CN107159070A - Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material - Google Patents
Self-repairing microcapsule and preparation method thereof, coating, coating and epoxy resin composite material Download PDFInfo
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- CN107159070A CN107159070A CN201710457708.3A CN201710457708A CN107159070A CN 107159070 A CN107159070 A CN 107159070A CN 201710457708 A CN201710457708 A CN 201710457708A CN 107159070 A CN107159070 A CN 107159070A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention provides a kind of preparation method of self-repairing microcapsule, comprise the following steps：A) emulsifying agent, urea, formaldehyde, reaction promoter, ethyl phenylacetate are mixed with water, emulsifies, obtains emulsion；B) by emulsion heating, reaction, self-repairing microcapsule is obtained.Present invention also provides a kind of self-repairing microcapsule, the cyst wall of the self-repairing microcapsule is Lauxite, and core includes ethyl phenylacetate.Present invention also provides a kind of coating and epoxy resin composite material including above-mentioned self-repairing microcapsule.Solvent-borne type self-repairing microcapsule technique prepared by the present invention is simple, and microcapsules regular appearance, stability is good.Because the core ethyl phenylacetate of self-repairing microcapsule has swelling action to epoxy resin, using the principle, solvent-borne type self-repairing microcapsule can repair epoxy resin-base crackle.
Description
Technical field
The present invention relates to Micro-Encapsulation Technique field, more particularly to self-repairing microcapsule and preparation method thereof, coating with
Coating.
Background technology
Polymer composites are influenceed during machine-shaping and use by environment, external force etc., surface and interior
Portion inevitably produces micro-crack.If this micro-crack can not be detected and repaired in time, composite wood can be caused by continuing extension
The MATRIX CRACKING of material or interlayer degumming, so as to cause the mechanical hydraulic performance decline of composite, thus may trigger macrocrack and go out
Existing brittle fracture, finally makes Failure Analysis of Composite Materials, and trigger major accident.
For this problem, scientists propose Smart self-repairing material concept.Smart self-repairing material is to imitate life
The principle that object tissue damage is healed automatically, polymer composites can automatically be repaiied to either internally or externally micro-crack
It is multiple, so that the mechanical property of reinforcing material, extends service life, is widely used in the fields such as automobile, space flight, aeronautical manufacture, it is right
Reduce equipment Maintenance Cost, reduce equipment repair time, extension equipment service life, it is ensured that weaponry is sent out in military struggle
Wave and be respectively provided with very important meaning in terms of maximum efficiency.
Self-healing system can be divided into Intrinsical self-healing system and hide type self-healing system；Its type of being caught in ambush reviews one's lessons by oneself complex
Series structure is simple, and repairing effect is good, receives extensive attention.The type self-healing system of hiding is with microcapsules, glass fibre or arteries and veins
The renovation agent of pipe parcel is unit, is embedded in polymeric matrix and is repaired；The repair process of microcapsules self-repair material is：
Crack Extension to microcapsules in matrix cause it to rupture, and the renovation agent in microcapsules flows to cracks under capillary action, are urging
Polymerisation repair crack occurs for renovation agent in the presence of agent.Because the preparation technology of microcapsule composite material is simple, it can repair
Extensively, a variety of damages to material can be repaired multiple matrix, the focus and emphasis as self-repair material.
According to different repair mechanisms, microcapsules self-healing system can be divided into chemical reaction type self-healing system and physics is handed over
Connection type self-healing system.The reparation reaction of chemical reaction type self-healing system mainly includes ring-opening metathesis polymerization, the ring of cycloolefin
The ring-opening polymerisation of oxygen tree fat and the reaction of the class of click chemistry three.What physical crosslinking type self-healing system mainly used solvent is swelled work
Use repair crack.
For chemical reaction type reparation system, renovation agent must be in catalyst or curing agent (for epoxy resin
For) could occur under catalytic action to repair reaction, and then repair crack.If catalyst is solid, and discord matrix
Learn reaction, then can Direct Uniform Dispersed precipitate in the base, such as DCPD/Grubbs repair system, epoxy resin/trifluoromethyl
Sulfonic acid scandium etc..If catalyst be liquid or catalyst can and matrix chemically react, need to be wrapped in microcapsules so that
Obtain it and reactivity is not lost in preparation process, and catalyst micro capsule and renovation agent microcapsules are broken simultaneously in Crack Extension
Split generation and repair reaction, the double microcapsules of such as epoxy resin/mercaptan, the double microcapsules of propargyl amine of azide/tri-, PETM sulfydryls
Compound/hexamethylene diisocyanate trimer etc..Therefore chemical reaction type self-healing system is according to catalyst or curing agent
Existence form, renovation agent microcapsules/catalyst system and double microcapsule systems can be divided into.
Chemical reaction type and the advantage and disadvantage of solvent microcapsule self-healing system are as shown in table 1；
The comparison table of the chemical reaction type of table 1 and solvent microcapsule self-healing system
Traditional microcapsule preparation method is roughly divided into chemical method, physical method and physico-chemical process from principle.
Situ aggregation method wherein in chemical method has the advantages that without Special Equipment, reaction speed is fast and reaction condition is gentle,
Therefore self-repair type microcapsules are generally prepared using situ aggregation method.According to whether needed in preparation technology previously prepared urea-
Formaldehyde prepolymer, but prepare that urea-formaldehyde performed polymer regulation pH speed is slow, technique is relatively complicated.
The content of the invention
Present invention solves the technical problem that be to provide a kind of preparation method of self-repairing microcapsule, the application provide from
The preparation method for repairing microcapsules is simple, and the self-repairing microcapsule prepared has preferable repairing effect as repair materials.
In view of this, this application provides a kind of preparation method of self-repairing microcapsule, comprise the following steps：
A), emulsifying agent, urea, formaldehyde, reaction promoter, ethyl phenylacetate are mixed with water, emulsifies, obtain emulsion；
B), by emulsion heating, reaction, self-repairing microcapsule is obtained.
It is preferred that, the preparation process of the emulsion is specially：
A1), emulsifying agent is mixed with water, heats, obtain emulsifier solution；
A2), urea, reaction promoter, water are mixed with the emulsifier solution, by obtained solution adjust pH value to
3.4~3.6；
A3), by ethyl phenylacetate and step A2) obtained solution mixes, formalin added after emulsification, breast is obtained
Liquid.
It is preferred that, the emulsifying agent be acid polyethylene anhydride emulsifying agent, polyvinyl alcohol emulsifying agent, polyethers emulsifying agent or
Polyesters emulsifying agent；The reaction promoter is resorcinol and ammonium chloride.
It is preferred that, the programming rate of the heating is 1~3 DEG C/min, the temperature of the heating to 50~60 DEG C, the liter
Insulation is not less than 4h after temperature.
It is preferred that, the addition of the urea is 5.0~6.0 parts by weight, and the addition of the ethyl phenylacetate is 40.0
~60.0 parts by weight, the addition of the formalin is 12.0~13.0 parts by weight, and the concentration of the formalin is
37wt%.
Present invention also provides a kind of self-repairing microcapsule, including cyst wall and core, the cyst wall is Lauxite, described
Core includes ethyl phenylacetate.
It is preferred that, the particle diameter of the self-repairing microcapsule is 100~250 μm, and wall thickness is 150~200nm.
Present invention also provides a kind of coating, including epoxy resin with it is prepared by the preparation method described in such scheme or
Self-repairing microcapsule described in such scheme.
It is preferred that, the content of the self-repairing microcapsule is 1wt%~15wt% of the epoxy resin.
Present invention also provides a kind of coating, substrate surface is coated on as the coating described in such scheme and obtained.
Present invention also provides a kind of epoxy resin composite material, as described in epoxy resin, curing agent and such scheme
Self-repairing microcapsule described in prepared by preparation method or such scheme is prepared.
It is preferred that, the curing agent is 10wt%~15wt% of the epoxy resin, and the self-repairing microcapsule is institute
State 1wt%~15wt% of epoxy resin.
This application provides a kind of preparation method of self-repairing microcapsule, it is first by emulsifying agent, urea, formaldehyde, reaction
Accelerator, ethyl phenylacetate are mixed with water, emulsification, obtain emulsion；By emulsion heating, reaction, self-repairing microcapsule is obtained.
The application has directly synthesized self-repairing microcapsule using one-step method, without previously prepared urea-formaldehyde performed polymer；Synthesis from
The cyst wall for repairing microcapsules is to react obtained Lauxite by urea and formaldehyde condensation polymer, and core is ethyl phenylacetate.The application
The self-repairing microcapsule of preparation is solvent-borne type self-repairing microcapsule, because ethyl phenylacetate has swelling action to epoxy resin,
Therefore, self-repairing microcapsule can be repaired by the crackle of its epoxy resin composite material formed or splitting by its coating formed
Line.
Brief description of the drawings
Fig. 1 is the OM photos that the embodiment of the present invention 1 does not observe microcapsules building-up process in the same time；
Fig. 2 is microcapsules electromicroscopic photograph prepared by the embodiment of the present invention 1；
Fig. 3 is self-repairing microcapsule/epoxy resin TDCB sample schematic diagrames prepared by the embodiment of the present invention 1；
Before and after self-repairing microcapsule/epoxy resin TDCB sample crack forming mechanisms that Fig. 4 is prepared for the embodiment of the present invention 1
SEM pictures；
Fig. 5 is the cut OM photos of Smart self-repairing coating different repair times prepared by the embodiment of the present invention 2；
Fig. 6 is the outline drawing of tension failure sample prepared by the embodiment of the present invention 3；
Fig. 7 is the self-repair efficiency control cylindricality of microcapsules/epoxy resin composite material prepared by the embodiment of the present invention 3
Figure；
Fig. 8 is that the cross-section morphology after the reparation of microcapsules/epoxy resin composite material prepared by the embodiment of the present invention 3 shines
Piece；
Fig. 9 is the crackle interface topography photo of microcapsules/epoxy resin composite material prepared by the embodiment of the present invention 3.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
For prior art polymer composites under the influence of external force and environment, easily there is the present situation of crackle, this hair
Bright embodiment discloses a kind of preparation method of self-repairing microcapsule, comprises the following steps：
A), emulsifying agent, urea, formaldehyde, reaction promoter, ethyl phenylacetate are mixed with water, emulsifies, obtain emulsion；
B), by emulsion heating, reaction, self-repairing microcapsule is obtained.
The application uses one-step method fabricated in situ Lauxite self-repairing microcapsule, and this method does not need previously prepared urine
Element-formaldehyde prepolymer, but the cyst wall of microcapsules, phenylacetic acid are directly solidify to form by urea and formaldehyde condensation polymer in acid condition
Ethyl ester forms the core of microcapsules as renovation agent.
Specifically, during self-repairing microcapsule is prepared, first by emulsifying agent, urea, formaldehyde, reaction promoter,
Ethyl phenylacetate is mixed with water, emulsification, obtains emulsion；During this, in order to realize being sufficiently mixed for raw material, the system of the emulsion
It is specially for process：
A1), emulsifying agent is mixed with water, heats, obtain emulsifier solution；
A2), urea, reaction promoter, water are mixed with the emulsifier solution, by obtained solution adjust pH value to
3.4~3.6；
A3), by ethyl phenylacetate and step A2) obtained solution mixes, formalin added after emulsification, breast is obtained
Liquid.
During emulsion is prepared, emulsifying agent is mixed with water first, the emulsifying agent is not readily dissolved, and the application is preferred
It is heated so that emulsifying agent fully dissolves, the temperature of the heating is 50~100 DEG C, and the time is 1~2h.The emulsifying agent is
Emulsifying agent well known to those skilled in the art, has no particular limits to this application, example, and the emulsifying agent is polyethylene
Anhydrides emulsifying agent, polyvinyl alcohol emulsifying agent, polyethers emulsifying agent or polyesters emulsifying agent；In a particular embodiment, it is described
Emulsifying agent is ethylene maleic acid anhydride copolymer.The mass ratio of the emulsifying agent and water is (2.0~3.5)：100；The emulsifying agent
Content it is too small, the surface tension of emulsifier solution not enough, is unfavorable for emulsifying soln；Content is excessive, and emulsifying agent will be reduced no longer
Solution surface tension, and produce the synthesis that micella disturbs microcapsules.
After emulsifier solution is obtained, then urea, reaction promoter, water are mixed with emulsifier solution, then will obtained
Solution adjust pH value to 3.4~3.6.This process is the preparation process of wall material solution.The reaction promoter is resorcinol
With ammonium chloride, the reaction promoter promotes cyst wall crosslinking, if without reaction promoter, capsule wall is not fine and close enough, and intensity
It is low.When the reaction promoter is resorcinol and ammonium chloride, this process is specially：At room temperature, by urea, resorcinol,
Ammonium chloride is according to (5.0~6.0)：(0.5~1.0)：(0.5~1.0) ratio is mixed with the deionized water of 200 parts by weight, then is added
Enter 50 parts by weight Emulsifier solution, it is well mixed to obtain the solution that pH is 2.7~3.0, finally adjust the pH value of solution to 3.4~
3.6。
Then the application mixes ethyl phenylacetate with solution obtained above, and formalin is added after emulsification, is obtained
To emulsion；This process is microcapsules emulsion process.This process is specially：Solution obtained above is added into 40.0~60.0 weight
Part ethyl phenylacetate, stirred using high-speed shearing emulsion machine, mixing speed is 700~200r/min, after emulsification pretreatment
To emulsion in add the formalins of 12.0~13.0 parts by weight, the concentration of the formalin is 37wt%.This
During, the addition of formaldehyde is used for and urea reaction, to obtain Lauxite, is used as the wall material of microcapsules.Formaldehyde has been dissolved in
Machine solvent, thus in order to avoid in emulsion process formaldehyde be dissolved in the core of microcapsules, the formaldehyde is preferably after the completion of emulsification
Add.In emulsification, the particle diameter distribution of microcapsules can be controlled by adjusting the stir speed (S.S.) of emulsification.
After emulsion is obtained, then by emulsion heating, reaction, self-repairing microcapsule is obtained.This process is that raw material is anti-
The process answered, i.e. urea are obtained using Lauxite as wall material with formaldehyde reaction, the micro- glue of selfreparing using ethyl phenylacetate as core
Capsule.The programming rate of the heating is 1~3 DEG C/min, and the temperature of the heating is to 50~60 DEG C, and the insulation after the heating is not
Less than 4h.
Present invention also provides a kind of microcapsules, it includes cyst wall and core, and the cyst wall is Lauxite, the core
Including ethyl phenylacetate.According to the present invention, the microcapsules are prepared according to the method described above.Herein described microcapsules are rule
Then spherical, rough surface, particle diameter is 100~250 μm, and wall thickness is 150~200nm.The heat endurance core solvent of microcapsules
Boiling point is determined；By to single microcapsules compression experiment and finite element modelling, calculate the modulus of elasticity of cyst wall for 2.11 ±
0.53GPa。
Present invention also provides a kind of coating, including epoxy resin and the self-repairing microcapsule described in such scheme.In tool
In body embodiment, the self-repairing microcapsule is 1wt%~15wt% of the epoxy resin.
Thus, present invention also provides a kind of coating, it is coated on substrate surface by above-mentioned coating and obtained.
Because the self-repairing microcapsule of above-mentioned preparation has swelling action to epoxy resin, using the principle, the application is also
A kind of epoxy resin composite material is provided, it is prepared by epoxy resin, curing agent and above-mentioned self-repairing microcapsule.
The preparation of above-mentioned epoxy resin composite material is prepared according to mode well known to those skilled in the art, tool
Body, the preparation method of the epoxy resin composite material is：Epoxy resin, curing agent, microcapsules are mixed, vacuum outgas bubble
After pour into mould, first cold curing 24h, then solidify 24h at 35 DEG C, curing and demolding obtain epoxy resin composite material.
The curing agent is 10wt%~15wt% of the epoxy resin, and the self-repairing microcapsule is the epoxy resin
1wt%~15wt%.
The present invention uses one-step method fabricated in situ self-repairing microcapsule, and the wall material of microcapsules is by urea and formaldehyde condensation polymer
Obtained Lauxite is reacted, core is solvent ethyl phenylacetate, and therefore, the self-repairing microcapsule of the application is a kind of solvent-borne type
Self-repairing microcapsule.Solvent-borne type self-repairing microcapsule prepared by the present invention then can use due to having swelling action to epoxy resin
In the selfreparing for realizing epoxy resin-base, there is toughening effect to epoxy resin-base.Solvent microcapsule prepared by the present invention/
Epoxy resin composite material can be healed micro-crack completely, recover fracture of composite materials toughness, and remediation efficiency is reached as high as
98.11%；Solvent microcapsule type Self-repair Composites also have multiple self-reparing capability, third time repair after remediation efficiency still
Up to 72%, this can heal completely mainly due to crackle interface after solvent selfreparing, and fracture every time can all trigger new fracture
Interface.Meanwhile, self-repairing microcapsule prepared by the application, which is also used as coating, is used for coating, with the crackle of reparation.
For a further understanding of the present invention, the preparation side of the self-repairing microcapsule provided with reference to embodiment the present invention
Method is described in detail, and protection scope of the present invention is not limited by the following examples.
1 self-repairing microcapsule of embodiment/epoxy resin TDCB samples
(1) prepared by emulsifier solution：1.25g deionized waters and 50g ethylene maleic acids anhydride copolymer (EMA) are added into beaker
Among, stir the solution and be heated to 80 DEG C of holding 1h, EMA is fully dissolved, obtain the 2.5%EMA aqueous solution；
(2) prepared by wall material solution：At room temperature, 5.00g urea, 0.50g resorcinols and 0.50g ammonium chlorides are added to
In reactor, addition 200g deionized waters are sufficiently stirred for dissolving and fed intake, and then add prepared by 50mL above-mentioned steps (1) 2.5%
EMA solution, is thoroughly mixed uniform, resulting solution pH=3.00~3.10, above-mentioned solution is adjusted using 5%NaOH solution
PH is adjusted to 3.5；
(3) microcapsules are emulsified：45g ethyl phenylacetate (renovation agent) is slowly added in solution prepared by step (2), is used
High-speed shearing emulsion machine is stirred, and emulsifying rate is 900r/min, after emulsification pretreatment certain time, and renovation agent emulsification is spherical liquid
Drop, 12.67g 37wt% formalins are added into obtained emulsion；
(4) reactor is moved into water-bath, emulsion is persistently stirred with 300r/min speed using three leaf paddle stirrers, with
Water-bath pot temperature is adjusted to 55 DEG C by the 1 DEG C/min rate of heat addition, keeps 4h, Fig. 1 is observation microcapsules were not synthesized in the same time
The OM photos of journey；After solution reaction is finished, the solid phase in reaction solution is cleaned with deionized water, then filtered, in room temperature
It is lower to spontaneously dry, obtain the microscapsule powder of good fluidity；Microscapsule powder is sieved, 100~200 μm of particle diameter is chosen
Microcapsules be used as synthesis selfreparing epoxy resin TDCB samples raw material；Fig. 2 is the Electronic Speculum of microcapsules manufactured in the present embodiment
Photo；
(5) TDCB samples are prepared using castable method：By epoxy resin (WSR618), curing agent (DETA), step (4)
The self-repairing microcapsule of preparation in mass ratio 100：12：5 ratio is well mixed, and silicon rubber mould is poured into after vacuum outgas bubble,
According to cold curing 24 hours, the order curing and demolding of 35 DEG C of solidifications 24 hours obtained TDCB samples；
(6) cupping machine is utilized, TDCB samples are broken, after sample section is fitted, sample is positioned over 25 DEG C of perseverance
In incubator, kept for 24 hours, detection TDCB samples remediation efficiency is found, the distribution of sample remediation efficiency about 98 ± 11%, material
Fracture toughness can be completely recovered to original state.Fig. 3 is self-repairing microcapsule manufactured in the present embodiment/epoxy resin TDCB
A (B)-A ' (B ') is sample fracture part in the schematic diagram of sample, figure, and sample can realize selfreparing here；Fig. 4 is this implementation
SEM pictures before and after self-repairing microcapsule/epoxy resin TDCB sample crack forming mechanisms prepared by example；(a) is schemed to repair preceding sample,
(b) is schemed for sample after repairing.
The microcapsules Smart self-repairing coating of embodiment 2
(1) prepared by emulsifier solution：1.25g deionized waters and 50g ethylene maleic acids anhydride copolymer (EMA) are added into beaker
Among, stir the solution and be heated to 80 DEG C of holding 1h, EMA is fully dissolved, obtain the 2.5%EMA aqueous solution；
(2) prepared by wall material solution：At room temperature, 5.00g urea, 0.50g resorcinols, 0.50g ammonium chlorides are added to
In reactor, addition 200g deionized waters are sufficiently stirred for dissolving and fed intake, and then add prepared by 50mL above-mentioned steps (1) 2.5%
EMA solution, is thoroughly mixed uniform, resulting solution pH=3.00~3.10, above-mentioned solution is adjusted using 5%NaOH solution
PH is adjusted to 3.5；
(3) microcapsules are emulsified：45g ethyl phenylacetate (renovation agent) is slowly added in solution prepared by step (2), is used
High speed shearing emulsification agent is stirred, and emulsifying rate is 900r/min, after emulsification pretreatment certain time, and renovation agent emulsification is spherical liquid
Drop, 12.67g 37wt% formalins are added into emulsion；
(4) reactor is moved into water-bath, emulsion is persistently stirred with 300r/min speed using three leaf paddle stirrers, with
Water-bath pot temperature is adjusted to 55 DEG C by the 1 DEG C/min rates of heat addition, keeps 4h；After solution reaction is finished, with deionized water to reaction
Solid phase in liquid is cleaned, and is then filtered, and is spontaneously dried at room temperature, obtains the microscapsule powder of good fluidity；
(5) microcapsules for preparing step (4) are mixed with epoxy resin, obtain the micro- glue of selfreparing that mass fraction is 15%
Capsule/epoxy coating；The coating is coated on slide, wherein, coating layer thickness is about 300 μm, and Microcapsules Size is about
200μm；It is about 40 μm of cut with scalpel width prefabricated.
Found with observation by light microscope, as shown in figure 5, Fig. 5 is coatings different time manufactured in the present embodiment
Scratch removal OM photos；Self-repairing microcapsule content is 15% in the coating, and part A is the cut repaired, B portions in picture
It is divided into the microcapsules of rupture, C portion is complete microcapsules；Coatings cut has been repaired 50% within the 2h times~
60%.The scratch removal function of solvent-borne type microcapsules can be applied in addition to it can realize the external aesthetical of coating and repair
In corrosion-inhibiting coating, the self-repair function of coating antiseptic is realized.
3 self-repairing microcapsules of embodiment/epoxy resin TDCB samples
(1) prepared by emulsifier solution：1.25g deionized waters and 50g ethylene maleic acids anhydride copolymer (EMA) are added into beaker
Among, stir the solution and be heated to 80 DEG C of holding 1h, EMA is fully dissolved, obtain the 2.5%EMA aqueous solution；
(2) prepared by wall material solution：At room temperature, 5.00g urea, 0.50g resorcinols, 0.50g ammonium chlorides are added to
In reactor, addition 200g deionized waters are sufficiently stirred for dissolving and fed intake, and then add prepared by 50mL above-mentioned steps (1) 2.5%
EMA solution, is thoroughly mixed uniform, resulting solution pH=3.00~3.10, above-mentioned solution is adjusted using 5%NaOH solution
PH is adjusted to 3.5；
(3) microcapsules are emulsified：45g ethyl phenylacetate (renovation agent) is slowly added in solution prepared by step (2), is used
High speed shearing emulsification agent is stirred, and emulsifying rate is 900r/min, after emulsification pretreatment certain time, and renovation agent emulsification is spherical liquid
Drop, 12.67g 37wt% formalins are added into emulsion；
(4) reactor is moved into water-bath, emulsion is persistently stirred with 300r/min speed using three leaf paddle stirrers, with
Water-bath pot temperature is adjusted to 55 DEG C by the 1 DEG C/min rates of heat addition, keeps 4h；After solution reaction is finished, with deionized water to reaction
Solid phase in liquid is cleaned, and is then filtered, and is spontaneously dried at room temperature, obtains the microscapsule powder of good fluidity；Will be micro-
Capsule powders are sieved, and the microcapsules for choosing 100~200 μm of particle diameter are used as the original of synthesis selfreparing epoxy resin TDCB samples
Material；
(5) microcapsules of 100 μm~200 μm of selection, specify mass fraction according to 1%, 2%, 5%, 10%, 15% respectively
It is added in epoxy resin, then according to epoxy resin (WSR618) and curing agent (DETA) mass ratio 100:12 ratios are added
TDCB silicon rubber moulds are poured into after curing agent, vacuum outgas bubble, according to cold curing 24 hours, the order of 35 DEG C of solidifications 24 hours
Solidification, prepares self-repair material sample, as shown in Figure 6.
(6) extension test at room temperature, tensile load is at the uniform velocity applied along sample center line, and draw speed is 1mm/min, until
Sample fracture, record tensile load and corresponding elongation displacement, with tensile strength calculated, elongation at break and draws stress-should
Varied curve, as shown in fig. 7, selfreparing effects of the Fig. 7 for microcapsules microcapsules/epoxy resin composite material of different microcapsule contents
Rate column diagram；As shown in Figure 7, when the addition of microcapsules is 1%, remediation efficiency is 47 ± 6%, when addition is 5%, is repaired
Efficiency is up to about 98 ± 11%, and this shows that the fracture toughness of material can be almost complete when microcapsules mass fraction is 5%
To original state, when addition increases to 15%, remediation efficiency is reduced to 83 ± 10% on the contrary, illustrates that the renovation agent of excess is assembled
In in crackle interface, add the plasticity of material, repairing effect reduced on the contrary.Fig. 8 is microcapsules/epoxy resin composite material
Reparation after cross-section morphology；As seen from the figure, crackle can flow out reparation by the solvent wrapped up in the microcapsules that rack.Figure
9 be the crackle interface topography of microcapsules/epoxy resin composite material after repairing, and as seen from the figure, interface does not have obvious crackle,
Show that the microcapsules of rupture discharge solvent, crackle is repaired under swelling action.Because the crack forming mechanism of solvent is fracture
Macromolecular chain rewind, other materials are not present in cracks, thus do not repair interface significantly.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (12)
1. a kind of preparation method of self-repairing microcapsule, comprises the following steps：
A), emulsifying agent, urea, formaldehyde, reaction promoter, ethyl phenylacetate are mixed with water, emulsifies, obtain emulsion；
B), by emulsion heating, reaction, self-repairing microcapsule is obtained.
2. preparation method according to claim 1, it is characterised in that the preparation process of the emulsion is specially：
A1), emulsifying agent is mixed with water, heats, obtain emulsifier solution；
A2), urea, reaction promoter, water are mixed with the emulsifier solution, by obtained solution adjust pH value to 3.4~
3.6；
A3), by ethyl phenylacetate and step A2) obtained solution mixes, formalin added after emulsification, emulsion is obtained.
3. preparation method according to claim 1 or 2, it is characterised in that the emulsifying agent emulsifies for acid polyethylene anhydride
Agent, polyvinyl alcohol emulsifying agent, polyethers emulsifying agent or polyesters emulsifying agent；The reaction promoter is resorcinol and chlorination
Ammonium.
4. preparation method according to claim 1 or 2, it is characterised in that the programming rate of the heating is 1~3 DEG C/
Min, the temperature of the heating is to 50~60 DEG C, and insulation is not less than 4h after the heating.
5. preparation method according to claim 2, it is characterised in that the addition of the urea is 5.0~6.0 weight
Part, the addition of the ethyl phenylacetate is 40.0~60.0 parts by weight, the addition of the formalin for 12.0~
13.0 parts by weight, the concentration of the formalin is 37wt%.
6. a kind of self-repairing microcapsule, including cyst wall and core, the cyst wall are Lauxite, the core includes phenylacetic acid second
Ester.
7. self-repairing microcapsule according to claim 6, it is characterised in that the particle diameter of the self-repairing microcapsule is 100
~250 μm, wall thickness is 150~200nm.
8. a kind of coating, including epoxy resin will with prepared by the preparation method described in any one of Claims 1 to 5 or right
Seek the self-repairing microcapsule described in 6~7 any one.
9. coating according to claim 8, it is characterised in that the content of the self-repairing microcapsule is the epoxy resin
1wt%~15wt%.
10. a kind of coating, is coated on substrate surface as the coating described in any one of claim 8~9 and obtains.
11. a kind of epoxy resin composite material, as the preparation side described in epoxy resin, curing agent and any one of Claims 1 to 5
Self-repairing microcapsule described in any one of prepared by method or claim 6~7 is prepared.
12. epoxy resin composite material according to claim 11, it is characterised in that the curing agent is the asphalt mixtures modified by epoxy resin
10wt%~15wt% of fat, the self-repairing microcapsule is 1wt%~15wt% of the epoxy resin.
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| CN114921156A (en) * | 2022-06-24 | 2022-08-19 | 中山大学 | Multifunctional coating based on microcapsules and application thereof |
| CN115230193A (en) * | 2022-07-01 | 2022-10-25 | 浙江大学 | Preparation method of interlayer graphene toughened CFRPs composite laminated board |
| CN115230193B (en) * | 2022-07-01 | 2024-04-26 | 浙江大学 | Preparation method of interlayer graphene toughened CFRPs composite material laminated plate |
| CN116376385A (en) * | 2023-04-11 | 2023-07-04 | 浙江驭能新材料科技有限公司 | Self-repairing coating applied to TPU car coating film and preparation method thereof |
| CN117080449A (en) * | 2023-10-16 | 2023-11-17 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
| CN117080449B (en) * | 2023-10-16 | 2024-02-06 | 瑞浦兰钧能源股份有限公司 | Self-repairing binder for battery and preparation method thereof |
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Application publication date: 20170915 |