CN102604469A - Latent self-repair microcapsule and preparation method thereof - Google Patents
Latent self-repair microcapsule and preparation method thereof Download PDFInfo
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- CN102604469A CN102604469A CN2012100310600A CN201210031060A CN102604469A CN 102604469 A CN102604469 A CN 102604469A CN 2012100310600 A CN2012100310600 A CN 2012100310600A CN 201210031060 A CN201210031060 A CN 201210031060A CN 102604469 A CN102604469 A CN 102604469A
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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 emulsifying machine, 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 value to 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, the manpower and cost are saved, and the method is environment-friendly.
Description
Technical field;
The invention belongs to the microcapsule preparing technical field, relate to a kind of resting form self-repairing microcapsule that is used for organic coating and preparation method thereof, compound microcapsule of particularly 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 traditional methods are to utilize molecular interaction to repair some thermoplastic resins mostly; Repair mechanisms are the intermolecular non-covalent interactions in interface, do not have new covalent linkage 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 both at home and abroad at present and process microcapsule, but adopt NSC 7352 (DCPD) to have following shortcoming: the catalyzer such as the RuCl that are used for the DCPD ring-opening reaction for the renovation agent of Self-repair Composites with NSC 7352
3, K
2RuCl
5, Ru (H
2O)
6-(tos)
2Expensive etc. price; The mechanical property of DCPD polymeric reaction product is lower; In self-repair procedure, DCPD is less with the probability that catalyzer can contact, the selfreparing weak effect.Also there is the researchist to use epoxy resin micro-capsule reparation crackle; This method need add the solidifying agent microcapsule; The disruptive probability is less simultaneously by the quality proportioning in the realization of epoxy resin micro-capsule and solidifying agent microcapsule, be difficult to break with corresponding quality proportioning, and after the capsules break; Two kinds of cores are difficult for mixing each other, are difficult to reach the ideal solidification effect.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 potential solidifies the reparation organic coating; With its with process microcapsule after epoxy resin and thinner 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 pyroprocessing again, can accomplish the patch work of organic coating crackle; These technology are in repair process; Do not need extra interpolation to repair catalyzer or initiator; Solve core materials and flowed into behind the crack and catalyzer or the little problem of initiator 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 a kind of resting form self-repairing microcapsule and preparation method who is used for organic coating of proposition; The resting form self-repairing microcapsule of its preparation uses the heating cure method to repair crackle in repair process, does not need extra interpolation to repair catalyzer or initiator, solves core materials and flows into behind the crack and catalyzer or the little problem of initiator contact probability; The microcapsule shelf lives 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 modifier three by capsule-core resin, capsule-core thinner 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 microcapsule; Capsule-core thinner 0.5-5 part; The capsule-core resting form solidifies modifier 1-18 part; It is 1 in molar ratio: the urea that 1.0-3.0 is made into and formaldehyde mixing solutions 2-33 part; Emulsifying agent 0.1-3 part; Skimmer 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 thinner of the present invention is one or more in chlorobenzene, 1-butylglycidyl ether, phenylcarbinol, ETHYLE ACETATE and the ethyl acetic acid benzene fat; According to the viscosity of the proportioning control core materials of thinner in core materials, to be applicable to the not crack of isomorphism type.
Capsule-core resting form curing modifier of the present invention is one or more in dodecyl suitable enedioic acid acid anhydride of generation, hexahydrophthalic acid anhydride, Tetra hydro Phthalic anhydride, imidazoles, Dyhard RU 100, boron trichloride-mono aminoethane complex compound, trolamine and the boron trichloride benzylamine.
Emulsifying agent of the present invention is one or more in TX10 mixture, calcium dodecylbenzene sulphonate, sorbitan fatty acid ester, sorbitan monostearate, X 2073, sodium lauryl sulphate and the styrene-maleic anhydride copolymer.
Skimmer of the present invention is lower alcohols or polar organic compounds series, and the lower alcohols skimmer comprises methyl alcohol, ethanol, Virahol and propyl carbinol; Polar organic compounds series skimmer comprises amylalcohol, diisobutyl carbinol(DIBC), octanol, dehydration sorbic alcohol Triolein and W 166.
It is the situ aggregation method of the organic coating tiny 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 mixing solutions that in four-hole boiling flask, add mol ratio=1: 1.0-3.0; With trolamine or sodium hydroxide regulate potential of hydrogen 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 thinner, capsule-core resting form and solidify modifier according to part by weight 1: 0.05-0.5: the 0.05-0.8 thorough mixing, add 40-110ml zero(ppm) water, mix; 0.5%-2.5% adds emulsifying agent by weight ratio; In high-speed emulsifying machine,, form O/W type emulsion with the speed emulsification of 10000-30000r/min 10-20 minute; Urea-formaldehyde resin pre-polymerization liquid is mixed with emulsion; Fully stirring is dispersed in the water medium pre-polymerization liquid; Dripping Hydrogen chloride and sodium hydroxide 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 advantage: the one, the resting form self-repairing microcapsule of preparation is in repair process; Do not need extra interpolation to repair catalyzer or initiator, solve core materials and flow into behind the crack and catalyzer or the little problem of initiator contact probability; The 2nd, overcome the problem of the mobile difference of epoxy resin in the self-repair procedure; The 3rd, reduced the complicated work of manual detection, there are crack initiation and growth, coating to receive external force crimp in the coating, have tiny crack can impel the cyst wall of repairing microcapsule to break, capsule-core resting form renovation agent can flow out in capsule, fills crackle; The 4th, microcapsule ability stable existence is in organic coating under normal temperature, atmospheric pressure environment; Its whole technology is simple, and condition is prone to control, and preparation cost is low, good product quality, and repairing effect is good, saves the manpower financial capacity, environmental friendliness.
Embodiment:
Through the practical implementation instance the present invention is further specified below.
Embodiment 1:
Present embodiment in four-hole boiling flask, adds urea earlier and 37% formaldehyde solution 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 trolamine or sodium hydroxide acid adjustment basicity, generate the transparent water soluble urea formaldehyde prepolymer solution of thickness; Extracting epoxy resin, capsule-core thinner, capsule-core resting form solidify proportionally 1: 0.5: 0.25 thorough mixing of modifier, add 40-110ml zero(ppm) water, mix; 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; Urea-formaldehyde resin pre-polymerization liquid is mixed with emulsion; Fully stirring is dispersed in the water medium pre-polymerization liquid; Dripping Hydrogen chloride and sodium hydroxide regulates in pH to the 1.0-5.0 scope; Control 45-70 ℃ then and solidified 3 hours after 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 microcapsule 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 tiny crack, and the crackle filling effect is intact.
Embodiment 2:
Present embodiment in four-hole boiling flask, adds urea earlier and 37% formaldehyde solution is mixed; Mol ratio=1: 1.0-3.0; With trolamine or sodium hydroxide 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 thinner, capsule-core resting form solidify proportionally 1: 0.5: 0.4 thorough mixing of modifier, add 40-110ml zero(ppm) water, mix; 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; Urea-formaldehyde resin pre-polymerization liquid is mixed with emulsion; Fully stirring is dispersed in the water medium pre-polymerization liquid; Drip Hydrogen chloride and sodium hydroxide 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 microcapsule sample; The resting form curing performance experiment effect explanation of this sample: this microcapsule 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 tiny crack, and the crackle filling effect is intact.
Embodiment 3:
Present embodiment in four-hole boiling flask, adds urea earlier and 37% formaldehyde solution is mixed; Mol ratio=1: 1.0-3.0; With trolamine or sodium hydroxide 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 thinner, capsule-core resting form solidify proportionally 1: 0.5: 0.6 thorough mixing of modifier, add 40-110ml zero(ppm) water, mix; 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; Urea-formaldehyde resin pre-polymerization liquid is mixed with emulsion; Fully stirring is dispersed in the water medium pre-polymerization liquid; Drip Hydrogen chloride and sodium hydroxide 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 microcapsule sample; The resting form curing performance experiment effect explanation of this sample: this microcapsule 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 tiny crack, and the crackle filling effect is intact.
Claims (7)
1. resting form self-repairing microcapsule, it is characterized in that it is 1 according to weight proportion that the resting form self-repairing microcapsule solidifies the modifier three by capsule-core resin, capsule-core thinner 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 microcapsule; Capsule-core thinner 0.5-5 part; The capsule-core resting form solidifies modifier 1-18 part; It is 1 in molar ratio: the urea that 1.0-3.0 is made into and formaldehyde mixing solutions 2-33 part; Emulsifying agent 0.1-3 part; Skimmer 0.05-1 part; Deionized water 45-105 part.
2. resting form self-repairing microcapsule according to claim 1 is characterized in that described capsule-core resin 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.
3. resting form self-repairing microcapsule according to claim 1; It is characterized in that described capsule-core thinner is one or more in chlorobenzene, 1-butylglycidyl ether, phenylcarbinol, ETHYLE ACETATE and the ethyl acetic acid benzene fat; According to the viscosity of the proportioning control core materials of thinner in core materials, to be applicable to the not crack of isomorphism type.
4. resting form self-repairing microcapsule according to claim 1 is characterized in that described capsule-core resting form curing modifier is one or more in dodecyl suitable enedioic acid acid anhydride of generation, hexahydrophthalic acid anhydride, Tetra hydro Phthalic anhydride, imidazoles, Dyhard RU 100, boron trichloride-mono aminoethane complex compound, trolamine and the boron trichloride benzylamine.
5. resting form self-repairing microcapsule according to claim 1 is characterized in that described emulsifying agent is one or more in TX10 mixture, calcium dodecylbenzene sulphonate, sorbitan fatty acid ester, sorbitan monostearate, X 2073, sodium lauryl sulphate and the styrene-maleic anhydride copolymer.
6. resting form self-repairing microcapsule according to claim 1 is characterized in that described skimmer is lower alcohols or polar organic compounds series, and the lower alcohols skimmer comprises methyl alcohol, ethanol, Virahol and propyl carbinol; Polar organic compounds series skimmer comprises amylalcohol, diisobutyl carbinol(DIBC), octanol, dehydration sorbic alcohol Triolein and W 166.
7. the preparation method of resting form self-repairing microcapsule as claimed in claim 1; It is characterized in that selecting with urea, formaldehyde is the situ aggregation method of the organic coating tiny crack resting form self-repairing microcapsule of wall material feedstock production; Concrete steps are: the urea and the formaldehyde mixing solutions that in four-hole boiling flask, add mol ratio=1: 1.0-3.0; With trolamine or sodium hydroxide regulate potential of hydrogen 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 thinner, capsule-core resting form and solidify modifier according to part by weight 1: 0.05-0.5: the 0.05-0.8 thorough mixing, add 40-110ml zero(ppm) water, mix; 0.5%-2.5% adds emulsifying agent by weight ratio; In high-speed emulsifying machine,, form O/W type emulsion with the speed emulsification of 10000-30000r/min 10-20 minute; Urea-formaldehyde resin pre-polymerization liquid is mixed with emulsion; Fully stirring is dispersed in the water medium pre-polymerization liquid; Dripping Hydrogen chloride and sodium hydroxide 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-s, repeatedly flushing, vacuum-drying then, gets resting form self-repairing microcapsule product.
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| CN103194164A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | High temperature self-repairing conductive silver adhesive and preparation method thereof |
| CN103224343A (en) * | 2013-04-17 | 2013-07-31 | 重庆交通大学 | Manufacturing method of microcapsule for concrete crack self-repairing |
| CN103881504A (en) * | 2014-03-18 | 2014-06-25 | 北京工业大学 | Colored self-repairing heat reflecting coating and coating process thereof |
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| CN103224343A (en) * | 2013-04-17 | 2013-07-31 | 重庆交通大学 | Manufacturing method of microcapsule for concrete crack self-repairing |
| CN103194164B (en) * | 2013-04-26 | 2014-05-21 | 中国电子科技集团公司第三十八研究所 | High temperature self-repairing conductive silver adhesive and preparation method thereof |
| CN103194164A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | High temperature self-repairing conductive silver adhesive and preparation method thereof |
| CN103881504B (en) * | 2014-03-18 | 2016-04-06 | 北京工业大学 | A kind of colored selfreparing heat-reflective coating and coating process thereof |
| CN103881504A (en) * | 2014-03-18 | 2014-06-25 | 北京工业大学 | Colored self-repairing heat reflecting coating and coating process thereof |
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| CN105214580A (en) * | 2015-09-18 | 2016-01-06 | 中国石油大学(华东) | The preparation method of coatings microcapsules |
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| CN106281000A (en) * | 2015-12-30 | 2017-01-04 | 中国特种飞行器研究所 | Microcapsule selfreparing organic/inorganic polysiloxane coating materials and processing method |
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| CN108452750A (en) * | 2018-04-10 | 2018-08-28 | 安徽陵阳新材料有限公司 | A kind of preparation method of self-healing electrophoretic coating microcapsules |
| CN108452750B (en) * | 2018-04-10 | 2021-04-13 | 安徽陵阳新材料有限公司 | Preparation method of microcapsule for self-healing electrophoretic coating |
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| CN109550466A (en) * | 2018-12-04 | 2019-04-02 | 南昌大学 | A kind of Mobyneb microcapsules and preparation method thereof for material selfreparing |
| CN110294609A (en) * | 2019-06-21 | 2019-10-01 | 游雪花 | A kind of preparation method of concrete creak self-repair material |
| CN112961526A (en) * | 2021-03-03 | 2021-06-15 | 中国船舶重工集团公司第七二五研究所 | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule |
| CN112961526B (en) * | 2021-03-03 | 2021-11-23 | 中国船舶重工集团公司第七二五研究所 | Preparation method of magnetic particle enriched anticorrosion and antifouling integrated self-repairing microcapsule |
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| CN102604469B (en) | 2013-09-04 |
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