtained. According to the stress curve of the microcapsule, the ordinate corresponding to the vertex of the stress curve is the load strength of the capsule wall.
In the present invention, the fluidity means that the capsule core is continuously deformed to flow by any minute shearing force without any special case; the water refers to a specific environmental condition, namely, the capsule core can generate polymerization reaction in water and the dosage of the water is not limited at all.
In some embodiments of the present invention, preferably, the weight ratio of the capsule wall to the capsule core is 1:5-20, preferably 1:5-15. In the present invention, the weight ratio of the capsule wall to the capsule core is calculated by measuring the weight of the capsule wall and the capsule core, respectively.
In some embodiments of the present invention, it is preferred that the self-healing microcapsules have a particle size of 20-500 μm, preferably 40-200 μm. Wherein the particle size of the self-repairing microcapsule is measured by an optical microscopy method.
In some embodiments of the invention, preferably, the thickness of the capsule wall is 1-50 μm, preferably 4-15 μm; wherein the thickness of the capsule wall is measured by SEM scanning electron microscopy.
In some embodiments of the invention, preferably, the capsule wall comprises polyurethane; the core comprises isocyanate and/or derivatives thereof, optionally graphene and/or derivatives thereof.
According to a preferred embodiment of the invention, the capsule wall is polyurethane; the capsule core is isocyanate and/or derivatives thereof, and graphene and/or derivatives thereof.
In order to ensure that the capsule wall of the self-repairing microcapsule provided by the invention is easy to damage under the action of external force, the capsule core wrapped by the capsule wall can be caused to flow out, and the coating cracks are automatically filled, thereby realizing the rapid repair of the coating cracks. Preferably, the weight average molecular weight of the polyurethane is 5000-15000g/mol, wherein the weight average molecular weight is determined by gel chromatography methods.
In some embodiments of the present invention, preferably, in the capsule core, the weight ratio of the isocyanate and/or its derivative, the graphene and/or its derivative is 30-80:0 to 5; preferably 50 to 80:0.5-2. By adopting the optimal weight ratio, the corrosion resistance duration of the cured capsule core can be effectively prolonged, the service life of the repaired coating is prolonged, and the corrosion resistance duration of the whole coating is prolonged.
In some embodiments of the present invention, preferably, the isocyanate is selected from at least one of tert-butyl isocyanate, propyl isocyanate, toluene diisocyanate, p-toluene diisocyanate, m-toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.
In some embodiments of the present invention, preferably, the isocyanate derivative is selected from at least one of hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret, an addition product of hexamethylene diisocyanate and trimethylolpropane, and isophorone diisocyanate trimer.
In some embodiments of the present invention, preferably, the graphene is selected from at least one of single-layer graphene, double-layer graphene, multi-layer graphene, and few-layer graphene.
In some embodiments of the present invention, preferably, the graphene derivative is selected from at least one of graphene oxide, carbon nanotube, graphene and nitrogen-doped graphene.
The second aspect of the invention provides a preparation method of a self-repairing microcapsule, which comprises the following steps:
(1) Mixing water, an emulsifier and an optional surfactant to obtain emulsion A;
(2) Mixing isocyanate and/or derivatives thereof and optional graphene and/or derivatives thereof to obtain a mixed solution B;
(3) Under the condition of interfacial reaction, contacting the emulsion A and the mixed solution B with polyurethane;
wherein the weight average molecular weight of the polyurethane is 5000-15000g/mol.
The invention carries out interface reaction between the capsule core and the capsule wall in the emulsion to obtain the microcapsule, namely: and (3) carrying out an interfacial reaction on the mixed solution B and polyurethane in the emulsion A, namely, carrying out a polymerization reaction on the isocyanate and/or the derivative thereof in the mixed solution B and the polyurethane in the emulsion A to obtain the self-repairing microcapsule with the core-shell structure.
In the present invention, the manner of mixing the water, the emulsifier and the optional surfactant in step (1) has a wide range of options as long as the water, the emulsifier and the optional surfactant are uniformly mixed. Preferably, the mixing conditions in step (1) include: the temperature is 10-40 deg.C, preferably 20-30 deg.C, and the time is 10-60min, preferably 20-50min.
In some embodiments of the present invention, preferably, in step (1), the weight ratio of the water, the emulsifier and the surfactant is 40-100:1-30:0 to 5, preferably 80 to 100:1-10:0-3.
In the present invention, the water is used as a solvent for dissolving the emulsifier and the surfactant, and preferably, the water is selected from deionized water and/or distilled water; the emulsifier is used to disperse the polyurethane, and thus, the emulsifier may be various emulsifiers of amphoteric actives, preferably emulsifiers having nonionic surfactant properties.
In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of nonylphenol polyoxyethylene ether, phenethylphenol polyoxypropylene polyoxyethylene ether, octadecanol polyoxyethylene ether, fatty amine polyoxyethylene ether, polyoxyethylene stearate, polyglycerol fatty acid ester, glycerol polyoxyethylene ether, polyoxypropylene ether fatty acid ester, aralkylphenol polyoxyethylene ether formaldehyde condensate, polysorbate, glyceryl monostearate, n-butanol, ethylene glycol, and polyglycol.
In some embodiments of the invention, the polyglycol is selected from polyethylene glycol and/or polypropylene glycol, the polyglycol having a weight average molecular weight of from 1500 to 4000g/mol.
In a preferred embodiment, the emulsifier is a combination of fatty amine polyoxyethylene ether, glyceryl monostearate and ethylene glycol, more preferably, the molar ratio of fatty amine polyoxyethylene ether, glyceryl monostearate and ethylene glycol is 1:1-3:1-8, wherein the fatty amine polyoxyethylene ether is selected from at least one of octadecylamine polyoxyethylene ether, cocoamine polyoxyethylene ether and tallow amine polyoxyethylene ether. The adoption of the optimized emulsifier can further more uniformly emulsify the polyurethane, is more favorable for promoting the reaction of the capsule wall on the surface of the capsule core and can completely cover the capsule core.
In another preferred embodiment, the emulsifier is a combination of glyceryl monostearate and ethylene glycol, more preferably wherein the molar ratio of glyceryl monostearate to ethylene glycol is 1:1-12. The use of the preferred emulsifier can further emulsify the polyurethane more uniformly, and is more favorable for promoting the reaction of the capsule wall on the surface of the capsule core and completely covering the capsule core.
In some embodiments of the present invention, preferably, the surfactant is selected from at least one of stearic acid, sodium dodecylbenzenesulfonate, lecithin, amino acid, sodium lauryl sulfate, and sodium lauryl sulfate.
In a preferred embodiment, the surfactant is a combination of stearic acid and sodium lauryl sulfate, wherein the weight ratio of stearic acid to sodium lauryl sulfate is 1:0.5-5.
In another preferred embodiment, the surfactant is a combination of sodium lauryl sulfate and sodium lauryl sulfate, wherein the weight ratio of sodium lauryl sulfate to sodium lauryl sulfate is 2:0.5-10.
In the present invention, the manner of mixing the isocyanate and/or the derivative thereof, and optionally the graphene and/or the derivative thereof in the step (2) has a wide range of options as long as the isocyanate and/or the derivative thereof, and optionally the graphene and/or the derivative thereof are uniformly mixed. Preferably, the mixing conditions in step (2) include: the temperature is 40-80 deg.C, preferably 50-70 deg.C, and the time is 0.5-5 hr, preferably 1-3 hr.
In some embodiments of the present invention, preferably, in the step (2), the weight ratio of the isocyanate and/or the derivative thereof, the graphene and/or the derivative thereof is 30-80:0 to 5; preferably 50 to 80:0.5-2.
In some embodiments of the present invention, preferably, the weight ratio of the isocyanate and/or derivative thereof to the emulsifier is from 4 to 9:1, preferably 4 to 6:1. with the preferred weight ratio, capsule wall formation is facilitated.
In some embodiments of the present invention, preferably, the weight ratio of the isocyanate and/or derivative thereof to the polyurethane is 1:0.4-0.8, preferably 1:0.5-0.7. The preferable weight ratio is more favorable for promoting the reaction of the capsule wall on the surface of the capsule core and completely covering the capsule core.
In the present invention, unless otherwise specified, the contacting of the emulsion a and the mixed solution B with the polyurethane in step (3) means that the emulsion a and the mixed solution B are contacted with each other first, and then the emulsion a and the mixed solution B are contacted with the polyurethane; wherein the conditions of the contacting include: the temperature is 40-80 deg.C, preferably 50-70 deg.C, and the time is 0.5-2 hr, preferably 0.5-1 hr.
In a preferred embodiment, in step (3), the emulsion a is contacted with the mixed solution B, during which the solution becomes a suspension, and then polyurethane is added, and an interfacial reaction is performed under stirring, during which the solution becomes a milky suspension.
In some embodiments of the present invention, preferably, the interfacial reaction conditions comprise: the temperature is 40-80 ℃, preferably 50-70 ℃; the time is 1 to 15 hours, preferably 3 to 10 hours; the rotating speed is more than or equal to 100rpm, and preferably 500-1500rpm.
In the present invention, the isocyanate and/or its derivative, and the graphene and/or its derivative are defined as above, and the details of the present invention are not repeated.
In the present invention, there is a wide selection of sources of the polyurethane, which can be obtained commercially or by preparation, as long as the weight average molecular weight of the polyurethane is 5000 to 15000g/mol. Preferably, the polyurethane is obtained by polymerizing an isocyanate and/or a derivative thereof with at least one selected from the group consisting of a ketone, a diol and a phenol. Further preferably, the molar ratio of isocyanate and/or derivative thereof to at least one selected from the group consisting of ketone, diol and phenol in the polyurethane is 1:0.5 to 3, and may be, for example, 1:0.5, 1:1. 1:1.5, 1:2. 1:2.5 and 1:3, and any intermediate value therebetween, preferably 1:1-1.5, more preferably 1:1.
in a preferred embodiment, the polyurethane is obtained by polymerizing an isocyanate and/or a derivative thereof with a ketone, wherein the molar ratio of the isocyanate and/or the derivative thereof to the ketone is 1:0.5 to 3, more preferably 1:1-1.5; further preferably, the ketone is selected from at least one of acetone, cyclohexanone, and butanone.
In a preferred embodiment, the polyurethane is obtained by polymerization of an isocyanate and/or a derivative thereof and a diol, preferably wherein the molar ratio of isocyanate and/or a derivative thereof to diol is 1:0.5 to 3, more preferably 1:1-1.5; further preferably, the diol is at least one selected from the group consisting of butanediol, propanediol, polyether diol and polyglycol. Wherein the polyglycol is selected from polyethylene glycol and/or polypropylene glycol, and the weight average molecular weight of the polyglycol is 1500-4000g/mol; the polyether diol has a weight average molecular weight of 1500 to 4000g/mol.
In a preferred embodiment, the polyurethane is obtained by polymerization of isocyanate and/or derivatives thereof and phenol, preferably wherein the molar ratio of isocyanate and/or derivatives thereof to phenol is 1:0.5 to 3, more preferably 1:1-1.5; further preferably, the phenol is selected from at least one of 2,4, 6-tris (dimethylaminomethyl) phenol, catechol, hydroquinone and resorcinol.
The preparation method of the polyurethane provided by the invention comprises the following steps: adding ketone, dihydric alcohol or phenol into a container with the temperature of 120-180 ℃, filling nitrogen or helium into the container, ensuring that the pressure in the container is kept for 1-5h at 8-12kPa, then slowly cooling to room temperature at the speed of 1-10 ℃/min, adding isocyanate and/or derivatives thereof, then heating to 100 ℃ at the speed of 1-10 ℃/min, keeping for 1-5h, and then slowly cooling to room temperature at the speed of 1-5 ℃/min to obtain the polyurethane with the weight-average molecular weight of 5000-15000g/mol.
In the present invention, the method further comprises: and filtering, washing and drying the contacted product to obtain the self-repairing microcapsule, wherein the filtering, washing and drying are all conventional technical means in the field, and the invention is not limited to the above.
In a preferable embodiment, the product of the interfacial reaction is washed by deionized water, then filtered and cleaned by 1-20wt% acetone solution, the filtered microcapsule is placed in a vacuum drying oven at 25-50 ℃ for 1-10h, after full drying, the microcapsule is obtained, and the microcapsule is placed in a dryer for storage and standby.
In a third aspect, the present invention provides a self-repairing microcapsule provided in the first aspect and/or a self-repairing microcapsule prepared by the method provided in the second aspect, and the application of the self-repairing microcapsule in a coating.
The self-repairing microcapsule provided by the invention can make up a larger crack width range between 100nm and 1mm, and has the function of repairing cracks on line. When the coating has cracks, the capsule wall of the microcapsule contained in the coating is easy to damage under the action of external force, and the capsule core wrapped in the coating can flow out to automatically fill the cracks, so that the cracks are quickly repaired. The isocyanate and/or the derivative thereof in the capsule core can be cured when meeting water, namely, the isocyanate and/or the derivative thereof contained in the capsule core and the water are subjected to polymerization reaction, so that a curing catalyst, a curing agent or an initiator and the like are not required to be added into the coating in advance to initiate capsule curing, and the capsule core contains the graphene and/or the derivative thereof, so that the corrosion resistance duration of the cured capsule core is effectively prolonged, and the service life of the repaired coating and the corrosion resistance duration of the whole coating are prolonged.
In a fourth aspect, the invention provides an anticorrosive coating, which comprises the self-repairing microcapsules provided by the first aspect and/or the self-repairing microcapsules prepared by the method provided by the second aspect.
In a fifth aspect, the invention provides an anticorrosive coating comprising the self-repairing microcapsules provided in the first aspect and/or the self-repairing microcapsules prepared by the method provided in the second aspect.
The present invention will be described in detail below by way of examples.
The polyethylene glycol had a weight average molecular weight of 2000g/mol.
The particle size of the self-repairing microcapsule is measured by an optical microscopy method.
The thickness of the capsule wall is measured by a scanning electron microscope SEM method; the load strength of the capsule wall was measured using a NanoIndenter (Agilent G200NanoIndenter, agilent Technologies, inc., chandler, AZ)).
The weight average molecular weight of the polyurethane was measured by a gel chromatography method.
The SEM image of the self-repairing microcapsule is characterized by adopting a JSM-6700F type scanning electron microscope, and the test method comprises the following steps: the dried microcapsule powder was stuck to a stage with a double-sided tape, and observed with SEM after gold spraying.
The impedance values of the self-healing microcapsules were measured according to the American Standard ASTM G3-14 (2019) Standard Practice for considerations to Electrical Measurements in correction Testing.
The parameters of the self-healing microcapsules prepared in examples 1-10 are set forth in Table 1.
Example 1
(1) Into a 500mL glass vessel, 100mL of deionized water, 1g of an emulsifier (0.2 g of polysorbate, 0.3g of glyceryl monostearate, 0.2g of ethylene glycol, 0.3g of polyethylene glycol), 0.5g of a surfactant (0.3 g of sodium lauryl sulfate, 0.2g of sodium lauryl sulfate) were added, and the mixture was sufficiently stirred at 500rpm for 30 minutes to obtain emulsion A1.
(2) 5g of isocyanate (0.5 g of tert-butyl isocyanate, 4g of toluene diisocyanate, 0.5g of diphenylmethane diisocyanate) and 0.05g of single-layer graphene were mixed in a thermostatic water bath at 60 ℃ for 1.5 hours to obtain a mixed solution B1.
(3) Mixing the emulsion A1 with the mixed solution B1, keeping the mixture in a constant-temperature water bath at 60 ℃ for 50min, then adding the polyurethane C1, and fully stirring the mixture at the rotating speed of 800rpm for reaction for 4h. Washing with deionized water, filtering and cleaning with 10wt% acetone solution, standing the filtered microcapsule in a vacuum drying oven at 30 deg.C for 5 hr, drying, and storing in a drier. Is marked as a self-repairing microcapsule S1.
Wherein the preparation of the urethane C1 comprises the following steps: adding 5g of propylene glycol into a three-neck flask at 150 ℃, filling nitrogen into the three-neck flask, ensuring that the pressure in the three-neck flask is 10kPa, keeping for 4h, then slowly cooling to room temperature at 1 ℃/min, adding 10g of p-phenylene diisocyanate, then heating to 100 ℃ at 10 ℃/min, keeping for 4h, and then slowly cooling to room temperature at 1 ℃/min, thus obtaining polyurethane C1, wherein the weight average molecular weight of the polyurethane C1 is 7000g/mol.
The SEM image of the self-repairing microcapsule S1 is shown in figure 1, and as can be seen from figure 1, the self-repairing microcapsule S1 has a core-shell structure, namely, a core is a capsule core, and a shell is a capsule wall.
Example 2
(1) In a 500mL glass vessel, 100ml of deionized water, 1g of an emulsifier (the molar ratio of fatty amine polyoxyethylene ether, glyceryl monostearate, and ethylene glycol is 1.
(2) 5g of isocyanate (1 g of tert-butyl isocyanate and 4g of m-phenylene diisocyanate) and 0.1g of double-layer graphene are mixed in a constant-temperature water bath at 70 ℃ for 1 hour to obtain a mixed solution B2.
(3) Mixing the emulsion A2 with the mixed solution B2, keeping the mixture in a constant-temperature water bath at 70 ℃ for 50min, adding the polyurethane C2, and fully stirring and reacting for 8h at the rotating speed of 1000 rpm. Washing the emulsion with deionized water, filtering and cleaning with a 10% ethanol solution, placing the filtered microcapsule in a vacuum drying oven at 30 ℃ for 5h, fully drying, and placing in a dryer for storage, wherein the microcapsule is marked as a self-repairing microcapsule S2.
Wherein the preparation of the polyurethane C2 comprises the following steps: adding 6g of cyclohexanone into a three-neck flask at 150 ℃, filling nitrogen into the three-neck flask, ensuring that the pressure in the three-neck flask is 10kPa, keeping for 4h, then slowly cooling to room temperature at 3 ℃/min, adding 10g of p-phenylene diisocyanate, then heating to 100 ℃ at 10 ℃/min, keeping for 4h, and then slowly cooling to room temperature at 1 ℃/min, thus obtaining polyurethane C2, wherein the weight average molecular weight of the polyurethane C2 is 5000g/mol.
Wherein, the SEM image of the self-repairing microcapsule S2 is similar to that of figure 1.
Example 3
(1) Into a 500mL glass vessel, 100mL of deionized water, 1g of an emulsifier (the molar ratio of glycerin monostearate to ethylene glycol is 1: 5) and 0.5g of a surfactant (the weight ratio of stearic acid to sodium lauryl sulfate is 1: 3) were added, and the mixture was sufficiently stirred at 500rpm for 30 minutes to obtain an emulsion A3.
(2) 5g of isocyanate (0.5 g of t-butyl isocyanate and 4.5g of p-phenylene diisocyanate) and 0.2g of graphene were mixed in a thermostatic water bath at 60 ℃ for 1.5 hours to obtain a mixed solution B3.
(3) Mixing the emulsion A3 with the mixed solution B3, keeping the mixture in a constant-temperature water bath at 70 ℃ for 50min, adding the polyurethane C3, and fully stirring at the rotating speed of 900rpm for reaction for 5h. Washing the emulsion with deionized water, filtering and cleaning with a 10% methanol solution, placing the filtered microcapsule in a vacuum drying oven at 30 ℃ for 5h, fully drying, and placing in a dryer for storage, wherein the microcapsule is marked as a self-repairing microcapsule S3.
Wherein the preparation of the polyurethane C3 comprises the following steps: adding 4.5g of phenol into a 160 ℃ three-neck flask, filling nitrogen into the three-neck flask, ensuring that the pressure in the three-neck flask is 12kPa, keeping for 4h, then slowly cooling to room temperature at 5 ℃/min, adding 10g of p-phenylene diisocyanate, then heating to 100 ℃ at 10 ℃/min, keeping for 4h, and then slowly cooling to room temperature at 1 ℃/min, thus obtaining polyurethane C3, wherein the weight-average molecular weight of the polyurethane C3 is 12000g/mol.
Wherein, the SEM image of the self-repairing microcapsule S3 is similar to that of figure 1.
Example 4
The same procedure was followed as in example 1 except that 0.01g of graphene oxide was used, to finally obtain a self-repairing microcapsule S4.
Example 5
The same procedure was followed as in example 1, except for using 5g of isocyanate (of which 1g of t-butyl isocyanate, 2g of toluene diisocyanate, 2g of diphenylmethane diisocyanate), to finally obtain a self-healing microcapsule S5.
Example 6
The same procedure was followed as in example 1 except that 5g of isocyanate (4 g of toluene diisocyanate and 1g of diphenylmethane diisocyanate) was used to finally obtain a self-healing microcapsule S6.
Example 7
The procedure of example 1 was followed except for using 5g of the isocyanate derivative (hexamethylene diisocyanate trimer 2g, hexamethylene diisocyanate 3 g) and the same procedure, to finally obtain a self-repairing microcapsule S7.
Example 8
Following the procedure of example 1, except that 0.5g of surfactant (0.3 g of sodium lauryl sulfate, 0.2g of sodium lauryl sulfate) was not added, the same procedure was followed to finally obtain a self-repairing microcapsule S8.
Example 9
The same procedure was followed as in example 1 except that 3.6g of emulsifier (among them, 0.8g of polysorbate, 0.8g of glyceryl monostearate, 1.2g of ethylene glycol, 0.8g of polyethylene glycol) was used, to finally obtain a self-repairing microcapsule S9.
Example 10
According to the method of the embodiment 1, except that in the step (2), 0.05g of single-layer graphene is not added, the other steps are the same, and the self-repairing microcapsule S10 is finally obtained.
Comparative example 1
Following the procedure of example 1, except that in step (1), 1g of emulsifier (0.2 g polysorbate, 0.3g glyceryl monostearate, 0.2g ethylene glycol, 0.3g polyethylene glycol) was not added, the remaining steps were the same, and finally no microcapsules were obtained.
TABLE 1
Note: weight ratio refers to the weight ratio of the capsule core to the capsule wall.
As can be seen from the data in Table 1, the self-repairing microcapsule prepared by the method provided by the invention has a core-shell structure of a capsule core and a capsule wall; meanwhile, the load strength of the capsule wall of the microcapsule prepared by the method is 0.1-50mN, the microcapsule can be easily broken under the action of external force, the contained capsule core can flow out, and the microcapsule can be polymerized to automatically fill cracks when meeting water, so that the rapid repair of the cracks is realized.
Test example
The self-healing microcapsules prepared in examples 1-10 were subjected to a healing test.
The test method comprises the following steps: the self-repairing microcapsules S1 to S10 were dispersed in the epoxy resin E51 at a mass fraction of 5%, respectively, a coating having a thickness of about 1mm was formed on the surface of the carbon steel Q235, scratches having a width of 0.5mm were formed on the surface of the prepared coated sample, the sample was immersed in NaCl brine at a mass fraction of 3%, and the impedance values thereof were measured, and the results are shown in Table 2.
TABLE 2
TABLE 2
As can be seen from the data in Table 2, the coating layer containing the microcapsules provided by the invention has the resistance value which is gradually increased along with the increase of time under the condition that the cracks exist, and the microcapsules are indicated to gradually repair the cracks, namely the resistance value is shown to be increased along with the increase of time. The microcapsule provided by the invention can repair the crack width of 0.5mm, so that the corrosion prevention time of the cured capsule core is effectively prolonged, a better repair effect is achieved, and particularly, the time of resisting external corrosion of the repaired damaged part is remarkably prolonged due to the introduction of graphene and/or derivatives thereof; meanwhile, the microcapsule provided by the invention does not need to put a curing catalyst, a curing agent or an initiator and the like into the coating in advance to initiate capsule core curing, namely, the capsule core of the microcapsule has fluidity, and the capsule core is polymerized when meeting water, so that the capsule core curing is initiated.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A self-healing microcapsule, comprising: the capsule comprises a capsule wall and a capsule core, wherein the load strength of the capsule wall is 0.1-50mN, and the capsule core has fluidity and can generate polymerization reaction when meeting water.
2. The self-repairing microcapsule of claim 1, wherein the weight ratio of wall to core is 1:5-20, preferably 1:5-15.
3. The self-healing microcapsule according to claim 1 or 2, wherein the particle size of the self-healing microcapsule is from 20 to 500 μ ι η, preferably from 40 to 200 μ ι η;
preferably, the thickness of the capsule wall is 1-50 μm, preferably 4-15 μm.
4. The self-healing microcapsule of any one of claims 1 to 3, wherein the capsule wall comprises polyurethane;
the capsule core comprises isocyanate and/or a derivative thereof, optionally graphene and/or a derivative thereof;
preferably, the weight average molecular weight of the polyurethane is 5000 to 15000g/mol.
5. The self-repairing microcapsule of claim 4, wherein the weight ratio of the isocyanate and/or derivative thereof, graphene and/or derivative thereof in the capsule core is 30-80:0 to 5, preferably 50 to 80:0.5-2.
6. The self-healing microcapsule of claim 4 or 5, wherein the isocyanate is selected from at least one of t-butyl isocyanate, propyl isocyanate, toluene diisocyanate, p-toluene diisocyanate, m-toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate;
preferably, the isocyanate derivative is selected from at least one of hexamethylene diisocyanate trimer, hexamethylene diisocyanate biuret, an addition product of hexamethylene diisocyanate and trimethylolpropane, and isophorone diisocyanate trimer.
7. A method of making self-healing microcapsules, comprising the steps of:
(1) Mixing water, an emulsifier and an optional surfactant to obtain an emulsion A;
(2) Mixing isocyanate and/or derivatives thereof and optional graphene and/or derivatives thereof to obtain a mixed solution B;
(3) Under the condition of interfacial reaction, contacting the emulsion A and the mixed solution B with polyurethane;
wherein the weight average molecular weight of the polyurethane is 5000-15000g/mol.
8. The method according to claim 7, wherein in the step (1), the weight ratio of the water to the emulsifier to the surfactant is 40-100:1-30:0 to 5, preferably 80 to 100:1-10:0-3.
9. The method according to claim 7 or 8, wherein the emulsifier is selected from at least one of nonylphenol polyoxyethylene ether, phenethylphenol polyoxypropylene polyoxyethylene ether, octadecanol group polyoxyethylene ether, fatty amine polyoxyethylene ether, polyoxyethylene stearate, polyglycerol fatty acid ester, glycerol polyoxyethylene ether, polyoxypropylene ether fatty acid ester, aralkylphenol polyoxyethylene ether formaldehyde condensate, polysorbate, glycerol monostearate, n-butanol, ethylene glycol, and polyalkylene glycol;
preferably, the surfactant is selected from at least one of stearic acid, sodium dodecylbenzenesulfonate, lecithin, amino acid, sodium dodecylsulfate, and sodium lauryl sulfate.
10. The process according to any one of claims 7 to 9, wherein in step (2), the weight ratio of the isocyanate and/or the derivative thereof, graphene and/or the derivative thereof is 30-80:0 to 5; preferably 50 to 80:0.5 to 2;
preferably, the weight ratio of the isocyanate and/or derivative thereof to the emulsifier is from 4 to 9:1, preferably 4 to 6:1.
11. the process according to any one of claims 7 to 10, wherein the weight ratio of isocyanate and/or derivative thereof to polyurethane is 1:0.4-0.8, preferably 1:0.5-0.7.
12. The method of any one of claims 7-11, wherein the interfacial reaction conditions comprise: the temperature is 40-80 ℃, preferably 50-70 ℃; the time is 1 to 15 hours, preferably 3 to 10 hours; the rotating speed is more than or equal to 100rpm, preferably 500-1500rpm;
preferably, the method further comprises: and filtering, washing and drying the contacted product.
13. Use of the self-healing microcapsules of any one of claims 1 to 6 and/or the self-healing microcapsules produced by the process of any one of claims 7 to 12 in a coating.
14. Use according to claim 13, wherein the coating has a crack width of 100nm to 1mm, preferably 10 to 50 μm.
15. An anticorrosive coating comprising the self-healing microcapsules of any one of claims 1-6 and/or the self-healing microcapsules made by the process of any one of claims 7-12.
16. An anti-corrosion coating comprising the self-healing microcapsules of any one of claims 1 to 6 and/or the self-healing microcapsules produced by the process of any one of claims 7 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110444166.2A CN115232508A (en) | 2021-04-23 | 2021-04-23 | Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110444166.2A CN115232508A (en) | 2021-04-23 | 2021-04-23 | Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115232508A true CN115232508A (en) | 2022-10-25 |
Family
ID=83666750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110444166.2A Pending CN115232508A (en) | 2021-04-23 | 2021-04-23 | Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115232508A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702838A (en) * | 2012-06-28 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | Micro-crack self-repairing microcapsule and preparation method thereof |
| US20130196071A1 (en) * | 2012-02-01 | 2013-08-01 | Nanyang Technological University | Microencapsulation of reactive diisocyanates and the application to self-healing anticorrosion coatings |
| CN107096476A (en) * | 2017-06-13 | 2017-08-29 | 武汉纺织大学 | Polyurethane mixing microcapsule and preparation method thereof |
| CN108912870A (en) * | 2018-07-26 | 2018-11-30 | 成都新柯力化工科技有限公司 | A kind of selfreparing anti-corrosion outdoor building graphene coating and preparation method |
| CN109663549A (en) * | 2018-12-03 | 2019-04-23 | 南京工业大学 | A kind of preparation method of graphene microcapsules |
| CN111690318A (en) * | 2020-07-30 | 2020-09-22 | 九天起宏(江苏)检测有限公司 | Self-repairing waterborne polyurethane coating composition and coating |
| CN111790325A (en) * | 2020-07-17 | 2020-10-20 | 中山纳微新材料科技有限公司 | Double-shell self-repairing microcapsule and preparation method and application thereof |
| US20220202731A1 (en) * | 2019-04-05 | 2022-06-30 | Council Of Scientific & Industrial Research | Bio-compatible polyurethane microcapsules and process for the preparation thereof |
-
2021
- 2021-04-23 CN CN202110444166.2A patent/CN115232508A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130196071A1 (en) * | 2012-02-01 | 2013-08-01 | Nanyang Technological University | Microencapsulation of reactive diisocyanates and the application to self-healing anticorrosion coatings |
| CN102702838A (en) * | 2012-06-28 | 2012-10-03 | 中国船舶重工集团公司第七二五研究所 | Micro-crack self-repairing microcapsule and preparation method thereof |
| CN107096476A (en) * | 2017-06-13 | 2017-08-29 | 武汉纺织大学 | Polyurethane mixing microcapsule and preparation method thereof |
| CN108912870A (en) * | 2018-07-26 | 2018-11-30 | 成都新柯力化工科技有限公司 | A kind of selfreparing anti-corrosion outdoor building graphene coating and preparation method |
| CN109663549A (en) * | 2018-12-03 | 2019-04-23 | 南京工业大学 | A kind of preparation method of graphene microcapsules |
| US20220202731A1 (en) * | 2019-04-05 | 2022-06-30 | Council Of Scientific & Industrial Research | Bio-compatible polyurethane microcapsules and process for the preparation thereof |
| CN111790325A (en) * | 2020-07-17 | 2020-10-20 | 中山纳微新材料科技有限公司 | Double-shell self-repairing microcapsule and preparation method and application thereof |
| CN111690318A (en) * | 2020-07-30 | 2020-09-22 | 九天起宏(江苏)检测有限公司 | Self-repairing waterborne polyurethane coating composition and coating |
Non-Patent Citations (1)
| Title |
|---|
| 陈凯锋;梁宇;宋妍;张心悦;: "微胶囊修复技术在涂料中的应用研究" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109957969B (en) | Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material | |
| JP2012224714A (en) | Insulating varnish for low dielectric constant and insulated wire using the same | |
| CN105907354A (en) | Weather resistance adhesive and application thereof on solar cell backboard | |
| JP4616916B2 (en) | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitors | |
| CN111423717B (en) | Floating body material for waterborne photovoltaic system and preparation method thereof | |
| CN115232508A (en) | Self-repairing microcapsule, preparation method and application thereof, anticorrosive coating and anticorrosive coating | |
| CN113450945A (en) | Self-repairing anti-icing aluminum stranded wire with composite hole and preparation method thereof | |
| WO2011118027A1 (en) | Resin-coated aluminum alloy plate for bottomed cylindrical case for capacitor | |
| CN111690318B (en) | Self-repairing waterborne polyurethane coating composition and coating | |
| CN115232502A (en) | Self-repairing microcapsule and preparation method and application thereof | |
| CN105413487B (en) | A kind of polypropylene hollow fiber microporous membrane and preparation method thereof | |
| CN109135403B (en) | Self-repairing water-based paint based on PU/PUF (polyurethane/polyurethane elastomer) microcapsules and PCL (polycaprolactone) microcapsules and preparation method thereof | |
| CN115678413B (en) | Bi-component polyurethane waterproof paint and preparation method thereof | |
| CN115228400A (en) | Self-repairing microcapsule and preparation method and application thereof | |
| WO2023245958A1 (en) | Tear-resistant color-changing film and preparation method therefor | |
| CN111808521B (en) | Self-repairing waterborne polyurethane coating composition and coating | |
| CN114015349A (en) | Enameled wire anti-aging coating | |
| JP2016225046A (en) | Insulation wire | |
| KR102489778B1 (en) | Manufacturing method of Flexible Flat Cable or Flexible Printed Circuit capable of spontaneous double side etching and composition of double sided tape for double side etching | |
| JP2017045662A (en) | Insulated wire and varnish for forming insulating layer | |
| CN114591669B (en) | Waterproof coating with cracking resistance and preparation method thereof | |
| CN114808548B (en) | High partial discharge insulating material for new energy automobile oil-cooled motor and preparation method thereof | |
| CN116313510B (en) | Conductive carbon paste for high molecular tantalum capacitor and preparation method and application method thereof | |
| CN113801359B (en) | Chemical floor anticorrosion composite film and preparation process thereof | |
| CN114334473B (en) | Conductive enhancing liquid for paper substrate of super capacitor, paper substrate and preparation method |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221025 |