CN113058510B - Hybrid self-repairing microcapsule and preparation method thereof - Google Patents
Hybrid self-repairing microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of self-repairing microcapsule particles, in particular to a hybrid self-repairing microcapsule and a preparation method thereof. The method comprises the following steps: 1) adding urea, ammonium chloride and resorcinol into an emulsifier aqueous solution to obtain a mixed solution; 2) adding a self-repairing agent and a polyurethane prepolymer into the mixed solution to obtain an oil-in-water emulsion; 3) adding formaldehyde solution into the oil-in-water emulsion, and heating for reaction; adding imidazole-2-formaldehyde aqueous solution, and continuously reacting to obtain self-repairing microcapsules with surfaces modified by imidazole groups; 4) and re-dispersing the self-repairing microcapsule in an aqueous solution of an imidazole organic ligand, adding an aqueous solution of zinc salt, organic amine and a water-soluble corrosion inhibitor, and stirring to obtain the hybrid self-repairing microcapsule. The repairing agent coated by the self-repairing microcapsule is a reaction type repairing agent, and when the microcapsule is broken, the repairing agent flows out and fills microcracks, so that the self-repairing of the coating is realized.
Description
Technical Field
The invention relates to the technical field of self-repairing microcapsule particles, in particular to a hybrid self-repairing microcapsule and a preparation method thereof.
Background
Inspired by nature, the self-repairing microcapsule technology leads the interior of the material to form a bionic self-healing system by compounding microcapsules in the traditional matrix material in advance, and carries out targeted repair on cracks. The technical method is simple and convenient, does not need secondary maintenance, can greatly reduce the engineering maintenance cost, and has important significance for eliminating material damage caused by microcracks and prolonging the service life. Self-healing microcapsule technology provides a good solution to corrosion of metal substrates caused by coating microcracks. For example, patent application 201711424463.0 discloses an antiseptic primer containing self-repairing microcapsules, wherein when the microcapsules are damaged, the repairing liquid coated in the microcapsules automatically flows out, so that the self-repairing of the primer is realized. In order to improve the stability and self-repairing anticorrosion capability of the microcapsules, microcapsules with a multi-layer or special wall structure are recently used in an anticorrosion coating. For example, patent application CN201710501268 discloses a microcapsule with double-layer capsule walls and a corrosion inhibitor loaded between the capsule walls, in patent application CN201910353608.5, conductive polyaniline is used as a microcapsule wall material, so that the corrosion resistance of the microcapsule is further improved, and patent application CN201910856507.x discloses a self-repairing microcapsule with a calcium carbonate/polyaniline double-layer capsule wall structure.
The microcapsules can release the repairing agent after responding to mechanical rupture, and have no environmental responsiveness. Patent application CN111234566A discloses an acid-base pH-responsive composite silica nanocontainer, which improves the compatibility with a coating and enhances the self-repairing and anti-corrosion capability of the coating. However, at present, no microcapsule which has pH responsiveness, strong capsule wall structural stability and mechanical strength, and can release a repairing agent to fill microcracks and realize self-repairing exists.
Disclosure of Invention
Based on the defects, the invention provides a hybrid self-repairing microcapsule and a preparation method thereof. The microcapsule has a multilayer hybrid capsule wall structure, is more stable in capsule wall structure, can respond to environmental changes and crack propagation damage, and plays a role in repairing.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a hybrid self-repairing microcapsule which comprises a core material and a wall material, wherein the core material is a self-repairing agent, the wall material is a three-layer composite hybrid wall material, and the wall material sequentially comprises polyurethane, polyurea formaldehyde and a Metal Organic Framework (MOF) from inside to outside. The grain size range of the hybrid self-repairing microcapsule is 5-500 microns, and the grain size range of the MOF grains is 0.01-1 micron.
When the microenvironment around the hybrid microcapsule is acidic, the MOF on the surface of the microcapsule is decomposed, the released imidazole compound can play a role in corrosion inhibition, and when the microcapsule is further damaged, the reactive repairing agent in the microcapsule is released to fill microcracks, so that the corrosion is further prevented. In addition, the MOF on the surface of the microcapsule can also improve the structural stability of the microcapsule wall.
The invention also provides a preparation method of the hybrid self-repairing microcapsule, which comprises the following steps in parts by mass:
1) adding 2.5-50 parts of urea, 0.25-5 parts of ammonium chloride and 0.25-5 parts of resorcinol into 50-200 parts of emulsifier aqueous solution with the mass fraction of 1-10 wt% to obtain a mixed solution, and adjusting the pH of the mixed solution to 2.0-4.0;
2) adding 10-30 parts of self-repairing agent and 2-10 parts of polyurethane prepolymer into the mixed solution obtained in the step 1), and emulsifying at a stirring speed of 500-1200 rpm for 10-30 min to obtain an oil-in-water emulsion;
3) adding 3-10 parts of formaldehyde solution into the oil-in-water emulsion obtained in the step 2), and heating to 45-65 ℃ to react for 1-3 h; adding 0-5 parts of imidazole-2-formaldehyde aqueous solution with the pH value of 2.0-4.5, and continuously reacting for 1-3 h; further preferably adding 1.5-5 parts of imidazole-2-formaldehyde; after the reaction is finished, centrifuging at 1000-2000 rpm, washing, and repeating for 3-5 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group;
4) re-dispersing the self-repairing microcapsule obtained in the step 3) in an aqueous solution of an imidazole organic ligand, adding an aqueous solution of zinc salt, organic amine and a water-soluble corrosion inhibitor, stirring for 0.5-2 h, centrifuging at 1000-2000 rpm after the reaction is finished, washing, repeating for 3-5 times, and drying in vacuum to obtain the hybrid self-repairing microcapsule.
Preferably, in the step 1), the emulsifier includes one or more of gum arabic, polyvinyl alcohol, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, ethylene-maleic anhydride copolymer and styrene-maleic anhydride copolymer.
Preferably, in the step 2), the self-repairing agent is selected from a reactive self-repairing agent, and the reactive self-repairing agent comprises one or more of isocyanate, epoxy resin and siloxane;
the polyurethane prepolymer comprises one or more than two of toluene diisocyanate prepolymer, hexamethylene diisocyanate prepolymer, diphenylmethane diisocyanate prepolymer, dicyclohexylmethane diisocyanate prepolymer and isophorone diisocyanate prepolymer.
Preferably, the organic amine in the step 4) is triethylamine and/or ammonia water;
the mass ratio of the imidazole group modified self-repairing microcapsule to the zinc salt is 1: 1-10, wherein the molar ratio of zinc salt, imidazole organic ligand, organic amine, water-soluble corrosion inhibitor and water is 1: 2-100: 0 to 32: 0-5: 120-2255; further preferably, the molar ratio of zinc salt, imidazole organic ligand, organic amine, water-soluble corrosion inhibitor and water is 1: 2-100: 10-32: 2-5: 120 to 2255;
wherein the imidazole organic ligand comprises 2-methylimidazole and/or imidazole-2-formaldehyde;
the zinc salt comprises one or more of zinc nitrate hexahydrate, zinc chloride, zinc sulfate, zinc acetate and zinc gluconate;
the water-soluble corrosion inhibitor comprises one or more than two of benzotriazole, 2-mercaptobenzothiazole and waterborne imidazoline corrosion inhibitors.
Compared with the prior art, the invention has the following beneficial effects:
1. the hybrid self-repairing microcapsule provided by the invention has a polyurethane/polyurea organic capsule wall layer and an MOF (metal organic framework) capsule wall layer. The hard nano-particle layer endows the microcapsule with stronger structural stability, mechanical strength and structural compactness;
2. the MOF capsule wall layer has pH responsiveness, and under an acidic corrosion microenvironment, MOF is decomposed to release imidazole organic ligands, loaded water-soluble corrosion inhibitors and metal ions, so that a corrosion inhibition effect is achieved, and further spread of corrosion at a damaged part is prevented;
3. the repairing agent coated by the self-repairing microcapsule is a reactive repairing agent, when the microcapsule is broken, the repairing agent flows out and fills microcracks, a new polymer is formed along with the occurrence of polymerization reaction, and the self-repairing of a coating is realized;
4. the solvent used for preparing the hybrid microcapsule is water, and the organic solvent is not involved, so that the hybrid microcapsule is more environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope image of the hybrid self-repairing microcapsule prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the surface of the hybrid self-repairing microcapsule prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the hybrid self-healing microcapsules prepared in example 1 of the present invention;
FIG. 4 is a diagram showing the self-repairing effect of the hybrid self-repairing microcapsule prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
Adding 2.5g of urea, 0.25g of ammonium chloride and 0.25g of resorcinol into 90g of a gum arabic aqueous solution with the mass fraction of 10wt%, and adjusting the pH of the mixed solution to 3.5; adding a mixed solution of 18g of self-repairing agent isophorone diisocyanate and 4g of toluene diisocyanate prepolymer into the mixed solution, and emulsifying for 30min at a stirring speed of 1100 r/min to obtain an oil-in-water emulsion; adding 4g of formaldehyde solution into the oil-in-water emulsion, and heating to 55 ℃ to react for 1 h; adding 1.3g of imidazole-2-formaldehyde aqueous solution with the pH value of 3.5 into the reaction solution, and continuing the reaction for 2 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in a 2-methylimidazole aqueous solution, and adding the microcapsules into a zinc nitrate hexahydrate aqueous solution after uniform dispersion. Wherein the mass ratio of the self-repairing microcapsule to the zinc nitrate hexahydrate is 1: 2, zinc nitrate hexahydrate: 2-methylimidazole: benzotriazole: the molar ratio of the deionized water is 1: 100: 5: 2228, stirring for 0.5h, centrifuging after the reaction is finished, washing, repeating for 3 times, and vacuum drying to obtain the hybrid self-repairing microcapsule, as shown in fig. 1-4.
Example 2
Adding 2.5g of urea, 0.25g of ammonium chloride and 0.25g of resorcinol into 50g of a styrene-maleic anhydride copolymer aqueous solution with the mass fraction of 5 wt%, and adjusting the pH value of the mixed solution to 4; adding a mixed solution of 4.5g of self-repairing agent epoxy resin and 4g of toluene diisocyanate prepolymer into the mixed solution, and emulsifying for 10min at a stirring speed of 900 revolutions per minute to obtain an oil-in-water emulsion; adding 4g of formaldehyde solution into the oil-in-water emulsion, and heating to 55 ℃ to react for 3 h; adding 0.6g of imidazole-2-formaldehyde aqueous solution with the pH value of 4 into the reaction solution, and continuing the reaction for 2 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in the 2-methylimidazole aqueous solution, and adding a zinc nitrate hexahydrate aqueous solution after uniform dispersion. Wherein the mass ratio of the self-repairing microcapsule to the zinc nitrate hexahydrate is 1: 10, zinc nitrate hexahydrate: 2-methylimidazole: ammonia water: benzotriazole: the molar ratio of the deionized water is 1: 2: 16: 2: 157 stirring for 0.5h, centrifuging, washing after the reaction is finished, repeating for 3 times, and drying in vacuum to obtain the hybrid self-repairing microcapsule.
Example 3
Adding 50g of urea, 5g of ammonium chloride and 5g of resorcinol into 200g of a sodium dodecyl sulfate aqueous solution with the mass fraction of 5 wt%, and adjusting the pH value of the mixed solution to 3; adding a mixed solution of 30g of self-repairing agent siloxane and 10g of diphenylmethane diisocyanate prepolymer into the mixed solution, and emulsifying for 30min at a stirring speed of 700 revolutions per minute to obtain an oil-in-water emulsion; adding 10g of formaldehyde solution into the oil-in-water emulsion, and heating to 55 ℃ to react for 3 h; adding 4g of imidazole-2-formaldehyde aqueous solution into the reaction solution, and continuing to react for 3 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in an imidazole-2-formaldehyde aqueous solution, and adding a zinc acetate aqueous solution after uniform dispersion. Wherein the mass ratio of the self-repairing microcapsule to the zinc nitrate hexahydrate is 1: 5, zinc acetate: imidazole-2-carbaldehyde: aqueous imidazoline corrosion inhibitors: the molar ratio of the deionized water is 1: 4: 0.8: 120, stirring for 0.5h, centrifuging, washing after the reaction is finished, repeating for 3 times, and drying in vacuum to obtain the hybrid self-repairing microcapsule.
Example 4
Adding 2.5g of urea, 0.25g of ammonium chloride and 0.25g of resorcinol into 100g of polyvinyl alcohol aqueous solution with the mass fraction of 3 wt%, and adjusting the pH value of the mixed solution to 2.5; adding a mixed solution of 10g of self-repairing agent isophorone diisocyanate and 2g of hexamethylene diisocyanate prepolymer into the mixed solution, and emulsifying for 30min at a stirring speed of 500 revolutions per minute to obtain an oil-in-water emulsion; adding 3g of formaldehyde solution into the oil-in-water emulsion, and heating to 55 ℃ to react for 3 h; adding 1.5g of imidazole-2-formaldehyde aqueous solution with the pH value of 4 into the reaction solution, and continuing the reaction for 2 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in the 2-methylimidazole aqueous solution, and adding a zinc nitrate hexahydrate aqueous solution after uniform dispersion. Wherein the mass ratio of the microcapsule to the zinc nitrate hexahydrate is 1: 5, zinc nitrate hexahydrate: 2-methylimidazole: triethylamine: the molar ratio of the deionized water is 1: 16: 16: 2255, stirring for 0.5h, centrifuging after the reaction is finished, washing, repeating for 3 times, and vacuum drying to obtain the hybrid self-repairing microcapsule.
Example 5
Adding 2.5g of urea, 0.25g of ammonium chloride and 0.25g of resorcinol into 100g of a sodium dodecyl sulfate aqueous solution with the mass fraction of 1wt%, and adjusting the pH value of the mixed solution to 2.5; adding a mixed solution of 10g of self-repairing agent dicyclohexylmethane diisocyanate and 2g of hexamethylene diisocyanate prepolymer into the mixed solution, and emulsifying for 30min at a stirring speed of 500 revolutions per minute to obtain an oil-in-water emulsion; adding 3g of formaldehyde solution into the emulsion, and heating to 55 ℃ to react for 3 h; adding 1.5g of imidazole-2-formaldehyde aqueous solution with the pH value of 4 into the reaction solution, and continuing the reaction for 2 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in an imidazole-2-formaldehyde aqueous solution, and adding a zinc nitrate hexahydrate aqueous solution after uniform dispersion. Wherein the mass ratio of the self-repairing microcapsule to the zinc nitrate hexahydrate is 1: 5, zinc nitrate hexahydrate: imidazole-2-carbaldehyde: triethylamine: the molar ratio of the deionized water is 1: 16: 16: 2255, stirring for 0.5h, centrifuging after the reaction is finished, washing, repeating for 3 times, and drying in vacuum to obtain the hybrid self-repairing microcapsule.
Example 6
Adding 1.5g of urea, 0.15g of ammonium chloride and 0.15g of resorcinol into 80g of a gum arabic aqueous solution with the mass fraction of 5 wt%, and adjusting the pH of the mixed solution to 3.5; adding a mixed solution of 5g of self-repairing agent hexamethylene diisocyanate and 1g of isophorone diisocyanate prepolymer into the mixed solution, and emulsifying at a stirring speed of 1000 revolutions per minute for 20min to obtain an oil-in-water emulsion; adding 3g of formaldehyde solution into the emulsion, and heating to 55 ℃ to react for 4 hours; after the reaction is finished, centrifuging, washing and repeating for 3 times to obtain the self-repairing microcapsule with the surface modified by the imidazole group; and re-dispersing the obtained microcapsules in a 2-methylimidazole aqueous solution, and adding a zinc sulfate aqueous solution after uniform dispersion. Wherein the mass ratio of the self-repairing microcapsule to the zinc sulfate is 1: 1, zinc sulfate: 2-methylimidazole: the molar ratio of the deionized water is 1: 70: 1238, stirring for 0.5h, centrifuging after the reaction is finished, washing, repeating for 3 times, and drying in vacuum to obtain the hybrid self-repairing microcapsule.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of a hybrid self-repairing microcapsule comprises the following steps of:
1) adding 2.5-50 parts of urea, 0.25-5 parts of ammonium chloride and 0.25-5 parts of resorcinol into 50-200 parts of emulsifier aqueous solution with the mass fraction of 1-10 wt% to obtain a mixed solution, and adjusting the pH of the mixed solution to 2.5-4.0;
2) adding 10-30 parts of self-repairing agent and 2-10 parts of polyurethane prepolymer into the mixed solution obtained in the step 1), and then stirring and emulsifying for 10-30 minutes to obtain an oil-in-water emulsion;
3) adding 3-10 parts of formaldehyde solution into the oil-in-water emulsion obtained in the step 2), and heating to 45-65 ℃ to react for 1-4 h; adding 0.6-5 parts of imidazole-2-formaldehyde aqueous solution with the pH value of 2.0-4.5, continuously reacting for 1-3 hours, centrifuging after the reaction is finished, and washing to obtain a self-repairing microcapsule with the surface modified by imidazole groups, wherein the self-repairing agent comprises one or more than two of isocyanate, epoxy resin and siloxane;
the polyurethane prepolymer comprises one or more than two of toluene diisocyanate prepolymer, hexamethylene diisocyanate prepolymer, diphenylmethane diisocyanate prepolymer, dicyclohexylmethane diisocyanate prepolymer and isophorone diisocyanate prepolymer;
4) re-dispersing the self-repairing microcapsule obtained in the step 3) in an aqueous solution of an imidazole organic ligand, adding an aqueous solution of zinc salt, organic amine and a water-soluble corrosion inhibitor, stirring for 0.5-2 h, centrifuging after the reaction is finished, washing, and drying to obtain a hybrid self-repairing microcapsule, wherein the mass ratio of the imidazole group modified self-repairing microcapsule to the zinc salt is 1: 1-10, wherein the molar ratio of zinc salt, imidazole organic ligand, organic amine, water-soluble corrosion inhibitor and water is 1: 2-100: 10-32: 2-5: 120 to 2255; wherein the water-soluble corrosion inhibitor comprises one or more than two of benzotriazole, 2-mercaptobenzothiazole and waterborne imidazoline corrosion inhibitors;
the hybrid self-repairing microcapsule comprises a core material and a wall material, wherein the core material is a self-repairing agent, the wall material is a three-layer composite hybrid wall material, and the three-layer composite hybrid wall material sequentially comprises polyurethane, polyureaformaldehyde and a metal organic framework from inside to outside.
2. The method for preparing hybrid self-repairing microcapsules according to claim 1, wherein in the step 1), the emulsifier comprises one or more of gum arabic, polyvinyl alcohol, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, ethylene-maleic anhydride copolymer and styrene-maleic anhydride.
3. The preparation method of hybrid self-repairing microcapsules according to claim 1, wherein the organic amine in the step 4) is triethylamine.
4. The preparation method of hybrid self-repairing microcapsules according to claim 1, wherein the imidazole organic ligand in step 4) is 2-methylimidazole and/or imidazole-2-formaldehyde.
5. The preparation method of hybrid self-repairing microcapsules according to claim 1, wherein the zinc salt in step 4) is one or more of zinc nitrate hexahydrate, zinc chloride, zinc sulfate, zinc acetate and zinc gluconate.
6. A hybrid self-repairing microcapsule, which is prepared by the preparation method of any one of claims 1 to 5.
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| CN113463397B (en) * | 2021-07-27 | 2022-04-08 | 哈尔滨工业大学 | Self-repairing epoxy resin and preparation method of self-repairing epoxy resin/carbon fiber composite material |
| CN115010400A (en) * | 2022-05-17 | 2022-09-06 | 南昌大学 | Chlorine fixing-self-healing synergistic corrosion-resistant microcapsule and preparation method thereof |
| CN116426203B (en) * | 2023-04-11 | 2024-05-14 | 滨州学院 | Building surface coating material and preparation method and application thereof |
| CN116376385A (en) * | 2023-04-11 | 2023-07-04 | 浙江驭能新材料科技有限公司 | Self-repairing coating applied to TPU car coating film and preparation method thereof |
| CN116766807A (en) * | 2023-06-25 | 2023-09-19 | 湖南同丰艺达薄膜科技有限公司 | High-resistance decorative film and preparation method thereof |
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