CN102600778B - Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof - Google Patents
Nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof Download PDFInfo
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- CN102600778B CN102600778B CN201210049528.9A CN201210049528A CN102600778B CN 102600778 B CN102600778 B CN 102600778B CN 201210049528 A CN201210049528 A CN 201210049528A CN 102600778 B CN102600778 B CN 102600778B
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Abstract
The invention discloses a nanometer composite epoxy resin self-repairing microcapsule and a preparation method of the microcapsule. The preparation method comprises the following steps: dispersing silicon dioxide nanometer particles in water, dissolving oil-soluble cross-linking agent into ethyl phenylacetate, mixing oil with water, and shaking by hand to vibrate and emulsify into Pickering latex; dripping the Pickering latex into melamine formaldehyde pre-polymer solution, and finally obtaining a target product by carrying out in-situ cross-linking polymerization of the pre-polymer at the surface of the latex drops under an acidic condition. Due to use of the stable Pickering latex drops as the template of the prepared microcapsule, the prepared microcapsule is regularly spherical, the size distribution is featured with polydispersity; the silicon dioxide particles doped in the capsule wall effectively enhance the mechanical strength and the thermal stability of the microcapsule, and synchronously increase the brittleness of the microcapsule; in this way, better releasing effect is obtained when the capsule of core material ethyl phenylacetate is broken.
Description
Technical field
The present invention relates to intelligent macromolecule material field, be specifically related to a kind ofly with pik woods emulsion droplet template synthesis, be enclosed with microcapsules of epoxy resin renovation agent and preparation method thereof.
Background technology
The thermosetting resin that the epoxy resin of take is matrix is applied to various fields, auto industry for example, space flight and aviation, electronics industry etc.Yet the composite of epoxy resin-base, because the attribute of himself seems very crisp, when being subject to lasting load action, is easy at the inner micro-crack that produces of matrix.The growth of these crackles if left, the destruction that finally inevitably causes whole material recurring structure.Therefore, preparing a kind of repair crack automatically keeps the complete of structure extremely urgent with the intelligent response composite in the service life extending.According to bibliographical information (Nature, 2001,409:794-797) White has successfully prepared a kind of microcapsules of using for epoxy resin selfreparing.This encapsulation liquid renovation agent---endo-dicyclopentadiene (endo-DCPD), microcapsules and the heeling-in in advance of Gubbs ' catalyst are in epoxy resin-base.When crackle is grown in matrix, microcapsules rupture also discharges DPCD in crackle.Subsequently, there is ring-opening polymerisation generation dicyclopentadiene film after touching Grubbs ' catalyst in DCPD, fills whole crackle, and stoped the extension of crackle, played the effect of repairing.Bibliographical information (Macromolecules
,2007,40:8830-8832) Caruso prepares neat solvent type epoxy resin self-repairing microcapsule.It is nuclear material that this microcapsules be take the organic good solvent of epoxy resin, ethyl phenylacetate for example, chlorobenzene, phenylacetic acid etc.After capsules break, organic solvent goes because capillarity is siphoned in crackle, these solvents can make remaining amine curing agent in matrix continue cross-linking reaction with the epoxy monomer remaining in matrix at cracks swelling epoxy resin-base, have played good repair.Follow-up a lot of bibliographical informations (J. Mater. Chem., 2011,21:9060-9065, Macromolecules 2010,43:1855 – 1859, Macromol. Rapid Commun. 2011,32:82 – 87) all successfully prepared epoxy resin selfreparing microcapsules.These work have all proved that microcapsules heeling-in method is a kind of effective method of preparing selfreparing epoxy resin composite material.
The microcapsules major part of these parcel renovation agents is all for example, to be prepared by template by the stable emulsion of emulsifying agent (ethene-copolymer-maleic anhydride).Yet the stable emulsion droplet of this emulsifying agent is all unsettled on thermodynamics and kinetics, it can not provide enough structural stabilities to prevent that emulsion droplet from melting mutually, causes whole parcel efficiency not high, and the microcapsules that prepare also there will be irregular shape.Therefore in the preparation process of capsule, the stability of emulsion has faced huge challenge.Recent years bibliographical information pickering emulsion, be that a kind of solid nano particle by having suitable hydrophilic and hydrophobic carrys out stable emulsion, attracted the interest in each a lot of fields.The emulsion stable with respect to emulsifying agent, pickering emulsion is because nano particle irreversible suction-operated on oil-water interfaces has better stability, and the pickering emulsion preparing can even can keep enough stability in the several years at some months.Therefore with the selfreparing of pik woods emulsion droplet template synthesis epoxy resin, with microcapsules, can at utmost keep the parcel efficiency of renovation agent, guarantee that microcapsules have regular spherical, and the stable emulsion of emulsifying agent is microcapsules prepared by template relatively, because the existence of its solid nano particle can give microcapsules more different character, for example there is different rough surface, better release efficiency, finer and close cyst wall, thus be more suitable in selfreparing system.
Therefore, we with pik woods emulsion droplet template synthesis be enclosed with the microcapsules of the selfreparing system for epoxy resin of ethyl phenylacetate.On the basis of the various superperformances of the self-repairing microcapsule that this neat solvent type self-repairing microcapsule is prepared when keeping the stable emulsion of emulsifying agent to be template, due to pik woods emulsion droplet template inherent attribute, improve the release efficiency of the parcel efficiency renovation agent of nuclear material, and given microcapsules different surface topography.
Summary of the invention
Object of the present invention and content are to take the stable emulsion of emulsifying agent and prepare defect and the deficiency of epoxy resin self-repairing microcapsule as template for existing, a kind of nanometer composite epoxy resin self-repairing microcapsule and preparation method thereof are provided.The emulsifying agent that this method is relatively traditional is stablized emulsion droplet template, existing good stability, and owing to having increased solid nano particle in cyst wall, mechanical strength and the heat endurance of microcapsules are greatly improved, also increased the fragility of cyst wall, make microcapsules have more thoroughly and break under effect of stress, improved the release efficiency of nuclear material.
The epoxy resin self-repairing microcapsule that the present invention is prepared, that to take the pickering emulsion of the stable water bag ethyl phenylacetate of the random Nano particles of silicon dioxide of gas phase hydrophily be template, then in water, the in-situ cross-linked polymerisation by melamino-formaldehyde performed polymer forms fine and close cyst wall and is prepared from, and concrete technical scheme is as follows.
A kind of preparation method of nanometer composite epoxy resin self-repairing microcapsule, aerosil nano particle that its relative water mass fraction is 0.5%-5% is ultrasonic is scattered in water to obtain solution 1, the polyoxypropyleneglycol that is 0.1%-2% relative oil phase mass fraction and biphenyl methane diisocyanate prepolymer are dissolved in ethyl phenylacetate and obtain solution 1, and solution 1 is become to oil-in-water pickering emulsion with solution 2 mixing and emulsifyings; Oil-in-water pickering emulsion is added drop-wise in melamino-formaldehyde prepolymer solution, is adjusted to pH to 3-5, at 40-60 ℃, there is in-situ cross-linked polymerization on emulsion droplet surface and obtain described epoxy resin self-repairing microcapsule in performed polymer.
In above-mentioned preparation method, preparation process acid-base condition will be controlled proper, and pH is 3-5, not so more side reaction can occur, and even can not form the melamine resin cyst wall in experiment imagination.
In above-mentioned preparation method, aerosil nano particle adopts ultrasonic dispersing mode to be dispersed in water, and makes to reduce the reunion of Nano particles of silicon dioxide, guarantees that the particle diameter of pik woods stable particle is evenly distributed.
In above-mentioned preparation method, at described 40-60 ℃, mechanical agitation 200-600rpm, reaction 3-5h, obtains epoxy resin self-repairing microcapsule suspension.The epoxy resin self-repairing microcapsule suspension of gained is repeatedly washed, filtered, drying at room temperature, obtains epoxy resin self-repairing microcapsule.
In above-mentioned preparation method, the epoxy resin self-repairing microcapsule suspension finally preparing is washed repeatedly, filters, dry, goes out the melamine resin particulate generating in dereaction, affects the repairing effect of self-repairing microcapsule.
In above-mentioned preparation method, adopt acetic acid to adjust described pH.Described hydromining deionized water.
In above-mentioned preparation method, the microcapsules of relative substrate quality mark 5%-20% are joined in E51 liquid epoxies, add diethylenetriamine curing agent, then degasification 2-5min in a vacuum, cold curing 20-30h, and then 30-40 ℃ of curing 20-30h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.After the composite obtaining is freezing under liquid nitrogen, with razors slice, manufacture crackle, then observing the releasing effect of microcapsules wall thickness and nuclear material.
The present invention compares tool with current material with technology and has the following advantages:
1, preparation method of the present invention is simple, does not need special installation, under normal temperature and pressure, operates, and reacts simply controlled, and cost is low, is suitable for applying;
2, the present invention is by pik woods emulsion droplet template synthesis epoxy resin self-repairing microcapsule, and pik woods emulsion droplet template has improved the stability of emulsion droplet, and the microcapsules that make to prepare have regular spherical; The particle diameter polydispersity of pickering emulsion, distributes the particle diameter of the microcapsules that prepare also larger, therefore can produce response to crackle not of uniform size, improves remediation efficiency.
3, to take pik woods emulsion droplet be template in the present invention, on cyst wall, introduced the solid nano-silicon dioxide particle of one deck, mechanical strength and the heat endurance of cyst wall have been improved, and the fragility of raising microcapsules, make microcapsules have more thoroughly and break under effect of stress, improved the release efficiency of nuclear material.
The particle size of the epoxy resin self-repairing microcapsule that 4, prepared by the present invention and wall thickness can be by regulating nanometer stable particle content, water-oil factor and feeding intake of melamino-formaldehyde performed polymer to regulate optimization, to meet the demand under different service conditions.
Accompanying drawing explanation
Fig. 1 is the flying-spot microscope photo of microcapsules.
Fig. 2 is that in epoxy resin, microcapsules ethyl phenylacetate discharges petrographic microscope photo.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.To the epoxy resin self-repairing microcapsule obtaining in embodiment, adopt the ChemPhysChem 2007 such as Wang, the open method of 8:1157-1160 document is measured particle size and its distribution of pickering emulsion, adopt the Colloid Polym Sci. such as Wang, 2009, the open method of 287:1089-1097 document is carried out the nuclear material content measuring of microcapsules, adopt the Polymer 2009 such as Blaiszik, 50: the open method of 990-997 document carries out surface of microcapsule pattern and wall thickness pattern detects, at the releasing effect of polarized light microscopy Microscopic observation nuclear material ethyl phenylacetate.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
Be scattered in 5 ml deionized waters 50 mg aerosil nano particles are ultrasonic, 50 mg PPG-TDI are shaken up and are dissolved in 5 ml ethyl phenylacetates.Profit mixes mutually, and hand vibration emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Toward the 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines that add successively 3.35ml in two mouthfuls of flasks of 50ml, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Oil-in-water pickering emulsion obtained above is added drop-wise in the melamino-formaldehyde performed polymer aqueous solution, and adjusts pH=4 with acetic acid, with the heating rate of 5 ℃/min, be heated to 50 ℃, the mechanical agitation of 400 rpm, reaction 4 h.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h, obtain epoxy resin self-repairing microcapsule.0.75 g microcapsules are joined in 5 gE51 liquid epoxies, add 0.6 g diethylenetriamine curing agent, degasification 3min in a vacuum then, cold curing 24h, and then 35 ℃ of curing 24h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.The composite obtaining with liquid nitrogen frozen, manufactures crackle with razors slice, then observing the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 5 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope (see figure 1) is observed microcapsules to be had regular spherical, size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency (see figure 2) under petrographic microscope.
Embodiment 2
Be scattered in 5 ml deionized waters 37.5 mg aerosil nano particles are ultrasonic, 5 mg PPG-TDI are shaken up and are dissolved in 5 ml ethyl phenylacetates.Profit mixes mutually, and hand vibration emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Toward the 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines that add successively 3.35ml in two mouthfuls of flasks of 50ml, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Oil-in-water pickering emulsion obtained above is added drop-wise in the melamino-formaldehyde performed polymer aqueous solution, and adjusts pH=3 with acetic acid, with the heating rate of 5 ℃/min, be heated to 60 ℃, the mechanical agitation of 200 rpm, reaction 3 h.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h, obtain epoxy resin self-repairing microcapsule.0.25 g microcapsules are joined in 5 gE51 liquid epoxies, add 0.6 g diethylenetriamine curing agent, degasification 3min in a vacuum then, cold curing 20h, and then 35 ℃ of curing 30h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.The composite obtaining with liquid nitrogen frozen, manufactures crackle with razors slice, then observing the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 5 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope (see figure 1) is observed microcapsules to be had regular spherical, size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency under petrographic microscope (see figure 2).
Embodiment 3
Be scattered in 5 ml deionized waters 25 mg aerosil nano particles are ultrasonic, 100 mg PPG-TDI are shaken up and are dissolved in 5 ml ethyl phenylacetates.Profit mixes mutually, and hand vibration emulsification obtains the stable oil-in-water pickering emulsion of Nano particles of silicon dioxide.Toward the 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines that add successively 3.35ml in two mouthfuls of flasks of 50ml, 60 ℃ of lower magnetic forces stir 30 min, obtain the melamino-formaldehyde performed polymer aqueous solution.Oil-in-water pickering emulsion obtained above is added drop-wise in the melamino-formaldehyde performed polymer aqueous solution, and adjusts PH=5 with acetic acid, with the heating rate of 5 ℃/min, be heated to 40 ℃, the mechanical agitation of 600 rpm, reaction 5zz h.Speed with 2 ℃/min cools to room temperature.The suspension of gained washing 3 times, filter, drying at room temperature 24 h, obtain epoxy resin self-repairing microcapsule.1 g microcapsules are joined in 5 gE51 liquid epoxies, add 0.6 g diethylenetriamine curing agent, degasification 5min in a vacuum then, cold curing 30h, and then 35 ℃ of curing 204h, obtain the epoxy resin composite material that heeling-in has self-repairing microcapsule.The composite obtaining with liquid nitrogen frozen, manufactures crackle with razors slice, then observing the releasing effect of microcapsules wall thickness and nuclear material.The average grain diameter of these microcapsules is at 21 ± 3 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope is observed microcapsules regular spherical (see figure 1), size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency (see figure 2) under petrographic microscope.
Embodiment 4
The present embodiment except following characteristics with embodiment 1: be scattered in 8 ml deionized waters 80 mg aerosil nano particles are ultrasonic, 20 mgPPG-TDI shaken up and are dissolved in 2 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 17 ± 5 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope is observed microcapsules regular spherical (see figure 1), size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency (see figure 2) under petrographic microscope.
Embodiment 5
The present embodiment except following characteristics with embodiment 1: be scattered in 7.5 ml deionized waters 75 mg aerosil nano particles are ultrasonic, 25 mg PPG-TDI shaken up and are dissolved in 2.5 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 22 ± 7 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope is observed microcapsules regular spherical (see figure 1), size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency (see figure 2) under petrographic microscope.
Embodiment 6
The present embodiment except following characteristics with embodiment 1: be scattered in 6.6 ml deionized waters 66 mg aerosil nano particles are ultrasonic, 33 mg PPG-TDI shaken up and are dissolved in 3.3 ml ethyl phenylacetates.The average grain diameter of these microcapsules is at 21 ± 5 μ m, TG test obtains nuclear material content at 67wt %, flying-spot microscope is observed microcapsules regular spherical (see figure 1), size distribution has polydispersity, there is smooth inner surface and coarse outer surface, wall thickness is 500-700nm, observes nuclear material ethyl phenylacetate and have good release efficiency (see figure 2) under petrographic microscope.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. the preparation method of a nanometer composite epoxy resin self-repairing microcapsule, it is characterized in that the ultrasonic solution 1 that is scattered in water to obtain of aerosil nano particle that relatively water mass fraction is 0.5%-5%, the polyoxypropyleneglycol that is 0.1%-2% relative oil phase mass fraction and toluene diisocyanate prepolymer are dissolved in ethyl phenylacetate and obtain solution 2, and solution 1 is become to oil-in-water pickering emulsion with solution 2 mixing and emulsifyings; Oil-in-water pickering emulsion is added drop-wise in the melamino-formaldehyde performed polymer aqueous solution, is adjusted to pH to 3-5, at 40-60 ℃, there is in-situ cross-linked polymerization on emulsion droplet surface and obtain described epoxy resin self-repairing microcapsule in performed polymer.
2. preparation method according to claim 1, is characterized in that adopting acetic acid to adjust described pH.
3. preparation method according to claim 2, is characterized in that at described 40-60 ℃, mechanical agitation 200-600rpm, and reaction 3-5h, obtains epoxy resin self-repairing microcapsule suspension.
4. preparation method according to claim 3, is characterized in that repeatedly washing at the epoxy resin self-repairing microcapsule suspension gained, filters, and drying at room temperature, obtains epoxy resin self-repairing microcapsule.
5. preparation method according to claim 1, it is characterized in that the described melamino-formaldehyde performed polymer aqueous solution prepared by the following method: toward the 37 wt % formalins, 2 ml triethanolamines, 10 ml water and the 1.75 g melamines that add successively 3.35ml in two mouthfuls of flasks of 50ml, 60 ℃ of lower magnetic forces stir 30 min.
6. the epoxy resin self-repairing microcapsule being made by preparation method described in claim 1 ~ 3 any one.
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| CN103265793B (en) * | 2013-06-17 | 2016-01-20 | 泰山体育产业集团有限公司 | Can the carbon fiber reinforced epoxy resin-based composite of internal repair and preparation method |
| US10160882B2 (en) * | 2015-02-26 | 2018-12-25 | Polynt Composites USA, Inc. | Fillers |
| CN105833811B (en) * | 2016-03-27 | 2018-06-22 | 华南理工大学 | A kind of double-capsule selfreparing epoxy coating and preparation method thereof |
| CN107159070A (en) * | 2017-06-16 | 2017-09-15 | 中国人民解放军装甲兵工程学院 | Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material |
| CN107312140B (en) * | 2017-06-27 | 2020-03-31 | 沈阳化工研究院有限公司 | Self-repairing microcapsule for metal anticorrosive coating and preparation method thereof |
| CN108579629B (en) * | 2018-04-28 | 2021-01-26 | 北京航空航天大学 | Organic-inorganic hybrid nanocapsule and preparation method thereof |
| CN109679114B (en) * | 2018-12-12 | 2021-06-04 | 青岛古高生物科技有限公司 | Preparation method and application of Pickering emulsion with stable protein nanocages |
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| WO2021091046A1 (en) * | 2019-11-05 | 2021-05-14 | 주식회사 엘지생활건강 | Biodegradable microcapsule and method for manufacturing same |
| CN111450771A (en) * | 2020-04-01 | 2020-07-28 | 中国石油天然气股份有限公司 | Multifunctional integrated Pickering particle emulsifier and preparation method thereof |
| CN111298733A (en) * | 2020-04-03 | 2020-06-19 | 兰州交通大学 | Concrete structure self-immune self-repairing microcapsule and preparation method thereof |
| CN114097777B (en) * | 2021-12-08 | 2022-10-18 | 四川大学 | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof |
| CN115414877B (en) * | 2022-08-01 | 2024-01-05 | 浙江理工大学 | Method for preparing phase-change energy-storage microcapsule based on p-phenylenediamine stable Pickering emulsion |
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