CN103304775B - Epoxy microcapsule and preparation method thereof - Google Patents
Epoxy microcapsule and preparation method thereof Download PDFInfo
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- CN103304775B CN103304775B CN201310215224.XA CN201310215224A CN103304775B CN 103304775 B CN103304775 B CN 103304775B CN 201310215224 A CN201310215224 A CN 201310215224A CN 103304775 B CN103304775 B CN 103304775B
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- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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Abstract
The invention is applicable to the field of microcapsule preparation and self-repairing materials, and provides an epoxy resin microcapsule. The epoxy resin microcapsule comprises a capsule core and a capsule wall, wherein the capsule core consists of epoxy resin or a mixture containing the epoxy resin; and the capsule wall is obtained through a reaction between partial epoxy resin in the capsule core and a curing agent. The invention also provides a preparation method of the epoxy resin microcapsule. The preparation method of the epoxy resin microcapsule provided by the invention has a simple process.
Description
Technical field
The present invention relates to microcapsule preparation and self-repair material field, relate in particular to a kind of epoxy microcapsule and preparation method thereof.
Background technology
Self-repair material is the one of intelligent material, and it can respond according to the change of external environment factor, autonomous crackle or defect of repairing inside.The usual way of giving material self-regeneration function is: in body material, embed renovation agent in advance, and when matrix is because damaging by external force or other external environment factor effect, renovation agent is released, and cicatrizes a wound.This function greatly improves the reliability that engineering materials uses, and increases the service life, is thus widely used in rust proof paint, polymer parts, pottery or concrete member.The method of embedding renovation agent normally by filling for renovation agent in the fibre pipe of hollow or be wrapped in the tiny capsules of polymkeric substance, then bury and form matrix material in the base.Compared with hollow fiber conduit, microcapsule are not because having anisotropy, many to the corresponding factor of environment, and obtain and study more widely.
The preparation method of microcapsule is numerous, and the mechanism formed according to cyst wall and encapsulation condition are roughly divided into chemical method, Physical and physico-chemical processes three class.In chemical method, cyst material is on-the-spot synthesis, and most typical is interfacial polymerization and situ aggregation method.Interfacial polymerization ratio juris is dissolved in respectively by two kinds of reactive monomers in two kinds of immiscible solvents, and when wherein a kind of solution is scattered in another kind of solution, the monomer in two kinds of solution reacts at phase interface and forms cyst wall.In-situ polymerization rule is all dissolved in a kind of solvent (i.e. external phase or disperse phase) wherein by reactive monomer (or its solubility performed polymer) and catalyzer, then polymerization reaction take place, polymkeric substance because molecular weight increase and at two-phase interface place formation of deposits cyst wall.In the preparation process of the microcapsule for selfreparing, situ aggregation method is widely adopted, wherein common with the microcapsule synthesizing carbamide resin wall material.
As renovation agent, the selection of core obviously has conclusive impact to repairing effect.For crackle, the hole repaired in polymer, pottery or concrete substrate, epoxy resin is first-selected, because it and most matrix all have good adhesiveproperties, during solidification, shrinking percentage is low, stable performance, and storage period is long, meets the requirement of resting form renovation agent.Epoxy resin refers to the crosslinkable polymkeric substance of a large class containing ethylene oxide group in fact, and the trade mark is numerous and inexpensive, applicable multiple application purpose and occasion, and therefore consider from business application point, epoxy resin is also the ideal candidates of renovation agent.
For the self-repair material that mechanics triggers, general requirement microcapsule break under the stress of setting, during to ensure that damage occurs, renovation agent content can be released, reach the object of repairing, also require that adding the impact of matrix strength of microcapsule is little simultaneously, especially prepare pottery or concrete substrate component time because in this case microcapsule add the intensity normally reducing component.Only consider from amechanical angle, this just requires that microcapsule should have more spherical, even and controlled particle diameter and wall thickness, easily dispersion of not reuniting, and microcapsule wall is crisp, strong and non-leakage to core with basal body binding force.As for self-repair concrete, because usage quantity is large, also wish that microcapsule are inexpensive, can scale production in enormous quantities.At present extensively research can meet many requirements wherein with the urea aldehyde/epoxy microcapsule of situ aggregation method synthesis, but exist a lot of difficult in the morphology Control of capsule, show that sphericity is poor, surface irregularity, extensively, clad ratio is low for size distribution.The preparation process of urea aldehyde/epoxy microcapsule is also comparatively complicated, first will synthesize performed polymer, then emulsification together with epoxy resin, and then through acidifying, the links such as polymerization, filters, rinsing, dry just can obtain product.Because the reaction mechanism of urea and formaldehyde is complicated, the formation of cyst wall, molecular structure, molecular weight, degree of crosslinking etc. and the closely-related factor of cyst wall mechanical property of polymkeric substance depend on the reaction parameter such as kind, stir speed (S.S.), pH value, urea/formaldehyde mole ratio of temperature of reaction, temperature rise rate, tensio-active agent all consumingly, general being difficult to ensures that polymkeric substance very deposits at oil/water two-phase interface place, also be difficult to after cyst wall is formed ensure that wall thickness can evenly increase, and therefore will obtain the homogeneous microcapsule consistent with performance of form very difficult everywhere.Although there are some researches show, by adding suitable auxiliary agent in external phase, as ammonium chloride, phosphoric acid, hydrogen peroxide etc., cyst wall can be accelerated and form process, improving the surface smoothness of clad ratio and microcapsule.Or interpolation trimeric cyanamide, make its together with urea with formaldehyde condensation copolymerization, also can improve the form of microcapsule.Even change reaction monomers, lower the complicacy of reaction, synthesize with the epoxy microcapsule of other resin for wall material, gross morphology is better than urea aldehyde/epoxy microcapsule.But in general, situ aggregation method does not have an advantage in control Microcapsules Size, pattern and wall thickness, this be reason reaction monomers only in single-phase, there is competitive relation in oil/water interface deposition with depositing in the solution in polymerisate.Want encystation, just need to change oil/water character by tensio-active agent, make polymkeric substance preferentially in interface deposition, but cyst wall is once form, and needs to thicken rapidly, to improve intensity, to be out of shape because mutually colliding to prevent capsule and even to break.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of epoxy resin micro-capsule and preparation method thereof, aims to provide the preparation method of the simple epoxy resin micro-capsule of a kind of preparation technology.
The present invention realizes like this, epoxy resin micro-capsule is obtained by the preparation method of the epoxy resin micro-capsule based on surface reaction, described epoxy resin micro-capsule comprises capsule-core and cyst wall, the described capsule heart forms by epoxy resin or containing the mixture of epoxy resin, and described cyst wall is reacted by the part epoxy in capsule-core and solidifying agent and obtains.
A preparation method for described epoxy microcapsule, comprises the following steps:
The first step, is dispersed in the water containing tensio-active agent by epoxy resin or its mixture, forms emulsion.
Second step, adds solidifying agent or aqueous solution of curing agent, and mixes, obtain homogeneous system in described emulsion.
3rd step, changes described system temperature, stirs simultaneously, and solidifying agent and epoxy resin are reacted.
4th step, by throw out water rinse, dry, obtain epoxy resin micro-capsule.
The preparation method of the epoxy resin micro-capsule based on surface reaction provided by the invention, because epoxy resin is generally oil soluble, is easy to after adding suitable tensio-active agent be dispersed in water formation emulsion.Utilize the high reaction activity of Oxyranyle, in aqueous phase, add the epoxy hardener of proper concn, epoxy is solidified in oil/water interface.Control curative concentration, temperature of reaction and reaction times, making solidification in turn by showing to proceed to inwards to a certain degree stop, just can obtain the microcapsule of the coated uncured epoxy resin of cured epoxy resin of certain wall thickness.Benefit of the present invention is, with the home position polymerization reaction of simple interface solidification substituted in reaction complexity, cyst wall is formed by part capsule-core curing reaction, for commaterial, not only enormously simplify preparation technology, also be beneficial to and the parameter of microcapsule is controlled, be particularly suitable for preparing the self-repair material microcapsule of specifying the mechanics required to trigger.
Accompanying drawing explanation
The scanning electron photomicrograph of the epoxy resin micro-capsule that Fig. 1 provides for the technical program first embodiment.
The scanning electron photomicrograph of the epoxy resin micro-capsule that Fig. 2 provides for the technical program second embodiment.
The scanning electron photomicrograph of the microcapsule that Fig. 3 provides for the technical program comparative example.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A kind of epoxy resin micro-capsule, described epoxy resin micro-capsule comprises capsule-core and cyst wall, and the described capsule heart forms by epoxy resin or containing the mixture of epoxy resin, and described cyst wall is reacted by the part epoxy in capsule-core and solidifying agent and obtains.
Described epoxy resin is bisphenol type epoxy, bisphenol F type epoxy, bisphenol S type epoxy or phenol aldehyde type epoxy resin.
A preparation method for described epoxy microcapsule, comprises the following steps:
The first step, is dispersed in the water containing tensio-active agent by epoxy resin or its mixture, forms emulsion.
Second step, adds solidifying agent or aqueous solution of curing agent, and mixes, obtain homogeneous system in described emulsion.
3rd step, changes described system temperature, stirs simultaneously, and solidifying agent and epoxy resin are reacted.
4th step, by throw out water rinse, dry, obtain epoxy resin micro-capsule.
In the described the first step, described epoxy resin is one-component, water insoluble, and the type of epoxy resin is not limit.The composition of described epoxy resin composition, except epoxy resin, also comprises one or more in curing catalyst, thinner, solvent, coupling agent, latent curing agent.
Described tensio-active agent is nonionic surface active agent or high molecular polymer nonionic and aniorfic surfactant, can be preferably SMA(phenylethylene-maleic anhydride segmented copolymer), gum arabic, polyoxyethylene polyoxypropylene (Pluronic series), ethylenediamine polyoxyethylene-oxypropylene block polyethers (Tetronic series), assorted block type polyethers (Tergitol series, Pluradot series, Plurafac series), tween (tween, Span Soxylat A 25-7), department class (span, sorbitan fatty acid ester), PVA(polyvinyl alcohol), PEG(polyoxyethylene glycol), alkylphenol polyoxyethylene (OP series, TX series, NP series), fatty alcohol-polyoxyethylene ether (peregal series, AEOn, JFC), APG(alkyl polyglycoside, alkyl glycoside) in one or both and two or more composite.
In the described the first step, the weight percent of described water, epoxy resin or its mixture, tensio-active agent is 100:5-30:2-10.
In described second step, described solidifying agent can be dissolved in the water of 0-90 DEG C, but not with the epoxy resin in the described the first step or its mixture miscible.Described solidifying agent except with the epoxy resin in the described the first step except, do not react with other component arbitrary in epoxy resin composition, namely described solidifying agent does not react with one or more in described curing catalyst, thinner, solvent, coupling agent, latent curing agent.
In described second step, described solidifying agent is tertiary amines solidifying agent or the primary polyamine class solidifying agent except aliphatics primary polyamine, is preferably m-xylene diamine (m-XDA), diaminodiphenyl-methane (DDM), diamino diphenyl sulfone (DDS), mphenylenediamine (m-PDA), alkane diamines in the Meng (MDA), N-aminoethyl piperazine (N-AEP), 1,3-bis-(gamma-amino propyl group)-5,5-dimethyl hydantion, hexanodioic acid two acyl trap (AADH), benzyldimethylamine (n, n '-dimthylbenzylamine, BDMA), 2-(dimethylamino methyl) phenol (DMP-10), 2,4,6-tri-(dimethylamino methyl) phenol (DMP-30), piperidines (piperidine), N, N'-lupetazin (n, n'-dimethylpiperazine), triethylenediamine (triethylenediamine), pyridine (pyridine), picoline (Methylpyridine), N-methyl piperidine (n-methylpiperidine), the mixing of one or more in 1,8-dichloro dicyclo (5,4,0)-7-hendecene (1,8-diazabicyclo [5.4.0] undec-7-ene).
In described second step, described solidifying agent does not comprise aliphatic polybasic uncle amine curing agent.
In described second step, the consumption of described solidifying agent is that 10 ~ 50% or controlled concentration of epoxy resin epoxy value are within the scope of 0.1 ~ 10wt%.
In described step the 3rd step, described temperature of reaction is 25-90 DEG C, stir speed (S.S.) 50-1000 rpm, and the reaction times is 5-90 minute.
Below, specifically by embodiment, epoxy resin micro-capsule that the technical program provides and preparation method thereof is described.
Embodiment 1
The first step, the SMA(Scripset520 of water intaking 100 milliliters and 10 milliliters 10wt%) aqueous solution, 6 milliliters of 4wt%PVA(Mw=1500) aqueous solution, mixing, adds 30 grams of bisphenol A type epoxy resin E-51(oxirane value=0.54).Mechanical stirring 15 minutes, rotating speed 400-600 rpm, obtains stable oil-in-water-type epoxy resin latex.
Second step, gets mphenylenediamine (molecular weight 108.14) 7 grams, and add 20 grams of water and make aqueous solution of curing agent, slowly add in described epoxy resin latex, stirring at low speed, rotating speed 100 rpms, obtains homogeneous system.
3rd step, is warming up to 70 DEG C by described homogeneous system simultaneously, insulation reaction 30 minutes, stop heating, to be cooled to room temperature stop again stir, obtain reaction solution.
3rd step, by described reacting liquid filtering, by filter cake 100 ml water rinsings, refilters, 3 times repeatedly, and then 40 DEG C of dryings 5 hours, obtain Beige powder product.
Carry out electron microscopy observation after being crushed by product, refer to Fig. 1, turn out to be the microcapsule of capsule-core/cyst wall structure, particle diameter 40-100 μm, thick about 2.7 μm of cyst wall.
Embodiment 2
The first step, fetches water 1000 milliliters, the SMA(Scripset520 of 100 milliliters of 10wt%) aqueous solution, 60 milliliters of 4wt%PVA(Mw=1500) aqueous solution, m-xylene diamine (molecular weight 136.13) 88 grams, mixing, as external phase.
Second step, get 300 grams of low viscosity epoxy E-58(hexahydrophthalic acid 2-glycidyl fat, oxirane value=0.58, viscosity 700mPas@25 DEG C) as disperse phase, by high-throughput SPG membrane emulsifier (SPG film specification: φ 10 × L125mm, 50 μm, aperture) emulsification, obtain the epoxy E-58 emulsion that droplet size is homogeneous.
3rd step, is warming up to 80 DEG C by emulsion, slow mixing speed 50 rpms, reacts after 15 minutes, is cooled to room temperature, stops stirring.
4th step, filter, 500 ml water rinsings, refilter, 3 times repeatedly, and last 40 DEG C of dryings 5 hours, obtain epoxy Beige powder.
Carry out electron microscopy observation after crushing, refer to Fig. 2, confirm sized by product homogeneous (particle diameter about 100 μm), the epoxy resin bag epoxy resin micro-capsule of capsule uniform wall thickness (=1.5 μm).
Embodiment 3
The first step, fetches water 100 milliliters, adds 4 grams of tween-80s and 1 gram of span-80 makes emulsifying agent, and mixing, adds 30 grams of bisphenol type epoxy E-51(oxirane value=0.54), mechanical stirring 15 minutes, rotating speed 500 rpms, obtains stable oil-in-water-type epoxy emulsion.
Second step, gets solidifying agent DMP-30(molecular weight 342.57) 23 grams, add 40 grams of water and make aqueous solution of curing agent, slowly add in epoxy emulsion, stirring at low speed, rotating speed 100 rpms.
3rd step, is warming up to 40 DEG C simultaneously, insulation reaction 20 minutes, stop heating, to be cooled to room temperature stop again stir.
4th step, by reacting liquid filtering, by filter cake 100 ml water rinsings, refilters, 3 times repeatedly, and then 40 DEG C of dryings 5 hours, obtain Beige powder.Electron microscopy observation confirms that product is the coated epoxy microcapsule of epoxy, particle diameter 40-70 μm.
Embodiment 4
The first step, fetches water 100 milliliters, adds 2 grams of gum arabics and makes emulsifying agent, mixing, add 30 grams of Racemic glycidol amine epoxy AG-80(4,4-diaminodiphenylmethane epoxy, oxirane value=0.8) in, mechanical stirring 15 minutes, rotating speed 500 rpms, obtains stable oil-in-water-type epoxy emulsion.
Second step, gets DDS (DDS, molecular weight 248.30) 16 grams, joins in the water of 40 grams 80 DEG C to dissolve to make the aqueous solution, slowly adds in epoxy emulsion, stirring at low speed, rotating speed 50 rpms.
3rd step, is warming up to 80 DEG C simultaneously, insulation reaction 30 minutes, stop heating, to be cooled to room temperature stop again stir.
4th step, by reacting liquid filtering, by filter cake 100 ml water rinsings, refilters, 3 times repeatedly, then 40 DEG C of dryings 5 hours, epoxy Beige powder.Electron microscopy observation confirms, product is the coated epoxy microcapsule of epoxy, particle diameter 20-60 μm.
Embodiment 5
The first step, fetch water 100 grams, the SMA(Scripset520 of 10 milliliters of 10wt%) aqueous solution, 6 milliliters of 4wt%PVA(Mw=1500) aqueous solution, mixing, add 30 Kehaiyin medicine epoxy resin MHR070(5,5-Dimethylhydantoin epoxy, Wuxi Meihua Chemical Co., Ltd.'s product, oxirane value 0.70 ~ 0.72) and 3 grams of titanic acid ester curing catalyst TC-114, mechanical stirring 15 minutes, rotating speed 500 rpms, obtains stable oil-in-water-type epoxy emulsion.Second step, gets 593 solidifying agent (affixture of diethylenetriamine and butylglycidyl ether, molecular weight 217.13, amine value=600 ~ 700mgKOH/g) 18 grams, add 20 grams of water and make aqueous solution of curing agent, slowly add in epoxy emulsion, stirring at low speed, rotating speed 100 rpms.
3rd step, is warming up to 80 DEG C simultaneously, insulation reaction 60 minutes, stop heating, to be cooled to room temperature stop again stir.
4th step, by reacting liquid filtering, by filter cake 100 ml water rinsings, refilters, 3 times repeatedly, and then 40 DEG C of dryings 5 hours, obtain Beige powder.Electron microscopy observation confirms, product is the coated epoxy microcapsule of epoxy, particle diameter 40-60 μm.
Embodiment 6
The first step, fetches water 100 grams, adds 3 grams of tween 20s, emulsifying agent made by 1.35 Ke Siban-60 and 0.25 gram polyoxyethylene glycol (PEG-6000), mixing, adds 30 grams of TDE-85 epoxy resin and (has another name called 712 epoxy resin, 4,5-epoxyclyclohexyl-1,2-diglycidyl diformate, 4,5-epoxy-cyclohexane-1,2-dioctyl phthalate 2-glycidyl fat, oxirane value=0.85), mechanical stirring 15 minutes, rotating speed 400-600 rpm, obtains stable oil-in-water-type epoxy emulsion.
Second step, gets benzyldimethylamine (molecular weight 135.21) 14 grams, adds 20 grams of water and makes aqueous solution of curing agent, slowly add in epoxy emulsion, stirs, rotating speed 300 rpms.
3rd step, is warming up to 80 DEG C simultaneously, insulation reaction 20 minutes, stop heating, to be cooled to room temperature stop again stir.
4th step, by reacting liquid filtering, by filter cake 100 ml water rinsings, refilters, 3 times repeatedly, and then 40 DEG C of dryings 5 hours, obtain Beige powder.Electron microscopy observation confirms, product is the coated epoxy microcapsule of epoxy, particle diameter 10-50 μm.
Comparative example 1
Fetch water 100 grams, the SMA(Scripset520 of 10 milliliters of 10wt%) aqueous solution, 6 milliliters of 4wt%PVA(Mw=1500) aqueous solution, mixing, add 30 grams of bisphenol type epoxy E-51(oxirane value=0.54), mechanical stirring 15 minutes, rotating speed 400-600 rpm, obtains stable oil-in-water-type epoxy emulsion; Get quadrol (molecular weight 60.10) 4 grams, add 20 grams of water and make aqueous solution of curing agent, slowly add in epoxy emulsion, stirring at low speed, rotating speed 100 rpms, is warming up to 70 DEG C simultaneously, insulation reaction 20 minutes, stops heating, to be cooled to room temperature, stops stirring; By reacting liquid filtering, by filter cake 100 ml water rinsings, refilter, 3 times repeatedly, then 40 DEG C of dryings 5 hours, obtain Beige powder.Product is carried out electron microscope observation, and finding substantially is the solid bead of epoxy, as shown in Figure 3.
As can be seen from above-mentioned comparative example, adopt quadrol, i.e. aliphatic amide, most of fatty amine curing agent meeting and epoxy miscible, be difficult to meet interfacial reaction conditions, and general curing reaction speed is very fast, and reaction is difficult to obtain the microcapsule of core/shell structure.
Disclosed in the technical program, the preparation method of epoxy resin micro-capsule has following features: the formation of (1) cyst wall is reacted based on the interface solidification of epoxy, and require that epoxy is in oil phase, solidifying agent is in aqueous phase; (2) only have part epoxy to participate in interface solidification reaction, remaining epoxy is wrapped in capsule as renovation agent becomes core.Certain core, except epoxy resin, can also comprise epoxy resin diluent, latent curing agent, curing catalyst and other additive that can improve epoxy mobility, improve bonding force, accelerate or delay core epoxy resin cure process; (3) wall material epoxy resin and core epoxy resin are same epoxy resin, and wall material is by the ethylene oxide group open loop in core epoxy molecule, then is formed with the addition of solidifying agent molecule; (4) cyst wall can be formed fast, usually completes in one hour.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an epoxy resin micro-capsule, described epoxy resin micro-capsule comprises capsule-core and cyst wall, and described capsule-core forms by epoxy resin or containing the mixture of epoxy resin, and described cyst wall is reacted by the part epoxy in capsule-core and solidifying agent and obtains; Described solidifying agent not with epoxy resin or its mixture miscible.
2. epoxy resin micro-capsule as claimed in claim 1, it is characterized in that, described solidifying agent is tertiary amines solidifying agent or the primary polyamine class solidifying agent except aliphatics primary polyamine.
3. epoxy resin micro-capsule as claimed in claim 1, it is characterized in that, described solidifying agent is m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, mphenylenediamine, the Meng alkane diamines, N-aminoethyl piperazine, 1, 3-bis-(gamma-amino propyl group)-5, 5-dimethyl hydantion, hexanodioic acid two acyl trap, benzyldimethylamine, 2-(dimethylamino methyl) phenol, 2, 4, 6-tri-(dimethylamino methyl) phenol, piperidines, N, N'-lupetazin, triethylenediamine, pyridine, picoline, N-methyl piperidine, 1, 8-dichloro dicyclo (5, 4, 0) mixing of one or more in-7-hendecene.
4. epoxy resin micro-capsule as claimed in claim 1, is characterized in that, the described mixture containing epoxy resin comprises epoxy resin, also comprises one or more in curing catalyst, thinner, solvent, coupling agent, latent curing agent.
5. a preparation method for epoxy resin micro-capsule, comprises step:
Epoxy resin or its mixture are dispersed in the water containing tensio-active agent, form emulsion;
In described emulsion, add solidifying agent or aqueous solution of curing agent, and mix, obtain homogeneous system; Described solidifying agent not with epoxy resin or its mixture miscible;
Change described system temperature, stir simultaneously, solidifying agent and epoxy resin are reacted; And
By throw out water rinse, dry, obtain epoxy resin micro-capsule.
6. the preparation method of epoxy resin micro-capsule as claimed in claim 5, it is characterized in that, the weight percent of described water, epoxy resin or its mixture, tensio-active agent is 100:5-30:2-10.
7. the preparation method of epoxy resin micro-capsule as claimed in claim 5, it is characterized in that, the consumption of described solidifying agent is that 10 ~ 50% or controlled concentration of epoxy resin epoxy value are within the scope of 0.1 ~ 10wt%.
8. the preparation method of epoxy resin micro-capsule as claimed in claim 5, is characterized in that, described solidifying agent and epoxy resin react for 25-90 DEG C, stir speed (S.S.) 50-1000 rpm, and the reaction times is 5-90 minute.
9. the preparation method of epoxy resin micro-capsule as claimed in claim 5, it is characterized in that, described tensio-active agent is nonionic surface active agent or high molecular polymer aniorfic surfactant.
10. the preparation method of epoxy resin micro-capsule as claimed in claim 5, it is characterized in that, described tensio-active agent be in SMA, gum arabic, polyoxyethylene polyoxypropylene, ethylenediamine polyoxyethylene-oxypropylene block polyethers, tween, class of department, PVA, PEG, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, APG one or both and two or more composite.
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| PCT/CN2013/080880 WO2014194560A1 (en) | 2013-06-03 | 2013-08-06 | Epoxy microcapsule and preparation method thereof |
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| CN110938192A (en) * | 2019-12-05 | 2020-03-31 | 肇庆市海特复合材料技术研究院 | Preparation method of microcapsule rapid curing agent with epoxy resin as wall material |
| CN113480199B (en) * | 2021-08-02 | 2022-11-01 | 四川文理学院 | Enhanced basalt fiber impregnating compound and preparation method thereof |
| CN113908782B (en) * | 2021-08-13 | 2024-05-24 | 深圳市深赛尔股份有限公司 | Environment-friendly epoxy resin self-repairing microcapsule and preparation process thereof |
| CN114854385B (en) * | 2022-03-21 | 2023-11-03 | 中国石油化工股份有限公司 | Asphaltene dispersion inhibitor with wrapping shell and preparation method thereof |
| CN114891318A (en) * | 2022-05-20 | 2022-08-12 | 重庆大学 | Novel intelligent insulating material for realizing self-healing of electric tree damage and preparation method and application thereof |
| CN116278238B (en) * | 2022-11-28 | 2023-09-12 | 江苏耀鸿电子有限公司 | High-temperature-resistant epoxy resin-based copper-clad plate and preparation method thereof |
| CN117645430A (en) * | 2023-11-30 | 2024-03-05 | 吉林省水利科学研究院(吉林省水利科技推广总站、吉林省水利水电工程质量检测中心、吉林省灌溉试验中心站) | Double microcapsule preparation method for self-repairing concrete freeze-thawing damage |
Citations (2)
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| CN101319055A (en) * | 2007-11-27 | 2008-12-10 | 中山大学 | Epoxy resin micro-capsule and its preparation method |
| CN101530772A (en) * | 2009-03-13 | 2009-09-16 | 清华大学深圳研究生院 | Preparing method for phase transited stored energy microcapsule covered with an organic polymer material |
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| KR20020071793A (en) * | 2002-06-05 | 2002-09-13 | 조석형 | Preparation of epoxy type adhesives |
| WO2005054393A1 (en) * | 2003-12-03 | 2005-06-16 | Three Bond Co., Ltd. | Microcapsule type adhesive composition |
| JP5228644B2 (en) * | 2007-10-05 | 2013-07-03 | 日立化成株式会社 | Microcapsule type latent curing agent for epoxy resin and method for producing the same, one-pack epoxy resin composition and cured epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101319055A (en) * | 2007-11-27 | 2008-12-10 | 中山大学 | Epoxy resin micro-capsule and its preparation method |
| CN101530772A (en) * | 2009-03-13 | 2009-09-16 | 清华大学深圳研究生院 | Preparing method for phase transited stored energy microcapsule covered with an organic polymer material |
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