CN102604469B - Latent self-repair microcapsule and preparation method thereof - Google Patents
Latent self-repair microcapsule and preparation method thereof Download PDFInfo
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- CN102604469B CN102604469B CN2012100310600A CN201210031060A CN102604469B CN 102604469 B CN102604469 B CN 102604469B CN 2012100310600 A CN2012100310600 A CN 2012100310600A CN 201210031060 A CN201210031060 A CN 201210031060A CN 102604469 B CN102604469 B CN 102604469B
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Abstract
The invention belongs to the technical field of preparation of a microcapsule, and relates to a latent self-repair microcapsule for an organic coating and a preparation method of the latent self-repair microcapsule. The method comprises the steps of feeding urea and formaldehyde mixed solution into a four-mouth flask, adjusting the pH value to 7.5-11.8 with triethanolamine, and ensuring that the temperature is slowly increased for reaction for 3 hours, so as to produce viscous transparent water-soluble urea-formaldehyde prepolymer solution; sufficiently mixing a capsule-core epoxy resin, a capsule-core diluting agent, and a capsule-core latent curing modifier proportionally, adding distilled water, stirring, adding an emulsifying agent, emulsifying for 10-20min in a high-speed emulsifyingmachine, so as to form O/W type emulsion, mixing the urea-formaldehyde prepolymer solution and the emulsified liquid and sufficiently stirring to disperse in an aqueous medium, adjusting the pH valueto 1.0 to 5.0, centrifugating the particle suspension after curing at a controlled temperature for 3 hours, performing flushing for a plurality of times, and then performing vacuum drying to obtain the microcapsule. The method has the advantages that the technology is simple, the condition is easy to control, the preparation cost is low, the product quality is good, the repair effect is good, themanpower and cost are saved, and the method is environment-friendly.
Description
Technical field;
The invention belongs to the microcapsules preparing technical field, relate to a kind of resting form self-repairing microcapsule for organic coating and preparation method thereof, particularly compound microcapsules of a kind of resting form renovation agent formula and preparation method thereof.
Background technology:
At present, the technology of traditional reparation crackle mainly contains welding, repairing, new resin in-situ solidifying etc., these conventional methods are to utilize intermolecular interaction to repair some thermoplastic resins mostly, repair mechanisms are the intermolecular non-covalent interactions in interface, do not have new covalent bond to form, and need a large amount of hand labours; The self-repairing microcapsule technology that is used for the coating crack reparation has the characteristics of self diagnosis and selfreparing, remedies the leak that the manual detection holiday exists, and reduces the work workload.How to do renovation agent with dicyclopentadiene both at home and abroad at present and make microcapsules, but adopt dicyclopentadiene (DCPD) to have following shortcoming for the renovation agent of Self-repair Composites: the catalyst such as the RuCl that are used for the DCPD ring-opening reaction
3, K
2RuCl
5, Ru (H
2O)
6-(tos)
2Etc. the price costliness; The mechanical property of DCPD polymeric reaction product is lower; In self-repair procedure, DCPD is less with the probability that catalyst can contact, the selfreparing weak effect.Also there is the researcher to use epoxy resin micro-capsule reparation crackle, this method need add the curing agent microcapsules, the probability that the realization of epoxy resin micro-capsule and curing agent microcapsules is broken simultaneously by the quality proportioning is less, be difficult to break with corresponding quality proportioning, and after the capsules break, two kinds of cores are difficult for mixing mutually, are difficult to the solidification effect that reaches desirable.Simultaneously, epoxy resin viscosity is bigger, and is mobile poor in self-repair procedure, makes troubles for the curing of epoxy resin.Shortcoming based on above method existence, inquire into a kind of latent curing agent that utilizes and have the ability that organic coating is repaired in potential curing, with its with make microcapsules after epoxy resin and diluent mix according to special proportioning, be dispersed in the organic coating, the method for the ability to cure that having hides repairs crackle is necessary.Organic coating runs into breakage, rise and split, under the situation that crackle produces, will automatically the resting form microcapsule wall be torn, and core materials flows out fills up crackle, passes through the later stage high-temperature process again, can finish the patch work of organic coating crackle; These technology are in repair process, do not need extra the interpolation to repair catalyst or initator, solve core materials and flowed into behind the crack problem little with catalyst or initator contact probability, can solve the problem of the mobile difference of epoxy resin in the self-repair procedure, can improve remediation efficiency.
Summary of the invention:
The objective of the invention is to overcome the shortcoming that prior art exists, seek to design proposition a kind of resting form self-repairing microcapsule and preparation method for organic coating, the resting form self-repairing microcapsule of its preparation uses the heating cure method to repair crackle in repair process, do not need extra the interpolation to repair catalyst or initator, solve core materials and flow into behind the crack problem little with catalyst or initator contact probability, the microcapsules storage life of its preparation is longer, and capsule-core repair materials viscosity is controlled.
To achieve these goals, it is 1 according to weight proportion that the resting form self-repairing microcapsule that the present invention relates to solidifies the dressing agent three by capsule-core resin, capsule-core diluent and capsule-core resting form: 0.05-0.5: 0.05-0.8 is combined into core materials; The weight proportion of each component is capsule-core resin 5-20 part in the microcapsules; Capsule-core diluent 0.5-5 part; The capsule-core resting form solidifies dressing agent 1-18 part; It is 1 in molar ratio: the urea that 1.0-3.0 is made into and formaldehyde mixed solution 2-33 part; Emulsifying agent 0.1-3 part; Defoamer 0.05-1 part; Deionized water 45-105 part.
Capsule-core resin of the present invention comprises multiple functional radical glycidyl ether resin, multiple functional radical epihydric alcohol amine resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, linear phenolic epoxy resin and halogenated epoxy resin.
Capsule-core diluent of the present invention is one or more in chlorobenzene, 1-butyl glycidyl ether, phenmethylol, ethyl acetate and the ethyl acetic acid benzene fat, according to the viscosity of the proportioning control core materials of diluent in core materials, to be applicable to the not crack of isomorphism type.
Capsule-core resting form curing dressing agent of the present invention is one or more in dodecyl suitable enedioic acid acid anhydride of generation, hexahydrophthalic acid anhydride, phthalic anhydride, imidazoles, dicyandiamide, boron chloride-mono aminoethane complex compound, triethanolamine and the boron chloride benzylamine.
Emulsifying agent of the present invention is one or more in APES compound, calcium dodecyl benzene sulfonate, sorbitan fatty acid ester, sorbitan monostearate, neopelex, lauryl sodium sulfate and the styrene-maleic anhydride copolymer.
Defoamer of the present invention is lower alcohols or polar organic compounds series, and the lower alcohols defoamer comprises methyl alcohol, ethanol, isopropyl alcohol and n-butanol; Polar organic compounds series defoamer comprises amylalcohol, diisobutyl carbinol (DIBC), octanol, dehydration sorbic alcohol Triolein and polypropylene glycol.
It is the situ aggregation method of the organic coating micro-crack resting form self-repairing microcapsule of wall material feedstock production that the preparation method of the resting form self-repairing microcapsule that the present invention relates to selects with urea, formaldehyde, concrete steps are: the urea and the formaldehyde mixed solution that add mol ratio=1: 1.0-3.0 in four-hole boiling flask, with triethanolamine or NaOH regulate acid-base value to pH in the 7.5-11.8 scope, and slowly be warming up to 60-85 ℃ of reaction 3 hours, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Get epoxies capsule-core resin, capsule-core diluent, capsule-core resting form and solidify dressing agent according to part by weight 1: 0.05-0.5: 0.05-0.8 fully mixes, and adds 40-110ml distilled water, mixes; 0.5%-2.5% adds emulsifying agent by weight ratio; In high-speed emulsifying machine, with the speed emulsification of 10000-30000r/min 10-20 minute, form O/W type emulsion; Lauxite pre-polymerization liquid is mixed with emulsion, fully stirring is dispersed in the aqueous medium pre-polymerization liquid, dripping watery hydrochloric acid and NaOH regulates in pH to the 1.0-5.0 scope, temperature control 45-70 ℃ solidifies after 3 hours that the particle suspension liquid that makes is centrifugal, repeatedly flushing, vacuum drying then, obtains resting form self-repairing microcapsule product.
The present invention compared with prior art, have following advantage: the one, the resting form self-repairing microcapsule of preparation is in repair process, do not need extra the interpolation to repair catalyst or initator, solve core materials and flow into behind the crack problem little with catalyst or initator contact probability; The 2nd, overcome the problem of the mobile difference of epoxy resin in the self-repair procedure; The 3rd, reduced the loaded down with trivial details work of manual detection, there are crack initiation and growth, coating to be subjected to external force crimp in the coating, have micro-crack can impel the cyst wall of repairing microcapsules to break, capsule-core resting form renovation agent can flow out in capsule, fills crackle; The 4th, microcapsules energy stable existence is in organic coating under normal temperature, atmospheric pressure environment; Its whole technology is simple, and condition is easily controlled, and preparation cost is low, good product quality, and repairing effect is good, saves the manpower financial capacity, environmental friendliness.
The specific embodiment:
The present invention will be further described below by concrete embodiment.
Embodiment 1:
Present embodiment adds urea earlier in four-hole boiling flask and 37% formalin is mixed, mol ratio=1: 1.0-3.0; To pH to 7.5-11.8 scope, and slowly be warming up to 60-85 ℃ of reaction 3 hours with triethanolamine or NaOH acid adjustment basicity, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Extracting epoxy resin, capsule-core diluent, capsule-core resting form solidify dressing agent proportionally fully to be mixed at 1: 0.5: 0.25, adds 40-110ml distilled water, mixes; Add emulsifying agent by proportioning 0.5%-2.5%, the control high-speed emulsifying machine forms O/W type emulsion with the speed emulsification of 10000-30000r/min 10-20 minute; Lauxite pre-polymerization liquid is mixed with emulsion, fully stirring is dispersed in the aqueous medium pre-polymerization liquid, dripping watery hydrochloric acid and NaOH regulates in pH to the 1.0-5.0 scope, control 45-70 ℃ then and solidify 3 hours by centrifugal, repeated multiple times flushing and vacuum drying, obtain the sample of microcapsule product; The resting form curing performance experiment effect explanation of this sample: this microcapsules sample was solidified 6 hours in 140 ℃ of environment, the microcapsule granule capsule-core solidifies, under identical condition of cure, microcapsule granule of the present invention is used for the selfreparing of organic coating micro-crack, and the crackle filling effect is intact.
Embodiment 2:
Present embodiment adds urea earlier in four-hole boiling flask and 37% formalin is mixed, mol ratio=1: 1.0-3.0, with triethanolamine or NaOH acid adjustment basicity to pH to 7.5-11.8 scope, and slowly be warming up to 60-85 ℃ of reaction 3 hours, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Extracting epoxy resin, capsule-core diluent, capsule-core resting form solidify dressing agent proportionally fully to be mixed at 1: 0.5: 0.4, adds 40-110ml distilled water, mixes; Add emulsifying agent by proportioning 0.5%-2.5%; The control high-speed emulsifying machine forms O/W type emulsion with the speed emulsification of 10000-30000r/min 10-20 minute; Lauxite pre-polymerization liquid is mixed with emulsion, fully stirring is dispersed in the aqueous medium pre-polymerization liquid, drip watery hydrochloric acid and NaOH and regulate in pH to the 1.0-5.0 scope, control 45-70 ℃ of curing then and washed and vacuum drying through centrifugal, repeated multiple times afterwards in 3 hours, obtain the microcapsules sample; The resting form curing performance experiment effect explanation of this sample: this microcapsules sample was solidified 4.5 hours in 120 ℃ of environment, the microcapsule granule capsule-core solidifies, under identical condition of cure, microcapsule granule of the present invention is used for the selfreparing of organic coating micro-crack, and the crackle filling effect is intact.
Embodiment 3:
Present embodiment adds urea earlier in four-hole boiling flask and 37% formalin is mixed, mol ratio=1: 1.0-3.0, with triethanolamine or NaOH acid adjustment basicity to pH to 7.5-11.8 scope, and slowly be warming up to 60-85 ℃ of reaction 3 hours, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Extracting epoxy resin, capsule-core diluent, capsule-core resting form solidify dressing agent proportionally fully to be mixed at 1: 0.5: 0.6, adds 40-110ml distilled water, mixes; By proportioning 0.5%-2.5%, add emulsifying agent; The control high-speed emulsifying machine forms O/W type emulsion with the speed emulsification of 10000-15000r/min 10-20 minute; Lauxite pre-polymerization liquid is mixed with emulsion, fully stirring is dispersed in the aqueous medium pre-polymerization liquid, drip watery hydrochloric acid and NaOH and regulate in pH to the 1.0-5.0 scope, control 45-70 ℃ of curing then and washed and vacuum drying through centrifugal, repeated multiple times afterwards in 3 hours, obtain the microcapsules sample; The resting form curing performance experiment effect explanation of this sample: this microcapsules sample was solidified 2.5 hours in 100 ℃ of environment, the microcapsule granule capsule-core solidifies, under identical condition of cure, microcapsule granule of the present invention is used for the selfreparing of organic coating micro-crack, and the crackle filling effect is intact.
Claims (1)
1. the preparation method of a resting form self-repairing microcapsule, it is characterized in that selecting with urea, formaldehyde is the situ aggregation method of the organic coating micro-crack resting form self-repairing microcapsule of wall material feedstock production, concrete steps are: the urea and the formaldehyde mixed solution that add mol ratio=1:1.0-3.0 in four-hole boiling flask, with triethanolamine or NaOH regulate acid-base value to pH in the 7.5-11.8 scope, and slowly be warming up to 60-85 ℃ of reaction 3 hours, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Get epoxies capsule-core resin, capsule-core diluent, capsule-core resting form and solidify dressing agent and fully mix according to part by weight 1:0.05-0.5:0.05-0.8, add 40-110ml distilled water, mix; 0.5%-2.5% adds emulsifying agent by weight ratio; In high-speed emulsifying machine, with the speed emulsification of 10000-30000r/min 10-20 minute, form O/W type emulsion; Lauxite pre-polymerization liquid is mixed with emulsion, fully stirring is dispersed in the aqueous medium pre-polymerization liquid, dripping watery hydrochloric acid and NaOH regulates in pH to the 1.0-5.0 scope, temperature control 45-70 ℃ solidifies after 3 hours that the particle that makes is centrifugal through suspension, repeatedly flushing, vacuum drying then, gets resting form self-repairing microcapsule product; It is that 1:0.05-0.5:0.05-0.8 is combined into core materials according to weight proportion that its resting form self-repairing microcapsule of making solidifies the dressing agent three by capsule-core resin, capsule-core diluent and capsule-core resting form; The weight proportion of each component is capsule-core resin 5-20 part in the microcapsules; Capsule-core diluent 0.5-5 part; The capsule-core resting form solidifies dressing agent 1-18 part; Urea and formaldehyde mixed solution 2-33 part that is made into for 1:1.0-3.0 in molar ratio; Emulsifying agent 0.1-3 part; Defoamer 0.05-1 part; Deionized water 45-105 part.
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| JPH0798449A (en) * | 1993-09-28 | 1995-04-11 | Dainippon Printing Co Ltd | Liquid crystal-contained microcupsule and its production |
| CN1927443B (en) * | 2005-09-06 | 2010-12-08 | 西北工业大学 | Ureaformaldehyde resin coating epoxy microcapsule for material self-repair and preparing method thereof |
| CN1927444B (en) * | 2005-09-06 | 2012-01-04 | 西北工业大学 | Ureaformaldehyde resin bilaminar membrane coating epoxy resin microcapsule and preparing method thereof |
| CN101289298B (en) * | 2008-05-20 | 2012-06-06 | 深圳大学 | Self-repair concrete using urea-formaldehyde resin type high molecule microcapsule and method of manufacture |
| CN102205225B (en) * | 2011-06-02 | 2013-02-27 | 北京科技大学 | Method for preparing enhanced epoxy resin/curing agent double-wall microcapsule |
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