CN116393057A - Graphene oxide modified bio-based microcapsule and preparation method and application thereof - Google Patents
Graphene oxide modified bio-based microcapsule and preparation method and application thereof Download PDFInfo
- Publication number
- CN116393057A CN116393057A CN202310444373.7A CN202310444373A CN116393057A CN 116393057 A CN116393057 A CN 116393057A CN 202310444373 A CN202310444373 A CN 202310444373A CN 116393057 A CN116393057 A CN 116393057A
- Authority
- CN
- China
- Prior art keywords
- bio
- microcapsule
- grafted
- curing agent
- epoxy resin
- 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 175
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 100
- 239000011248 coating agent Substances 0.000 claims abstract description 90
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- 239000003822 epoxy resin Substances 0.000 claims abstract description 77
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 77
- 239000002775 capsule Substances 0.000 claims abstract description 62
- 239000004094 surface-active agent Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 38
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 19
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 19
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 4
- 239000004626 polylactic acid Substances 0.000 claims abstract description 4
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 105
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 85
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 85
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 85
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 85
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011162 core material Substances 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 21
- 235000019198 oils Nutrition 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000011343 solid material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000004359 castor oil Substances 0.000 claims description 9
- 235000019438 castor oil Nutrition 0.000 claims description 9
- 238000005253 cladding Methods 0.000 claims description 9
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 9
- 239000003549 soybean oil Substances 0.000 claims description 9
- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- -1 maleic acid diamine Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000004888 barrier function Effects 0.000 abstract description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000035876 healing Effects 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 9
- 239000013003 healing agent Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 229960001777 castor oil Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229920006025 bioresin Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the fields of graphene oxide materials, bio-based materials and self-repairing coatings, and relates to a graphene oxide modified bio-based microcapsule, and a preparation method and application thereof. The bio-based microcapsule is microcapsule A and/or microcapsule B; the microcapsule A and the microcapsule B both comprise a capsule wall, a capsule core and a capsule wall outer wrapping layer; the microcapsule A and the microcapsule B are the same in capsule wall material and are polymethyl methacrylate, polysulfone or polylactic acid, the microcapsule A and the microcapsule B are the same in capsule wall outer wrapping material, and the microcapsule A and the microcapsule B are the same in bio-based surfactant and GO grafted with amino molecules; the capsule core of the microcapsule A comprises a composition of a bio-based curing agent and GO grafted with the bio-based curing agent; the capsule core of microcapsule B comprises a combination of bio-based epoxy resin and GO grafted with bio-based epoxy resin. The microcapsule prepared by the invention can improve the intrinsic barrier property of the bio-based coating and the corrosion resistance of the coating while endowing the coating with self-healing property.
Description
Technical Field
The invention belongs to the fields of graphene oxide materials, bio-based materials and self-repairing coatings, and relates to a graphene oxide modified bio-based microcapsule, and a preparation method and application thereof.
Background
The compact structure of the epoxy composite coating has a barrier effect on the matrix, can prevent penetration of corrosion factors, and is widely applied to the fields of ocean ships, petroleum pipelines, drilling platforms and the like. However, most epoxy coating materials are petroleum-based, non-biodegradable and derived from non-renewable resources, and are prone to environmental pollution. With the increasing depth of sustainable development concepts, bio-based coatings represented by cardanol-based, castor-oil-based, soybean-oil-based are attracting attention.
However, compared with the petroleum-based coating, the biological-based coating has a certain gap between corrosion resistance and mechanical properties, when the biological-based coating is exposed to natural environment, the surface is more easily damaged by external force to cause microcracks, the protection effect on a substrate is greatly reduced, and the long-term corrosion resistance of the coating is severely challenged.
The self-healing coating is one of methods for effectively prolonging the service life of the coating, and is divided into intrinsic self-healing and external self-healing, wherein the external self-healing mainly endows the coating with self-healing capability by loading fillers such as microcapsules, liquid core fibers, carbon nanotubes and the like in the coating. The microcapsule is widely applied due to simple preparation process and high healing efficiency.
The existing microcapsules are mainly applied to petroleum-based coatings and are special for fewer bio-based coatings. In previous work, we prepared a high biobased microcapsule using cardanol based healing agent and cardanol surfactant [ authorized bulletin number: CN115322613B ]. The service life of the coating can be remarkably prolonged through the self-healing effect. However, we have found experimentally that embedding microcapsules in a bio-based coating, petroleum-based polymethyl methacrylate as the capsule wall, has a general compatibility with bio-based materials and forms gaps with the coating. In addition, the liquid core material is coated in the microcapsule, so that a channel which is easy to permeate by corrosion factors is formed, and the self-healing microcapsule is added in the bio-based coating, so that the self-healing capability of the coating is successfully endowed, but the corrosion resistance and mechanical property of the bio-based coating are greatly reduced. In addition, the healing area formed after the rupture of the existing microcapsules is also easy to be a defect, and the overall performance of the coating is affected.
GO is a two-dimensional structural material containing a large number of oxygen-containing functional groups: carboxyl (-COOH), epoxy (-O-), hydroxyl (-OH), and is easy to graft with different functional groups, and has been used as a filler with high barrier and mechanical properties in the field of anticorrosive coatings. However, there are few reports on modification of microcapsules, particularly in the field of modification of bio-based microcapsules.
Disclosure of Invention
Aiming at the problems of corrosion resistance and mechanical property reduction of a bio-based coating caused by the existing bio-based microcapsule, the invention develops a microcapsule which is applicable to the bio-based microcapsule and the bio-based epoxy coating and wraps specific functionalized GO and bio-based healing agent and a high-efficiency preparation technology thereof so as to improve the corrosion resistance and mechanical property of the bio-based coating embedded with the bio-based microcapsule.
The invention is characterized in that: the GO with specific size is modified by grafting different functional groups, and hydrophilic and hydrophobic properties are adjusted to be respectively added into the capsule core and the capsule wall outer cladding. The capsule core is a bio-based healing agent with a repairing effect on the bio-based coating and modified GO grafted with the bio-based healing agent, and is encapsulated in a capsule wall material; when microcracks appear in the bio-based coating, the capsule wall of the microcapsule is broken, a capsule core material is released, a crack area is healed, and a modified GO material contained in the capsule core is dispersed at a healing part, so that the corrosion resistance of the healing part is improved, and the self-healing of the coating is realized; the outer coating of the capsule wall is modified GO (M-GO) grafted with amino molecules and a bio-based surfactant, the M-GO is uniformly embedded and wrapped on the outer surface of the capsule wall through electrostatic adsorption, amino on the modified GO can react with bio-based resin, the binding force between the microcapsule and the bio-based coating is enhanced, and when the coating is subjected to microcrack, the microcapsule can be opened better, thereby releasing healing factors and inhibiting penetration of corrosion factors.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a graphene oxide modified bio-based microcapsule, which is microcapsule A and/or microcapsule B; the microcapsule A and the microcapsule B comprise a capsule wall, a capsule core and a capsule wall outer wrapping layer; the microcapsule A and the microcapsule B are the same in capsule wall material, the microcapsule A and the microcapsule B are the same in capsule wall outer wrapping material, and the microcapsule A and the microcapsule B are different in capsule core material;
the material of the capsule wall comprises polymethyl methacrylate, polysulfone or polylactic acid, and preferably polymethyl methacrylate;
the material of the capsule wall outer cladding comprises a bio-based surfactant and GO (M-GO) grafted with amino molecules;
the microcapsule A comprises a core material and a combination of a bio-based curing agent and GO (Ami-GO) grafted with the bio-based curing agent;
the microcapsule B comprises a capsule core material of a composition of bio-based epoxy resin and GO (E-GO) grafted with the bio-based epoxy resin.
Wherein the polymethyl methacrylate, mw-195000; the polysulfone, mw-80000; the polylactic acid has Mw of 200000.
Wherein, the preparation method of the GO (M-GO) grafted with amino molecules refers to the prior art: L.Zhou, P.Zhang, L.Shen, L.Chu, J.Wu, Y.Ding, B.Zhong, X.Zhang, N.Bao, modified graphene oxide/waterborne epoxy composite coating with enhanced corrosion resistance Prog Org Coat 172 (2022) 107100.
Wherein, the preparation of the GO (Ami-GO) of the grafted bio-based curing agent can be carried out according to the following method:
(i) An 80kHz ultrasonic stripping concentration of GO/DMF solution of 1 g/L;
(ii) Mixing a bio-based curing agent, N' -Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and the GO/DMF solution obtained in the step (i), stirring at 80 ℃ for 24 hours, and obtaining a reaction solution after the reaction is finished; wherein the mass molar ratio of GO to the bio-based curing agent, N' -dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 50mg:1.5mmol:1.5mmol:1.5mmol;
(iii) Washing the reaction solution obtained in the step (ii) with ethanol for 5-6 times to obtain Ami-GO.
The preparation method of the GO (E-GO) grafted with the bio-based epoxy resin refers to the prior art: Y.Zhang, L.Chu, Z.Dai, N.Bao, M.B.de Rooij, L.Gao, W.Tan, L.Shen, synergistically enhancing the performance of cardanol-rich epoxy anticorrosive coatings using cardanol-based reactive diluent and its functionalized graphene oxide Prog Org Coat 171 (2022) 107060.
In some embodiments, the bio-based surfactant is any one of a cardanol-based surfactant, a castor oil-based surfactant, and a soybean oil-based surfactant; the amino molecules in the GO grafted with the amino molecules are maleic acid diamine or p-phenylenediamine; the bio-based curing agent is any one of a cardanol-based curing agent, a castor oil-based curing agent and a soybean oil-based curing agent; the bio-based epoxy resin is prepared by compounding any one of cardanol-based glycidyl ether, castor oil-based glycidyl ether and soybean oil-based glycidyl ether with epoxy resin according to any proportion.
In some embodiments, preferably, the bio-based surfactant is a cardanol-based surfactant; the amino molecules in the GO grafted with the amino molecules are maleic acid diamine; the bio-based curing agent is a cardanol-based curing agent; the bio-based epoxy resin is prepared from cardanol glycidyl ether and epoxy resin according to a mass ratio of 3:7, compounding.
In some embodiments, the mass ratio of bio-based curing agent to GO grafted bio-based curing agent in the core material is 1:0.01 to 0.03; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin in the capsule core material is 1:0.01 to 0.03; the mass ratio of the bio-based surfactant to the grafted amino molecules in the outer cladding of the capsule wall is 10:0.01 to 0.03; the mass ratio of the capsule wall to the capsule core to the capsule wall outer cladding is 1-2: 1.01 to 1.03:10.01 to 10.03.
In some embodiments, preferably, the mass ratio of bio-based curing agent to GO grafted bio-based curing agent in the core material is 1:0.03; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin in the capsule core material is 1:0.03; the mass ratio of the bio-based surfactant to the grafted amino molecules in the outer cladding of the capsule wall is 10:0.03; the mass ratio of the capsule wall to the capsule core to the capsule wall outer cladding is 1:1.03:10.03.
in some embodiments, the microcapsules have a particle size of 5 to 30 microns; wherein, the microcapsule with the grain size of 5-30 microns can realize the optimal self-repairing performance of the bio-based coating, the microcapsule with proper size and uniform grain size is dispersed in the coating, the mechanical property of the coating is uniformly improved, and the stability of the release speed after the microcapsule is broken is ensured.
Further, the invention discloses a preparation method of the graphene oxide modified bio-based microcapsule, which comprises the following steps:
(1) Adding a biological-based surfactant into water serving as a solvent, and stirring until the solid materials are completely dissolved to obtain an emulsifier aqueous solution;
(2) Dissolving a bio-based curing agent and a material of the capsule wall in dichloromethane, then adding GO grafted with the bio-based curing agent, and performing ultrasonic dispersion to obtain an oil phase; or dissolving the bio-based epoxy resin and the material of the capsule wall in dichloromethane, then adding GO grafted with the bio-based epoxy resin, and performing ultrasonic dispersion to obtain an oil phase;
(3) Adding GO grafted with amino molecules into part of the emulsifier aqueous solution obtained in the step (1), and performing ultrasonic dispersion to obtain a water phase;
(4) Adding the oil phase obtained in the step (2) into the water phase obtained in the step (3), and stirring and mixing uniformly to form emulsion;
(5) Adding the emulsion obtained in the step (4) into the water solution of the emulsifier obtained in the rest step (1), stirring for reaction, and after the reaction is finished, carrying out aftertreatment on the reaction solution to obtain the graphene oxide modified bio-based microcapsule.
In some embodiments, in step (1), the mass ratio of the bio-based surfactant to water is from 1 to 5:100; the mass ratio of the bio-based surfactant to the GO of the grafted amino molecule is 10:0.01 to 0.03.
In some embodiments, preferably, in step (1), the mass ratio of the bio-based surfactant to water is 5:100; the mass ratio of the bio-based surfactant to the GO of the grafted amino molecule is 10:0.03.
in some embodiments, the GO of the grafted bio-based curing agent exists in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO of the grafted bio-based curing agent in the mixed solution is 5-10 g/L; the GO grafted bio-based epoxy resin exists in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO grafted bio-based epoxy resin in the mixed solution is 5-10 g/L; the GO grafted amino molecules exist in the form of a mixed solution, the solvent in the mixed solution is water, and the concentration of the GO grafted amino molecules in the mixed solution is 5-10 g/L; the ultrasonic dispersion is carried out, the ultrasonic temperature is room temperature, and the ultrasonic frequency is 30-80 kHz.
In some embodiments, preferably, the GO of the grafted bio-based curing agent is present in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO of the grafted bio-based curing agent in the mixed solution is 10g/L; the GO grafted bio-based epoxy resin exists in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO grafted bio-based epoxy resin in the mixed solution is 10g/L; the GO grafted amino molecules exist in the form of a mixed solution, the solvent in the mixed solution is water, and the concentration of the GO grafted amino molecules in the mixed solution is 10g/L; the ultrasonic dispersion is carried out, the ultrasonic temperature is room temperature, and the ultrasonic frequency is 80kHz.
In some embodiments, in step (2), the mass ratio of the bio-based curing agent to the wall material is 1:1 to 2; the mass volume ratio of the bio-based curing agent to the dichloromethane is 1g:30 mL-50 mL; the mass ratio of the bio-based curing agent to the GO grafted bio-based curing agent is 1:0.01 to 0.03; the mass ratio of the bio-based epoxy resin to the capsule wall material is 1:1 to 2; the mass volume ratio of the bio-based epoxy resin to the dichloromethane is 1g:30 mL-50 mL; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin is 1:0.01 to 0.03.
In some embodiments, preferably, in step (2), the mass ratio of the bio-based curing agent to the wall material is 1:1, a step of; the mass volume ratio of the bio-based curing agent to the dichloromethane is 1g:30mL; the mass ratio of the bio-based curing agent to the GO grafted bio-based curing agent is 1:0.03; the mass ratio of the bio-based epoxy resin to the capsule wall material is 1:1, a step of; the mass volume ratio of the bio-based epoxy resin to the dichloromethane is 1g:30mL; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin is 1:0.03.
in some embodiments, in step (3), the portion of the aqueous emulsifier solution obtained in step (1) is used in an amount calculated as follows: the mass volume ratio of the GO grafted with the amino molecules to the emulsifier aqueous solution is 0.01 g-0.03 g:80mL, preferably 0.03g:80mL.
In some embodiments, in step (4), the mass ratio of wall material in the oil phase to GO grafted with amino molecules in the water phase is 1-2: 0.01 to 0.03; the stirring is carried out uniformly, the stirring speed is 1000-2000 r/min, and the stirring time is 10-15 min.
In some embodiments, preferably, in step (4), the mass ratio of wall material in the oil phase to GO grafted with amino molecules in the water phase is 1:0.03; the stirring is carried out uniformly, the stirring speed is 1000r/min, and the stirring time is 15min.
In some embodiments, in step (5), the stirring reaction is performed at a temperature of 30-50 ℃ for a period of 3-5 hours at a stirring rate of 300-500 r/min.
In some embodiments, preferably, in step (5), the stirring reaction is performed at a stirring temperature of 40 ℃ for a stirring time of 4 hours at a stirring rate of 300r/min.
The application of the graphene oxide modified bio-based microcapsule in preparing the self-healing bio-based coating is also within the protection scope of the invention.
In some embodiments, the above application is specifically: and stirring, dispersing and mixing the microcapsule A, the microcapsule B and the bio-based coating uniformly to obtain the self-healing bio-based coating.
In some embodiments, the bio-based coating is a cardanol coating, a castor oil coating, or a soybean oil epoxy coating; the total mass of the microcapsule A and the microcapsule B in the self-healing bio-based coating is 5-20wt%; the mass ratio of the microcapsule A to the microcapsule B is 1-2: 1.
in some embodiments, preferably, the bio-based coating is a cardanol coating; the total mass of the microcapsule A and the microcapsule B in the self-healing bio-based coating is 20wt%; the mass ratio of the microcapsule A to the microcapsule B is 1:1.
wherein, the material of the capsule core is a bio-based healing agent with a repairing effect on the self-healing bio-based coating and modified GO grafted with the bio-based healing agent, and is encapsulated in the capsule wall material; when microcrack appears in the self-healing bio-based coating, the capsule wall of the microcapsule is broken, the capsule core material is released, the crack area is healed, and the modified GO material contained in the capsule core is dispersed at the healing part, so that the self-healing of the coating is realized.
The bio-based coating is a coating layer formed by coating the bio-based coating on the surface of the metal substrate.
The graphene oxide modified bio-based microcapsule is applied to a bio-based coating to obtain a self-healing bio-based coating with high-efficiency corrosion resistance and self-healing capacity.
Wherein, preferably, the microcapsules can be added into the bio-based coating in a stirring and dispersing way. And coating the bio-based coating added with the microcapsules on a metal substrate to obtain the self-healing bio-based coating. When the self-healing bio-based coating surface is subjected to external force action to generate micro-cracks, the micro-capsules are broken under the stress expansion action, the wrapped healing agent and modified GO are released, the crack area is repaired, and the corrosion resistance and mechanical properties of the bio-based coating are improved.
The beneficial effects are that:
(1) The microcapsule prepared by the invention wraps two repairing agents and modified GO grafted with the corresponding repairing agent, one is a bio-based curing agent, the other is a bio-based epoxy resin, the two repairing agents are released and cured after the microcapsule is broken, crack positions are repaired, and the released modified GO can play a role in enhancing the barrier and mechanical properties of a healing area.
(2) According to the invention, GO is modified in a manner of grafting amino groups, so that the mutual binding force of the microcapsule and a coating matrix is enhanced, and the dispersibility and healing efficiency of the microcapsule are improved (the existence of GO when microcracks occur can enable the microcapsule to be rapidly broken so as to release healing factors).
(3) The modified GO grafted with amino is coated on the surface of the bio-based microcapsule, so that penetration of corrosion factors can be effectively prevented, the corrosion resistance of the coating is improved, and the prepared microcapsule can improve the intrinsic barrier property of the bio-based coating while endowing the coating with self-healing property.
(4) The bio-based surfactant used in the invention can improve the preparation efficiency and morphology of the bio-based microcapsule, and meanwhile, see patent CN115322613B.
(5) The bio-based healing agent in the single microcapsule cannot react alone and has no healing effect after release, so that the microcapsule A and the microcapsule B are required to be used in the coating simultaneously after being uniformly mixed. When the coating cracks, the microcapsules A, B break at the same time releasing the internally encapsulated bio-based cure and bio-based resin to react and heal the crack areas.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is an infrared spectrum of Ami-GO prepared in example 1.
Fig. 2 is an SEM photograph of the GO-modified cardanol curing agent microcapsule prepared in example 1.
Fig. 3 is a particle size distribution of the GO-modified cardanol curing agent microcapsule prepared in example 1.
Fig. 4 is an SEM photograph of the GO-modified cardanol epoxy resin microcapsule prepared in example 1.
Fig. 5 is a particle size distribution of the GO-modified cardanol epoxy resin microcapsule prepared in example 1.
Fig. 6 is a comparison of the "X" scratch healing before and after addition of the bio-based coatings of the two microcapsules of example 1.
Fig. 7 is a graph of electrochemical impedance Bode of bio-based coatings incorporating the two microcapsules of example 1.
Fig. 8 is an SEM photograph of the cardanol curing agent microcapsule prepared in comparative example 1.
Fig. 9 is a particle size distribution of cardanol curing agent microcapsules prepared in comparative example 1.
Fig. 10 is an SEM photograph of the cardanol epoxy resin microcapsule prepared in comparative example 1.
Fig. 11 is a particle size distribution of cardanol epoxy resin microcapsules prepared in comparative example 1.
Fig. 12 is a graph of electrochemical impedance Bode of a bio-based coating to which the cardanol curing agent microcapsules and cardanol resin microcapsules prepared in comparative example 1 were added.
Fig. 13 is a graph of electrochemical impedance Bode of a bio-based coating to which cardanol curative microcapsules and cardanol epoxy resin microcapsules prepared in comparative example 2 were added.
Detailed Description
The invention will be better understood from the following examples.
Polymethyl methacrylate, mw-195000, used in the examples of the present invention.
Example 1
Preparation of modified GO:
the preparation method of the GO (M-GO) grafted with amino molecules comprises the following steps: the preparation method can be referred to the work of Zhang Pengbo et al, L.Zhou, P.Zhang, L.Shen, L.Chu, J.Wu, Y.Ding, B.Zhong, X.Zhang, N.Bao, modified graphene oxide/waterborne epoxy composite coating with enhanced corrosion resistance, prog Org Coat 172 (2022) 107100, wherein the amino molecule in the GO grafted with the amino molecule is diamine maleate, and the GO grafted with the diamine maleate, namely M-GO, is synthesized.
The preparation method of the GO (E-GO) grafted with the bio-based epoxy resin comprises the following steps: the preparation method can refer to the work of Zhang Yingying et al, Y.Zhang, L.Chu, Z.Dai, N.Bao, M.B.de Rooij, L.Gao, W.Tan, L.Shen, synergistically enhancing the performance of cardanol-rich epoxy anticorrosive coatings using cardanol-based reactive diluent and its functionalized graphene oxide, prog Org Coat 171 (2022) 107060, and the GO, namely E-GO, of the grafted cardanol-based epoxy resin is synthesized.
The preparation method of the GO (Ami-GO) grafted with the bio-based curing agent comprises the following steps:
(i) Stripping a GO/DMF solution with a concentration of 1g/L in a flask by ultrasonic at 80 kHz;
(ii) Mixing a cardanol-based curing agent (PLR 718A), N' -Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and the GO/DMF solution obtained in the step (i), stirring at 80 ℃ for 24 hours, and obtaining a reaction solution after the reaction is finished; wherein, GO: PLR718A: DCC: the DMAP dose ratio was 50mg:1.5mmol:1.5mmol:1.5mmol.
(iii) Washing the reaction solution obtained in the step (ii) with ethanol for 5-6 times to obtain Ami-GO.
The infrared spectrum of Ami-GO is shown in FIG. 1, and the infrared spectrum of Ami-GO shows that GO is successfully grafted with cardanol-based curing agent 718A.
Preparation of GO modified cardanol curing agent microcapsules:
(1) 10g of cardanol surfactant (NSF 3007C) is added into 200g of deionized water, and stirred at normal temperature until the solid material is completely dissolved, so as to obtain an aqueous solution containing 5wt% of cardanol surfactant;
(2) 1g of cardanol curing agent (PLR 718A) and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 is added into 30mL of dichloromethane and stirred until the mixture is completely dissolved; then adding 3mL of ethanol mixed solution containing Ami-GO (the concentration of the Ami-GO in the mixed solution is 10 g/L), and carrying out ultrasonic treatment at room temperature and frequency of 80kHz for 15min until the solid materials are completely dispersed to obtain an oil phase;
(3) Adding 3mL of an M-GO-containing water mixed solution (the concentration of the M-GO in the mixed solution is 10 g/L) into 80mL of an aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, and carrying out ultrasonic treatment at room temperature for 15min at 80kHz until solid materials are completely dispersed to obtain a water phase;
(4) Slowly dripping the oil phase containing Ami-GO obtained in the step (2) into the water phase obtained in the step (3), and mechanically stirring for 15min at a rotating speed of 1000rpm to form emulsion;
(5) Pouring the emulsion obtained in the step (4) into 120mL of aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, stirring at 300rpm for 4h at 40 ℃ in an open mode, allowing methylene dichloride to completely volatilize, obtaining suspension of polymethyl methacrylate coated cardanol curing agent microcapsule, and obtaining GO modified cardanol curing agent microcapsule through centrifugation, washing and vacuum drying.
As shown in fig. 2, the GO-modified cardanol curing agent microcapsule is in a regular sphere shape, and modified GO sheets are embedded and wrapped on the outer surface of the microcapsule.
As shown in fig. 3, the average particle size of the GO-modified cardanol curative microcapsules was about 14 μm.
Preparation of GO modified cardanol epoxy resin microcapsules:
(1) 10g of cardanol surfactant (NSF 3007C) is added into 200g of deionized water, and stirred at normal temperature until the solid material is completely dissolved, so as to obtain an aqueous solution containing 5wt% of cardanol surfactant;
(2) 0.3g of cardanol glycidyl ether (PLR 602A) and 0.7g of epoxy resin (E51) were mixed to obtain a mixture; 1g of the mixture and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 is added into 30mL of dichloromethane and stirred until the mixture is completely dissolved; then adding 3mL of ethanol mixed solution containing E-GO (the concentration of E-GO in the mixed solution is 10 g/L), and carrying out ultrasonic treatment at room temperature and frequency of 80kHz for 15min until the solid materials are completely dispersed to obtain an oil phase;
(3) Adding 3mL of an M-GO-containing water mixed solution (the concentration of the M-GO in the mixed solution is 10 g/L) into 80mL of an aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, and carrying out ultrasonic treatment at room temperature for 15min at 80kHz until solid materials are completely dispersed to obtain a water phase;
(4) Slowly dripping the oil phase containing E-GO obtained in the step (2) into the water phase obtained in the step (3), and mechanically stirring for 15min at a rotating speed of 1000rpm to form emulsion;
(5) Pouring the emulsion obtained in the step (4) into 120mL of aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, stirring at 300rpm for 4h at 40 ℃ in an open mode, allowing methylene dichloride to volatilize completely, obtaining suspension of polymethyl methacrylate coated cardanol epoxy resin microcapsule, and obtaining GO modified cardanol epoxy resin microcapsule through centrifugation, washing and vacuum drying.
As shown in fig. 4, the GO-modified cardanol epoxy resin microcapsule is in a regular sphere shape, and a part of the modified GO sheet is wrapped on the outer surface of the microcapsule.
As shown in fig. 5, the average particle size of the GO-modified cardanol epoxy resin microcapsules was about 12 μm.
Preparation of self-repairing bio-based coating:
the substrate material is steel plate, the surface of the steel plate is polished to be smooth by 800-mesh sand paper, the surface is cleaned by ethanol, and the steel plate is naturally air-dried in the air. The GO modified cardanol curing agent microcapsule and the GO modified cardanol epoxy resin microcapsule prepared by the method are respectively added into cardanol paint according to the mixing amount of 10wt% (the mixing amount of the GO modified cardanol curing agent and the cardanol epoxy resin microcapsule is 1:1, and the mixing amount of the GO modified cardanol curing agent microcapsule and the cardanol epoxy resin microcapsule is 10 wt%) and uniformly stirred, and then the paint is coated on the surface of a steel plate by scraping, and the self-repairing coating is obtained after the paint is cured for 24 hours at room temperature.
As shown in fig. 6, the bio-based coating with 10wt% of the go-modified cardanol curing agent microcapsule and 10wt% of the go-modified cardanol epoxy resin microcapsule added thereto produced an "X" scratch on the surface, which was almost completely disappeared after self-healing for 24 hours at room temperature.
As shown in fig. 7, the Bode plot showed a decrease in low frequency impedance to 5.51x10 after the bio-based coating added with 10wt% go modified cardanol curative microcapsules and 10wt% go modified cardanol epoxy resin microcapsules was immersed in 3.5wt% nacl solution for 30 days 9 Ω·cm -1 Nearby, it is indicated that brine has entered the coating, but has not yet contacted the substrate. Compared with the microcapsules which are not modified in the comparative examples 1 and 2, the low-frequency impedance value of the coating is greatly improved, and the corrosion resistance is greatly enhanced.
Comparative example 1: no addition of modified GO
Preparation of cardanol curing agent microcapsules:
(1) 10g of cardanol surfactant (NSF 3007C) is added into 200g of deionized water, and stirred at normal temperature until the solid material is completely dissolved, so as to obtain an aqueous solution containing 5wt% of cardanol surfactant;
(2) 1g of cardanol curing agent (PLR 718A) and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 adding the mixture into 30mL of dichloromethane, and stirring until the mixture is completely dissolved to obtain an oil phase;
(3) Slowly adding the oil phase obtained in the step (2) into 80mL of aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, and mechanically stirring at 1000rpm for 15min to form emulsion;
(4) Pouring the emulsion obtained in the step (3) into 120mL of aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, stirring at 300rpm for 4 hours at 40 ℃ in an open mode, allowing methylene dichloride to completely volatilize, obtaining suspension of polymethyl methacrylate coated cardanol curing agent microcapsule, and obtaining the cardanol curing agent microcapsule through centrifugation, washing and vacuum drying.
As shown in fig. 8, the cardanol curing agent microcapsules are in regular spherical shape, and have smooth surfaces without holes and depressions.
As shown in FIG. 9, the cardanol curing agent microcapsules had an average particle size of about 9.8. Mu.m.
Preparation of cardanol epoxy resin microcapsules:
(1) 10g of cardanol surfactant (NSF 3007C) is added into 200g of deionized water, and stirred at normal temperature until the solid material is completely dissolved, so as to obtain an aqueous solution containing 5wt% of cardanol surfactant;
(2) 0.3g of cardanol diluent (PLR 602A) and 0.7g of epoxy resin (E51) were mixed to obtain a mixture; 1g of the mixture and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 adding the mixture into 30mL of dichloromethane, and stirring until the mixture is completely dissolved to obtain an oil phase;
(3) Slowly adding the oil phase obtained in the step (2) into 80mL of aqueous solution (prepared in the step (1)) containing 5wt% of anionic cardanol surfactant, and mechanically stirring at 1000rpm for 15min to form emulsion;
(4) Pouring the emulsion obtained in the step (3) into 120mL of aqueous solution (prepared in the step (1)) containing 5wt% of cardanol surfactant, stirring at 300rpm for 4 hours at 40 ℃ in an open mode, allowing methylene dichloride to volatilize completely, obtaining suspension of polymethyl methacrylate coated cardanol epoxy resin microcapsule, and obtaining the cardanol epoxy resin microcapsule through centrifugation, washing and vacuum drying.
As shown in fig. 10, the cardanol epoxy resin microcapsule has a regular sphere shape, and has a smooth surface without holes and depressions.
As shown in FIG. 11, the average particle size of the cardanol epoxy resin microcapsules was about 8.9 μm.
Preparation of self-repairing bio-based coating:
the substrate material is steel plate, the surface of the steel plate is polished to be smooth by 800-mesh sand paper, the surface is cleaned by ethanol, and the steel plate is naturally air-dried in the air. And respectively adding 10wt% (the mixing amount of the cardanol curing agent and the cardanol epoxy resin microcapsule is 1:1, and the mixing amount of the cardanol curing agent and the cardanol epoxy resin microcapsule is 10 wt%) into the cardanol-based coating, uniformly stirring, then scraping the coating on the surface of a steel plate, and curing at room temperature for 24 hours to obtain the self-repairing coating.
As shown in FIG. 12, the bio-based coating with 10wt% cardanol curing agent (unmodified GO) and 10wt% GO cardanol epoxy resin microcapsule (unmodified GO) added with NSF3007C as emulsifier, after soaking in 3.5wt% NaCl solution for 30 days, the Bode plot showed a decrease in resistance to 1.1X10 7 Near Ω cm-1, it is shown that brine has entered the coating, but the corrosion resistance is improved to some extent compared to the microcapsules of comparative example 2 in which the petroleum-based surfactant was used as the emulsifier.
Comparative example 2: without addition of modified GO and use of petroleum-based surfactants as emulsifiers
Preparation of cardanol curing agent microcapsules:
(1) Adding 10g of petroleum-based surfactant (PVA) into 200g of deionized water, and stirring at normal temperature until the solid material is completely dissolved to obtain an aqueous solution containing 5wt% of PVA;
(2) 1g of cardanol curing agent (PLR 718A) and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 adding the mixture into 30mL of dichloromethane, and stirring until the mixture is completely dissolved to obtain an oil phase;
(3) Slowly adding the oil phase obtained in the step (2) into 80mL of aqueous solution containing 5wt% PVA (prepared in the step (1)) and mechanically stirring at 1000rpm for 15min to form emulsion;
(4) Pouring the emulsion obtained in the step (3) into 120mL of aqueous solution containing 5wt% of PVA (prepared in the step (1)), stirring at 300rpm for 4 hours at 40 ℃ in an open mode, allowing methylene dichloride to volatilize completely to obtain suspension of polymethyl methacrylate coated cardanol curing agent microcapsule, and obtaining the cardanol curing agent microcapsule with an average particle size of about 10.5 mu m through centrifugation, washing and vacuum drying.
Preparation of cardanol epoxy resin microcapsules:
(1) Adding 10g of petroleum-based surfactant (PVA) into 200g of deionized water, and stirring at normal temperature until the solid material is completely dissolved to obtain an aqueous solution containing 5wt% of PVA;
(2) 0.3g of cardanol diluent (PLR 602A) and 0.7g of epoxy resin (E51) were mixed to obtain a mixture; 1g of the mixture and 1g of polymethyl methacrylate are mixed according to the mass ratio of 1:1 adding the mixture into 30mL of dichloromethane, and stirring until the mixture is completely dissolved to obtain an oil phase;
(3) Slowly adding the oil phase obtained in the step (2) into 80mL of aqueous solution containing 5wt% PVA (prepared in the step (1)) and mechanically stirring at 1000rpm for 15min to form emulsion;
(4) Pouring the emulsion obtained in the step (3) into 120mL of aqueous solution containing 5wt% of PVA (prepared in the step (1)), stirring at 300rpm for 4 hours at 40 ℃ in an open mode, allowing methylene dichloride to volatilize completely, obtaining suspension of polymethyl methacrylate coated cardanol epoxy resin microcapsules, and obtaining the cardanol epoxy resin microcapsules with an average particle size of 11 mu m through centrifugation, washing and vacuum drying.
Preparation of self-repairing bio-based coating:
the substrate material is steel plate, the surface of the steel plate is polished to be smooth by 800-mesh sand paper, the surface is cleaned by ethanol, and the steel plate is naturally air-dried in the air. And adding the prepared cardanol curing agent microcapsule and cardanol epoxy resin microcapsule into the cardanol-based coating according to 10wt% (the mixing amount of the curing agent and the resin microcapsule is 1:1, and the adding amount of the curing agent and the resin microcapsule is 10 wt%) respectively, stirring uniformly, then scraping the coating on the surface of a steel plate, and curing at room temperature for 24 hours to obtain the self-repairing coating.
As shown in FIG. 13, the bio-based coating of cardanol curing agent microcapsule with PVA as an emulsifier and cardanol epoxy resin microcapsule with PVA as an emulsifier was added at 10wt%, and after soaking in 3.5wt% NaCl solution for 30 days, the Bode plot showed a decrease in resistance to 5.2X10 6 Ω·cm -1 Nearby, it is indicated that brine has entered the coating, which breaks down by the corrosive medium and loses its corrosion protection ability.
Comparative example 3: adding unmodified GO
The preparation of bio-based curing agent microcapsules/bio-based epoxy resin preparation microcapsules by adding unmodified graphene oxide is attempted, and effective encapsulation of the surface of the microcapsules with the same electronegativity (due to the existence of a surfactant) is difficult to realize due to the electronegativity of the surface of the unmodified GO, so that the unmodified GO encapsulated microcapsules are not successfully prepared.
The invention provides a graphene oxide modified bio-based microcapsule, a preparation method and an application thought and method thereof, and particularly the method and the method for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made to those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (11)
1. The graphene oxide modified bio-based microcapsule is characterized in that the bio-based microcapsule is microcapsule A and/or microcapsule B; the microcapsule A and the microcapsule B comprise a capsule wall, a capsule core and a capsule wall outer wrapping layer; the microcapsule A and the microcapsule B are the same in capsule wall material, the microcapsule A and the microcapsule B are the same in capsule wall outer wrapping material, and the microcapsule A and the microcapsule B are different in capsule core material;
the material of the capsule wall comprises polymethyl methacrylate, polysulfone or polylactic acid;
the material of the capsule wall outer cladding comprises a bio-based surfactant and GO grafted with amino molecules;
the microcapsule A comprises a core material and a composite of GO grafted with a bio-based curing agent;
the microcapsule B comprises a core material of a composition of bio-based epoxy resin and GO grafted with the bio-based epoxy resin.
2. The bio-based microcapsule according to claim 1, wherein the bio-based surfactant is any one of cardanol-based surfactant, castor oil-based surfactant and soybean oil-based surfactant; the amino molecules in the GO grafted with the amino molecules are maleic acid diamine or p-phenylenediamine; the bio-based curing agent is any one of a cardanol-based curing agent, a castor oil-based curing agent and a soybean oil-based curing agent; the bio-based epoxy resin is prepared by compounding any one of cardanol-based glycidyl ether, castor oil-based glycidyl ether and soybean oil-based glycidyl ether with epoxy resin according to any proportion.
3. The biobased microcapsule according to claim 1, wherein the mass ratio of biobased curing agent to grafted biobased curing agent GO in the core material is 1:0.01 to 0.03; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin in the capsule core material is 1:0.01 to 0.03; the mass ratio of the bio-based surfactant to the grafted amino molecules in the outer cladding of the capsule wall is 10:0.01 to 0.03; the mass ratio of the capsule wall to the capsule core to the capsule wall outer cladding is 1-2: 1.01 to 1.03:10.01 to 10.03; the particle size of the microcapsule is 5-30 microns.
4. A method for preparing a bio-based microcapsule according to any one of claims 1 to 3, comprising the steps of:
(1) Adding a biological-based surfactant into water serving as a solvent, and stirring until the solid materials are completely dissolved to obtain an emulsifier aqueous solution;
(2) Dissolving a bio-based curing agent and a material of the capsule wall in dichloromethane, then adding GO grafted with the bio-based curing agent, and performing ultrasonic dispersion to obtain an oil phase; or dissolving the bio-based epoxy resin and the material of the capsule wall in dichloromethane, then adding GO grafted with the bio-based epoxy resin, and performing ultrasonic dispersion to obtain an oil phase;
(3) Adding GO grafted with amino molecules into part of the emulsifier aqueous solution obtained in the step (1), and performing ultrasonic dispersion to obtain a water phase;
(4) Adding the oil phase obtained in the step (2) into the water phase obtained in the step (3), and stirring and mixing uniformly to form emulsion;
(5) Adding the emulsion obtained in the step (4) into the water solution of the emulsifier obtained in the rest step (1), stirring for reaction, and after the reaction is finished, carrying out aftertreatment on the reaction solution to obtain the graphene oxide modified bio-based microcapsule.
5. The method according to claim 4, wherein in the step (1), the mass ratio of the bio-based surfactant to water is 1 to 5:100; the mass ratio of the bio-based surfactant to the GO of the grafted amino molecule is 10:0.01 to 0.03.
6. The preparation method of claim 4, wherein the GO grafted bio-based curing agent exists in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO grafted bio-based curing agent in the mixed solution is 5-10 g/L; the GO grafted bio-based epoxy resin exists in the form of a mixed solution, the solvent in the mixed solution is ethanol, and the concentration of the GO grafted bio-based epoxy resin in the mixed solution is 5-10 g/L; the GO grafted amino molecules exist in the form of a mixed solution, the solvent in the mixed solution is water, and the concentration of the GO grafted amino molecules in the mixed solution is 5-10 g/L; the ultrasonic dispersion is carried out, the ultrasonic temperature is room temperature, and the ultrasonic frequency is 30-80 kHz.
7. The method according to claim 4, wherein in the step (2), the mass ratio of the bio-based curing agent to the capsule wall material is 1:1 to 2; the mass volume ratio of the bio-based curing agent to the dichloromethane is 1g:30 mL-50 mL; the mass ratio of the bio-based curing agent to the GO grafted bio-based curing agent is 1:0.01 to 0.03; the mass ratio of the bio-based epoxy resin to the capsule wall material is 1:1 to 2; the mass volume ratio of the bio-based epoxy resin to the dichloromethane is 1g:30 mL-50 mL; the mass ratio of the bio-based epoxy resin to the GO grafted with the bio-based epoxy resin is 1:0.01 to 0.03.
8. The method of claim 4, wherein in step (3), the amount of the aqueous emulsifier solution obtained in step (1) is calculated according to the following ratio: the mass volume ratio of the GO grafted with the amino molecules to the emulsifier aqueous solution is 0.01 g-0.03 g:80mL.
9. The method according to claim 4, wherein in the step (4), the mass ratio of the wall material in the oil phase to the GO grafted with the amino molecules in the water phase is 1-2: 0.01 to 0.03; the stirring is carried out uniformly, the stirring speed is 1000-2000 r/min, and the stirring time is 10-15 min.
10. The process according to claim 4, wherein in step (5), the stirring reaction is carried out at a stirring temperature of 30 to 50℃for 3 to 5 hours at a stirring rate of 300 to 500r/min.
11. The application of the graphene oxide modified biobased microcapsule in preparing a self-healing biobased coating according to any one of claims 1-3, wherein the microcapsule A and the microcapsule B are uniformly stirred, dispersed and mixed with the biobased coating to obtain the self-healing biobased coating; wherein the bio-based coating is cardanol coating, castor oil coating or soybean oil epoxy resin coating; the total mass of the microcapsule A and the microcapsule B in the self-healing bio-based coating is 5-20wt%; the mass ratio of the microcapsule A to the microcapsule B is 1-2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310444373.7A CN116393057A (en) | 2023-04-24 | 2023-04-24 | Graphene oxide modified bio-based microcapsule and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310444373.7A CN116393057A (en) | 2023-04-24 | 2023-04-24 | Graphene oxide modified bio-based microcapsule and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116393057A true CN116393057A (en) | 2023-07-07 |
Family
ID=87008939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310444373.7A Pending CN116393057A (en) | 2023-04-24 | 2023-04-24 | Graphene oxide modified bio-based microcapsule and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116393057A (en) |
-
2023
- 2023-04-24 CN CN202310444373.7A patent/CN116393057A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110835488B (en) | Coating based on graphene nano container, self-repairing coating and preparation method and application thereof | |
| CN112961526B (en) | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule | |
| CN109943202B (en) | Water-based epoxy nanofiber heavy-duty anticorrosive paint and preparation method thereof | |
| CN113980553A (en) | Self-repairing water-based anticorrosive coating, preparation method and application thereof | |
| JP2014530954A (en) | Corrosion, chip and fuel oil resistant compositions | |
| CN111808468A (en) | Small-size urea formaldehyde microcapsule, preparation and application in self-repairing coating | |
| CN115044279B (en) | Two-dimensional polydopamine reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof | |
| JP4536322B2 (en) | Low density sealing material, basic material and method for producing and using the same | |
| CN116393057A (en) | Graphene oxide modified bio-based microcapsule and preparation method and application thereof | |
| CN114539877A (en) | Anti-corrosion water-based epoxy coating based on divalent zinc ions and phytic acid modified graphene oxide and preparation method thereof | |
| CN113321985A (en) | PH stimulus response intelligent repair coating and preparation method thereof | |
| CN116640499B (en) | Polyurea waterproof composition and preparation method thereof | |
| CN112980296A (en) | MPA/KH567/rGO reinforced waterborne epoxy amino baking paint and preparation method thereof | |
| CN115948067B (en) | Functional filler, self-repairing anticorrosive paint and preparation method | |
| CN116814111A (en) | Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof | |
| KR102635964B1 (en) | Polymer dispersions and methods for making them | |
| CN114410190B (en) | Dual-functional microcapsule self-repairing anti-corrosion coating material, preparation method and coating | |
| CN101235238B (en) | Environmental protection dope and its preparation method | |
| CN113278318B (en) | Fiber and/or scale reinforced self-repairing anticorrosive coating and preparation method and application thereof | |
| JP2007216072A (en) | Asbestos treatment agent | |
| CN115322613B (en) | Bio-based microcapsule and preparation method and application thereof | |
| Kudryavtsev et al. | Advance in nanocomposites based on hybrid organo-silicate matrix | |
| CN107383994B (en) | Microencapsulated barium sulfate for improving boiling resistance of powder coating and preparation method thereof | |
| CN115888575A (en) | Method for synthesizing microcapsule in situ by enzyme catalysis and application of microcapsule in anticorrosive paint | |
| CN116334925B (en) | Impact-resistant coating for impact-resistant forming net, preparation method and coating 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 |