CN104624132A - Epoxy resin self-repairing microcapsule and preparation method thereof - Google Patents
Epoxy resin self-repairing microcapsule and preparation method thereof Download PDFInfo
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- CN104624132A CN104624132A CN201310548440.6A CN201310548440A CN104624132A CN 104624132 A CN104624132 A CN 104624132A CN 201310548440 A CN201310548440 A CN 201310548440A CN 104624132 A CN104624132 A CN 104624132A
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- 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
Abstract
The invention provides an epoxy resin self-repairing microcapsule and a preparation method thereof. The method comprises the following steps: mixing a water phase containing inorganic nanoparticles and water with an oil phase containing epoxy resin, monoolefin monomer, a polyene cross-linking agent and an initiator to form a stable oil-in-water emulsion; and heating the emulsion to realize emulsion polymerization in order to form the epoxy resin self-repairing microcapsule. The epoxy resin self-repairing microcapsule is prepared by adopting the inorganic nanoparticles as an emulsifier through an emulsion polymerization process via the method; and compared with methods adopting molecular emulsifiers, the method provided by the invention has the advantages of no need of subsequent emulsifier removal, simple process, and no pollution to environment. The epoxy resin self-repairing microcapsule prepared in the invention has the advantages of excellent stability, excellent leakproofness and high cladding rate.
Description
Technical field
The present invention relates to the technical field of composite materials with self-repair function, more specifically, the present invention relates to epoxy resin self-repairing microcapsule adopting emulsion polymerization synthesis and preparation method thereof.
Background technology
The concept of the composite of self-repair function first by US military in 20th century the mid-80 propose.Self-repairing system is the earliest the simple analog to animal blood vessels network, by hollow glass fibre Transducers Embedded in Concrete, injects acetal Polymer Solution as bonding agent in fiber.Due to the difficult point in hollow fibre network system manufacture method, this technology is difficult to realize automation preparation, is therefore difficult to enter commercial Application.
At present both at home and abroad the self-repairing microcapsule of most study is with the coated DCPD(dicyclopentadiene of uramit) microcapsule systems of monomer synthesize.The people (see documents and materials 1-3) such as J.S.Moore and the Scottos N.R. of Illinois, USA university are from the research being devoted to self-repair technology since eighties of last century the mid-90 always.This technology makes catalyst with ruthenium complex Grubbs, and at the microcapsules (capsule wall material is Lauxite) of the defect area initiation micron-scale of epoxy substrate, breaking discharges DCPD, and active ring-opening polymerization occurs the latter, reaches the effect of selfreparing.But there is following shortcoming in the above-mentioned self-healing system being key component with DCPD microcapsules: Grubbs catalyst price is high; Instability, easily decomposing higher than when 120 DEG C, and is subject to the impact of epoxy curing agent amine and weakens catalytic efficiency in building-up process; Although DCPD microcapsules have achieved good effect in the polymer matrix composite reparation of room temperature forming, but because DCPD exists α and β two kinds of isomers (congealing point is respectively 19.5 DEG C and 33 DEG C), so the selfreparing of composite that DCPD uses under not being suitable for low temperature; The mechanical property of DCPD polymeric reaction product is lower; Prepare in the process of Lauxite wall material traditional, main material is formaldehyde, and teratogenesis and the toxicity of the latter are proved, therefore prepares low formaldehyde or formaldehydeless phase-change microcapsule is very important.In addition, rich three professors of northeastern Japan university three bridge wait (documents and materials 4) to mix in concrete material by the Capsules including bonding agent, once concrete ftractures under external force, partial capsules breaks, adhering liquid flows into crackle, and adhering liquid can make concrete cracks again heal.But this Capsules size comparatively large (2-35mm) and uneven, is unfavorable for capsule and matrix compound, thus has a significant impact matrix mechanical strength.
Biliographic data:
The people such as non-patent literature data 1:Jones A.S.Rule J.D. and Moore J.S., Catalyst Morphology and Dissolution Kinetics of Self-Healing Polymers, Chem.Mater.2006; 18:1312-1317
Non-patent literature data 2:Keller M.W., White S.R. and Sottos N.R. etc., A Self-healing Poly (Dimethyl Siloxane) Elastomer, Adv.Funct.Mater., 2007; 17:2399-2404
Non-patent literature data 3:Rule J.D., Brown E.N. and Sottos N.R., Wax-protected Catalyst Microspheres for Efficient Self-healing Materials, Adv.Mater., 2005; 17:205-208
Non-patent literature data 4: Zhang Xiong, practises will and attains, Wang Shengxian and Yao Wu etc., the progress of Biological Modelling Self-healing Concrete, concrete, calendar year 2001; 137:10-13
Summary of the invention
The object of this invention is to provide a kind of preparation method of epoxy resin self-repairing microcapsule, the method can control the particle diameter of self-repairing microcapsule by emulsification pretreatment, thus obtained size is from several microns to nearly hundred microns and the epoxy resin micro-capsule be evenly distributed, thus the mechanics plyability between self-repairing microcapsule and matrix material is stablized.
A further object of the present invention is to provide a kind of preparation method of epoxy resin self-repairing microcapsule, and the method adopts inorganic nanoparticles as emulsifying agent and prepares epoxy resin self-repairing microcapsule by emulsion polymerization; Compared with adopting the method for molecule-type emulsifying agent, the method without the need to the process of follow-up removal emulsifying agent, technique in this way simple, cost is low and environmentally safe.
The micron order epoxy resin self-repairing microcapsule that a further object of the present invention is to provide a kind of stability and seal is excellent, clad ratio is high.
Foregoing invention object is achieved through the following technical solutions:
According to an aspect of the present invention, a kind of method preparing epoxy resin self-repairing microcapsule is provided, comprises:
A) nano inorganic composition granule be added to the water and disperseed, using the dispersion liquid obtained as aqueous phase;
B) epoxy resin, monoene hydrocarbon monomer, Polyene Hydrocarbons crosslinking agent and initator are mixed, using the mixed liquor obtained as oil phase;
C) by aqueous phase and oil phase mixing, and carry out stirring to form stable O/w emulsion; And
D) heating described emulsion makes it carry out emulsion polymerisation, and to be formed with epoxy resin be core, using the polymer of monoene hydrocarbon monomer and the copolymerization of Polyene Hydrocarbons crosslinking agent as the selfreparing epoxy resin micro-capsule of wall material.
Further, described method preferably includes and e) liquid containing epoxy resin self-repairing microcapsule that step d) obtains is carried out spraying dry, to obtain the dry powder of epoxy resin self-repairing microcapsule.
According to another aspect of the present invention, a kind of epoxy resin self-repairing microcapsule is provided, described microcapsules take epoxy resin as core, be shell portion with one or more monoene hydro carbons monomer polymerizations and through the polymer of Polyene Hydrocarbons cross-linking agents, wherein, described epoxy resin self-repairing microcapsule is prepared by said method.
Preparation method according to epoxy resin self-repairing microcapsule of the present invention has universality, can prepare the self-repairing microcapsule of a series of different core and wall material, and the composition of self-repairing microcapsule and shell controlled.Such as, the method can be used for multiple epoxy resin as core, such as, bisphenol A type resin E51 and novolac epoxy resin F44 etc., with various polymer for wall material, such as, polyacrylonitrile and polymethyl methacrylate etc., thus the self-repairing microcapsule obtaining different composition and performance.In addition, method technique of the present invention is simple, can one-step synthesis method, and the stability of the microcapsules of preparation and seal is excellent, green non-pollution.Method emulsification pretreatment of the present invention can control the particle diameter of self-repairing microcapsule, thus obtained size is from several microns to nearly hundred microns and the epoxy resin micro-capsule be evenly distributed, this capsule can with the good compound of matrix material and without embrittlement, little to matrix Effect on Mechanical Properties.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) figure of the epoxy resin self-repairing microcapsule prepared by embodiment 1;
Fig. 2 is transmission electron microscope (TEM) figure of the epoxy resin self-repairing microcapsule prepared by embodiment 1;
Fig. 3 is infrared spectrum (IR) figure of the epoxy resin self-repairing microcapsule prepared by embodiment 1;
Fig. 4 is thermal weight loss (TGA) curve map of the epoxy resin self-repairing microcapsule prepared by embodiment 1;
Fig. 5 is according to the process chart preparing epoxy resin self-repairing microcapsule method of the present invention.
Detailed description of the invention
Below specifically the specific embodiment of the present invention is described in detail.
According to an aspect of the present invention, provide a kind of method preparing epoxy resin self-repairing microcapsule, it comprises: a) be added to the water by nano inorganic composition granule and disperseed, using the dispersion liquid obtained as aqueous phase; B) epoxy resin, monoene hydrocarbon monomer, Polyene Hydrocarbons crosslinking agent and initator are mixed, using the mixed liquor obtained as oil phase; C) by aqueous phase and oil phase mixing, and carry out stirring to form stable O/w emulsion; And d) heat described emulsion and make it carry out emulsion polymerisation, to be formed with epoxy resin be core, using the polymer of monoene hydrocarbon monomer and the copolymerization of Polyene Hydrocarbons crosslinking agent as the selfreparing epoxy resin micro-capsule of wall material.
Further, described method also comprise e) step d) is obtained carry out spraying dry, to obtain the dry powder of epoxy resin self-repairing microcapsule containing the liquid of epoxy resin self-repairing microcapsule.Preferably, the drying means that described drying steps can be commonly used by other, as long as this drying means does not destroy the structure of microcapsules and forms.Such as, the method such as can adopt low temperature drying or naturally dry.
Nano-inorganic substance used in the methods of the invention can be the particles of inorganic material of any stable chemical nature.Such as, described nano-inorganic substance particle emulsifying agents can imvite, lithium algae soil, carborundum, silica, barium sulfate, calcium carbonate, iron oxide or titanium dioxide, can use wherein one or more.At least one in preferred use lithium algae soil and carborundum.
Further, the average particle size particle size of preferred described nano-inorganic substance particle emulsifying agents is 1nm ~ 1000nm, is preferably 20nm ~ 800 μm, is more preferably 80-700nm, most preferably is 100-600nm.
Further, preferred described monoene hydrocarbon monomer is selected from one or more in styrene, methyl styrene, methyl methacrylate, EMA, butyl methacrylate, Tert-butyl Methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate and acrylic acid tricaprylate.Preferably, the amount of described monoene hydrocarbon monomer is 20 ~ 80 % by weight relative to epoxide resin material.
Further, described Polyene Hydrocarbons crosslinking agent is preferably selected from one or more in divinylbenzene, GDMA, dimethyl propylene acid propylene glycol ester, tetramethylene dimethacrylate and dimethacrylate hexylene glycol ester.The amount of described Polyene Hydrocarbons crosslinking agent is preferably 5 ~ 80 % by weight relative to described epoxide resin material.
Further, described initator is azodiisobutyronitrile, ABVN, benzoyl peroxide or potassium peroxydisulfate.Be more preferably azodiisobutyronitrile.
Further, before oil phase is mixed with water, heating oil phase component makes it reach the temperature of 60 DEG C, thus each component of oil phase is mixed.Preferably, after oil phase is mixed with water, use homogenizer to carry out shear agitation, thus form stable O/w emulsion.
Further, the mixture of oil phase and aqueous phase is heated to more than 70 DEG C to carry out described polymerisation.
Further, described monoene hydrocarbon monomer is styrene, and described Polyene Hydrocarbons crosslinking agent is divinylbenzene, and described crosslinking agent is azodiisobutyronitrile.
Further, described epoxy resin is at least one in bisphenol A type resin E51 and novolac epoxy resin F44.
According to a further aspect in the invention, a kind of epoxy resin self-repairing microcapsule is provided, described microcapsules take epoxy resin as core, be shell portion with one or more monoene hydro carbons monomer polymerizations and through the polymer of Polyene Hydrocarbons cross-linking agents, wherein, described epoxy resin self-repairing microcapsule is prepared by said method.
Further, the particle diameter of prepared epoxy resin self-repairing microcapsule is 0.1 ~ 1000 μm, is preferably 1 ~ 50 μm.
Preparation method according to epoxy resin self-repairing microcapsule of the present invention has universality, can prepare the self-repairing microcapsule of a series of different core and wall material, and the composition of self-repairing microcapsule and shell controlled.Such as, the method can be used for multiple epoxy resin as core, such as, bisphenol A type resin E51 and novolac epoxy resin F44 etc., with various polymer for wall material, such as, polyacrylonitrile and polymethyl methacrylate etc., thus the self-repairing microcapsule obtaining different composition and performance.In addition, method technique of the present invention is simple, can one-step synthesis method, and the stability of the microcapsules of preparation and seal is excellent, green non-pollution.Method emulsification pretreatment of the present invention can control the particle diameter of self-repairing microcapsule, thus obtained micron order size and the epoxy resin micro-capsule be evenly distributed, this capsule can with the good compound of matrix material and without embrittlement, little to matrix Effect on Mechanical Properties.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Be to be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition, to have read disclosed in the present invention or instruction content after, those skilled in the art can make various amendment and/or improvement to the present invention, and these amendments or the forms improved fall within claims limited range of the present invention all equally.Again, the experimental technique used in following embodiment if no special instructions, is conventional method; Material used in following example, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1
0.5 g lithium algae soil particle (buy from Lockwood (Rockwood) company, average grain diameter is 105nm, and maximum particle diameter is 500 nm, minimum grain size 20 nm) is joined in 100 g water, obtains dispersion liquid as aqueous phase.By 1.0g bisphenol A type epoxy resin E51(buy from blue star new material company), 0.5g oil-soluble monomer styrene (St), 0.5g oil-soluble crosslinking agent divinylbenzene (DVB), 0.5g styrene and 0.002g initator azodiisobutyronitrile (AIBN) mixing, using this mixed liquor as oil phase.Described aqueous phase, oil phase are put into respectively 70 DEG C of baking ovens to heat 20 minutes and carry out preheating in 3 minutes, stirring makes each component of oil phase mix (mass ratio of the gross mass of its epoxy resin E51 and monomer and crosslinking agent is 1:1, divinylbenzene and styrene mass ratio 1:1).By aqueous phase and oil phase mixing, under employing 12000rpm rotating speed, high speed shear 30 seconds, obtains stable O/w emulsion.
This emulsion system is transferred to the reactor being preheated to 70 DEG C in advance, passes into inert nitrogen gas, rotating speed is mechanical agitation under 300rpm, 70 DEG C of polymerisations 12 hours.Along with the carrying out of polymerisation, divinylbenzene and styrene start copolyreaction occurs, and under the effect be separated, monomer and low molecule prepolymer migrate to oil-water interfaces from epoxy inner to be polymerized further, form the self-repairing microcapsule of core-shell structure copolymer.Detailed process can be shown in Figure 5.The dry powder of self-repairing microcapsule is obtained by spray drying process drying.
Stereoscan photograph observation is carried out to the self-repairing microcapsule of above-mentioned preparation, as shown in Figure 1.As seen from Figure 1: the size uniform of epoxy resin self-repairing microcapsule, average grain diameter is approximately about 10.0 μm.Results of IR as shown in Figure 2.Fig. 2 is the transmission electron microscope picture of prepared microcapsules, can find out that the seal of prepared epoxy resin self-repairing microcapsule is excellent.Further, as seen from Figure 3: the stretching vibration peak (1250-780cm of-C-O-C-of epoxy resin
-1) and DVB and St copolymer in phenyl ring skeletal vibration peak (1600-1450cm
-1article three, bands of a spectrum) high-visible.As shown in Figure 4, as seen from Figure 4: the complete decomposition temperature of core bisphenol A type epoxy resin E51 is about 330 DEG C, the complete decomposition temperature of wall material DVB and St copolymer is about 450 DEG C to thermogravimetric analysis further (TGA) test result.
In addition, as shown in Figure 5: the clad ratio of prepared epoxy resin self-repairing microcapsule is up to 87%.
After the microcapsules dry powder obtained after spraying dry is placed 30 days, detect the amount of the bisphenol A type epoxy resin E51 existing for microcapsule exterior surface, find that its content does not change substantially, this reflects seal and the excellent in stability of the epoxy resin self-repairing microcapsule prepared by the present embodiment.
Embodiment 2
0.5g silicon-carbide particle (is bought from Chemical Reagent Co., Ltd., Sinopharm Group, average grain diameter is 80nm, minimum grain size is 5nm, and maximum particle diameter is 230nm) and the aqueous solution of 0.2g potassium peroxydisulfate (1%KPS) join in 100g water, obtain dispersion liquid as aqueous phase.0.1g oil-soluble crosslinking agent ethylene glycol bisthioglycolate (methacrylic acid) ester (EGDMA) and 0.1g oil-soluble monomer methyl methacrylate (MMA) and 1.0g bisphenol A type epoxy resin E51 are mixed, using this mixed liquor as oil phase.Described aqueous phase, oil phase are put into respectively 70 DEG C of baking ovens to heat 20 minutes and carry out preheating in 3 minutes, stirring makes each component of oil phase mix (mass ratio of the gross mass of its epoxy resin E51 and monomer and crosslinking agent is 5:1, methyl methacrylate and ethylene glycol bisthioglycolate (methacrylic acid) ester mass ratio 1:1).By aqueous phase and oil phase mixing, under employing 1200rpm rotating speed, high speed shear 30 seconds, obtains stable O/w emulsion.
This emulsion system is transferred to the reactor being preheated to 70 DEG C in advance, passes into inert nitrogen gas, rotating speed is mechanical agitation under 300rpm, 70 DEG C of polymerisations 12 hours.Along with the carrying out of polymerisation, methyl methacrylate and ethylene glycol bisthioglycolate (methacrylic acid) ester start copolyreaction occurs, under the effect be separated, monomer and low molecule prepolymer migrate to oil-water interfaces from epoxy inner to be polymerized further, thus forms the self-repairing microcapsule of core-shell structure copolymer.Detailed process can be shown in Figure 5.This microcapsule emulsion using spray seasoning drying obtains the dry powder of self-repairing microcapsule.
ESEM and the observation of transmission electron microscope picture, infrared spectrum analysis and thermogravimetric analysis are carried out to the self-repairing microcapsule of above-mentioned preparation, its test result shows: the size uniform of epoxy resin self-repairing microcapsule, and draw particle size is approximately about 20.30 μm.Infrared spectrum analysis and thermal gravimetric analysis results are similar to the test result described in embodiment 1.
In addition, the clad ratio of the epoxy resin self-repairing microcapsule after tested prepared by the present embodiment is up to 89%, and seal and stability test result, as the test result of embodiment 1, are also all excellent.
Embodiment 3
0.5g lithium algae soil particle (is bought from Lockwood (Rockwood) company, average grain diameter is 105nm, maximum particle diameter is 500nm, minimum grain size 20nm) and 0.2g initator azodiisobutyronitrile (AIBN) join in 100g water, obtain dispersion liquid as aqueous phase.1.0g bisphenol A type epoxy resin F44(is bought from blue star new material company) purchased from Shanghai Resin Factory, 0.1g oil-soluble crosslinking agent divinylbenzene (DVB) and 0.1g styrene (St) mixing, using this mixed liquor as oil phase.Described aqueous phase, oil phase are put into respectively 70 DEG C of baking ovens to heat 20 minutes and carry out preheating in 5 minutes, stir and each component of oil phase is mixed (mass ratio of its epoxy resin F44 and monomer gross mass is 5:1, divinylbenzene and styrene mass ratio 1:1).The aqueous phase of above-mentioned preparation is mixed mutually with oil phase, and is warming up to 70 DEG C, adopt homogenizer stirring and emulsifying 30 seconds under the rotating speed of 9000 revs/min, obtain oil-in-water emulsion.
This emulsion system is transferred to the reactor being preheated to 70 DEG C in advance, passes into inert nitrogen gas, rotating speed is mechanical agitation under 300rpm, polymerisation 12 hours at 70 DEG C.Along with the carrying out of polymerisation, divinylbenzene and styrene start copolyreaction occurs, and under the effect be separated, monomer and low molecule prepolymer migrate to oil-water interfaces from epoxy inner to be polymerized further, form the self-repairing microcapsule of core-shell structure copolymer, detailed process can be shown in Figure 5.。The dry powder of self-repairing microcapsule is obtained by spray drying process drying.
Carry out stereoscan photograph observation, infrared spectrum analysis and thermogravimetric analysis to the self-repairing microcapsule of above-mentioned preparation, its test result shows: the size uniform of epoxy resin self-repairing microcapsule, and average grain diameter is about about 25.1 μm.Infrared spectrum analysis and thermal gravimetric analysis results are similar to the test result described in embodiment 1.
In addition, the clad ratio of the epoxy resin self-repairing microcapsule after tested prepared by the present embodiment is up to 87.5%, and seal and stability test result, as the test result of embodiment 1, are also all excellent.
Claims (16)
1. prepare a method for epoxy resin self-repairing microcapsule, comprising:
A) nano inorganic composition granule be added to the water and disperseed, using the dispersion liquid obtained as aqueous phase;
B) epoxy resin, monoene hydrocarbon monomer, Polyene Hydrocarbons crosslinking agent and initator are mixed, using the mixed liquor obtained as oil phase;
C) by aqueous phase and oil phase mixing, and carry out stirring to form stable O/w emulsion; And
D) heating described emulsion makes it carry out emulsion polymerisation, and to be formed with epoxy resin be core, using the polymer of monoene hydrocarbon monomer and the copolymerization of Polyene Hydrocarbons crosslinking agent as the selfreparing epoxy resin micro-capsule of wall material.
2. method according to claim 1, wherein, described method comprises further:
E) liquid containing epoxy resin self-repairing microcapsule that step d) obtains is carried out spraying dry, to obtain the dry powder of epoxy resin self-repairing microcapsule.
3. method according to claim 1, wherein, described nano-inorganic substance particle emulsifying agents is selected from least one in imvite, lithium algae soil, carborundum, silica, barium sulfate, calcium carbonate, iron oxide and titanium dioxide.
4. the method according to any one of claim 1-3, wherein, the average particle size particle size of described nano-inorganic substance particle emulsifying agents is 1nm ~ 600nm.
5. the method according to any one of claim 1-4, wherein, described monoene hydrocarbon monomer is selected from one or more in styrene, methyl styrene, methyl methacrylate, EMA, butyl methacrylate, Tert-butyl Methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate and acrylic acid tricaprylate.
6. the method according to any one of claim 1-5, wherein, the amount of described monoene hydrocarbon monomer is 20 ~ 80 % by weight relative to epoxide resin material.
7. the method according to any one of claim 1-6, wherein, described Polyene Hydrocarbons crosslinking agent is selected from one or more in divinylbenzene, GDMA, dimethyl propylene acid propylene glycol ester, tetramethylene dimethacrylate and dimethacrylate hexylene glycol ester.
8. the method according to any one of claim 1-7, wherein, the amount of described Polyene Hydrocarbons crosslinking agent is 5 ~ 80 % by weight relative to described epoxide resin material.
9. the method according to any one of claim 1-8, wherein, described initator is azodiisobutyronitrile, ABVN, benzoyl peroxide or potassium peroxydisulfate.
10. the method according to any one of claim 1-9, wherein, before oil phase is mixed with water, heating oil phase component makes it reach the temperature of 60 DEG C, thus each component of oil phase is mixed.
11. methods according to any one of claim 1-10, wherein, after oil phase is mixed with water, use homogenizer to carry out shear agitation, thus form stable O/w emulsion.
12. methods according to any one of claim 1-11, wherein, are heated to more than 70 DEG C to carry out described polymerisation by the mixture of oil phase and aqueous phase.
13. methods according to any one of claim 1-12, wherein, described monoene hydrocarbon monomer is styrene, and described Polyene Hydrocarbons crosslinking agent is divinylbenzene, and described crosslinking agent is azodiisobutyronitrile.
14. methods according to any one of claim 1-13, wherein, described epoxy resin is at least one in bisphenol A type resin E51 and novolac epoxy resin F44.
15. 1 kinds of epoxy resin self-repairing microcapsules, described microcapsules take epoxy resin as core, be shell portion with one or more monoene hydro carbons monomer polymerizations and through the polymer of Polyene Hydrocarbons cross-linking agents, wherein, described epoxy resin self-repairing microcapsule is prepared by the method according to any one of claim 1-14.
16. epoxy resin self-repairing microcapsules according to claim 15, wherein, the particle diameter of described epoxy resin self-repairing microcapsule is 1 ~ 50 μm.
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