CN108892407A - A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof - Google Patents
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof Download PDFInfo
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- CN108892407A CN108892407A CN201810842869.9A CN201810842869A CN108892407A CN 108892407 A CN108892407 A CN 108892407A CN 201810842869 A CN201810842869 A CN 201810842869A CN 108892407 A CN108892407 A CN 108892407A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/12—Multiple coating or impregnating
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- 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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Abstract
The invention belongs to microcapsules self-repair material preparation technical fields, more particularly to being related to a kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, microcapsules self-repair material uses epoxy resin for renovation agent core material, melamine-urea element-formaldehyde resin is prepared as the monoshell microcapsule self-repair material of internal layer wall material using situ aggregation method first, again by sol-gel method, prepare using inorganic SiO2 polymer as the double shell microcapsule self-repair material of outer layer wall material；The present invention, as epoxy resin emulsifying agent, compared with conventional emulsifier, has the characteristic of asepsis environment-protecting using graphene oxide；The present invention utilizes the good biocompatibility of inorganic SiO2 polymer and excellent acid-proof alkaline, using it as outer layer wall material, the compatibility for improving microcapsules self-repair material and cement concrete material, makes it preferably play self-healing properties in cement concrete material.
Description
Technical field
The invention belongs to microcapsules self-repair material preparation technical fields, and in particular to a kind of bivalve layer micro- glue of epoxy resin
Capsule self-repair material and preparation method thereof.
Background technique
Concrete material is main structural material in infrastructure construction in china, but because concrete material brittleness is larger,
Micro crack can be generated during long service, if can develop without repairing in time as macroscopical visible crack, influence
The structure durability of concrete material.Epoxy resin is a kind of polymer material with good repairing performance, by micro- to its
It is encapsulated, and be embedded into cement concrete material, occur crack, microencapsulation material meeting inside cement concrete material
It cracks under the stress that crack generates, flows out renovation agent, reach and cement concrete material micro crack is repaired
It is multiple.
Currently, by situ aggregation method, using Lauxite or melamine formaldehyde resin be wall material to epoxy resin into
Row cladding, can be formed with excellent covering property using epoxy resin as the core-shell microcapsule self-repair material of core material.By
It is poor in Lauxite or melamine formaldehyde resin polymer wall material acid-proof alkaline, make it in cement concrete alkalinity ring
Long-term existing stability is bad in border, and organic wall material and cement-based material have that compatibility is bad, is it in water
Long-term existing stability brings adverse effect in cement-based material.SiO2 microcapsule wall material has good biocompatibility, excellent
Good acid-proof alkaline and chemical stability, and there is good compatibility with cement-based material, it is organic microcapsule wall material
Good alternative materials.Therefore, using inorganic wall material coating technology, by SiO2 wall material to organic wall material microcapsules epoxy resin from
Repair materials carry out secondary cladding, and the microcapsules self-repair material for having excellent compatibility with cement concrete material can be made,
It makes it easier in conjunction with cement concrete material, is more advantageous to the prosthetic for playing epoxy resin micro-capsule self-repair material
Energy.
Chinese patent CN104772086A discloses a kind of epoxy resin micro-capsule and preparation method thereof at present；Mainly with ring
Oxygen resin is capsule-core raw material, using the inorganic particulate of absorption solidification agent as cyst wall raw material, by the way that capsule-core and cyst material to be dispersed in
In aqueous solution, under proper condition, capsule-core surface is caused to the absorption of inorganic particulate and curing agent using core materials and occurs to gather
Reaction is closed, is formed using epoxy resin film and inorganic particulate as the epoxy microcapsule of cyst wall component.The preparation method of the microcapsules has
There is the features such as yield height, simple process, at low cost, solvent-free volatilization, synthesized microcapsules have excellent heat resistance,
Self-repair material field has potential value.
Summary of the invention
In order to overcome the shortcomings of the prior art, the object of the present invention is to provide a kind of double shells epoxy resin micro-capsules
The preparation method of self-repair material, this method is by situ aggregation method, using melamine-urea-formaldehyde resin to asphalt mixtures modified by epoxy resin
Rouge carries out the epoxy resin micro-capsule self-repair material material that cladding constitutes core-shell structure, then by sol-gel method, by positive silicon
The SiO2 inorganic polymer that sour tetrem ester hydrolysis, polymerization generate prepares bivalve layer epoxy resin micro-capsule certainly as outer layer wall material
Repair materials, so that the epoxy resin micro-capsule self-repair material of preparation has better resistance to acid and alkali, with inorganic cement
Concrete material has better compatibility, preferably plays prosthetic of the microcapsules self-repair material in cement-based material
Energy.
In view of the above problems, the invention proposes a kind of bivalve layer epoxy resin micro-capsule self-repair material and its
Preparation method.For this method using graphene oxide as epoxy resin emulsifying agent, graphene oxide has biggish specific surface area,
Oxygen-containing hydrophilic radical rich in structure, amphipathic characteristic makes it can be used as epoxy resin emulsifying agent, and traditional epoxy
Resin emulsifier (such as lauryl sodium sulfate, neopelex, Span80, Tween80 and tristerin),
Often there is certain toxicity and be difficult to degrade, a large amount of use will cause more serious problem of environmental pollution.Therefore, of the invention
Using graphene oxide as epoxy resin emulsifying agent, excellent dispersion effect can reach under less volume, and will not make
At problem of environmental pollution.
In order to achieve the above purpose, it is achieved by the following technical programs：
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, preparation process includes monoshell layer epoxy
The preparation of resin microcapsule self-repair material and double shell microcapsule self-repair material prepare two stages, wherein the micro- glue of monoshell layer
Capsule self-repair material preparation process includes following three steps：
(1) graphene oxide emulsifier is mixed with epoxy resin and diluent, deionized water is added dropwise, 2000~
4000r/min is emulsified under shear agitation effect, is obtained uniform and stable epoxy resin latex, is adjusted lotion by acid regulator
PH value is 3-4；
(2) melamine, urea element, formaldehyde and deionized water are mixed evenly, obtain low-molecular weight water-soluble pre-polymerization
Liquid solution obtains aqueous solution prepolymer solution, and the pH value of mixed liquor is adjusted to 9-10 by alkaline conditioner；
(3) it by low-molecular weight water-soluble prepolymer solution, is slowly dropped in above-mentioned epoxy resin latex, stirring 1-2 is small
Acid regulator is slowly added dropwise in Shi Hou, and the pH of mixed solution is adjusted to 2-3, continues to stir 2h, it is outstanding to obtain microencapsulated phase change material
Supernatant liquid obtains the monoshell layer epoxy that melamine-urea element-formaldehyde resin is wall material after the washing of this suspension, filtering, drying
Resin microcapsule self-repair material.
Preferably, graphene oxide used is the graphene oxide aqueous dispersions prepared using Hummers method, GO content
For 7.4g/L, the thickness of lamella is about 1.027nm, and length and width is about 600nm.
Preferably, the epoxy resin latex is made of the raw material of following parts by weight：100 parts of epoxy resin, 8~15
Part diluent, 10-15 parts of graphene oxide water solutions, 150-300 parts of deionized waters, the low-molecular weight water-soluble performed polymer are molten
Liquid is made of 15-60 parts of melamines, 45-180 parts of urea elements, 125-500 parts of formalins.
Preferably, the epoxy resin is by epoxy vinyl ester resin, glycidyl epoxies, bisphenol F type epoxy
Resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, multiple functional radical glycidyl ether resin, aminoepoxy resin,
One of glycidyl ester type epoxy resin, epoxidation of olefins, phenol formaldehyde epoxy vinyl ester resin or a variety of compositions.
Preferably, the diluent is by acetone, methyl ethyl ketone, cyclohexanone, benzene,toluene,xylene, n-butanol, styrene, fourth
One of base glycidol ether, glycol glycidyl ethers, diethylene glycol glycidol ether or a variety of compositions, incorporation are ring
The 8~15% of oxygen resin quality.
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, prepares monoshell microcapsule above-mentioned
On the basis of self-repair material, double shell microcapsule self-repair material is prepared, preparation process includes following two step：
(1) a certain amount of tetraethyl orthosilicate, deionized water and dehydrated alcohol are weighed, a certain amount of alkaline conditioner is added
PH value is adjusted to 10, being sufficiently stirred hydrolyzes tetraethyl orthosilicate, by the microcapsules self-repair material and matter of above-mentioned preparation
Measuring score is 2% cetyltrimethylammonium bromide aqueous solution according to mass ratio 1:3 after mixing, makes microcapsule granule in water
It is uniformly dispersed in solution；
(2) above-mentioned tetraethyl orthosilicate hydrolyzate is added in above-mentioned micro-capsule dispersion liquid, it, will after being sufficiently stirred for 24 hours
Obtained solid powder is washed, filters, is obtained after drying using melamine-urea element-formaldehyde resin as internal layer wall material, inorganic polymeric
Object SiO2For the double shell microcapsule self-repair material of outer layer wall material.
Preferably, the alkaline conditioner is any one in ammonia spirit or silane coupling agent.
Preferably, double shell microcapsule self-repair material includes the raw material composition of following parts by weight：100 parts of positive silicic acid four
Ethyl ester, 50-200 part deionized water, 50-200 parts of dehydrated alcohols, 10-20 parts of alkaline conditioners, 30-100 parts of monoshell layer asphalt mixtures modified by epoxy resin
Grease microcapsule self-repair material, 100-300 parts of cetyltrimethylammonium bromide aqueous solutions.
Preferably, the silane coupling agent is vinyl silanes, amino silane, epoxy radicals silicone hydride, hydrosulphonyl silane and methyl
One of acryloxy silane is a variety of.
Using above-mentioned technical solution, beneficial effects of the present invention are as follows：
(1) present invention is using graphene oxide as emulsifier, and graphene oxide is the oxide of graphene, with stratiform
Structure has excellent mechanics harmony, light, electric property.After oxidation processes, hydroxyl rich in, carboxyl, carbonyl thereon
The oxygen-containing functional groups such as base and epoxy group, keep its chemical property more active compared with graphene, and show hydrophilic and hydrophobic amphiphilic
Performance has superior dispersibility in water, can be used as amphiphilic surfactant；
(2) using melamine-urea element-formaldehyde resin as internal layer wall material in the present invention, using organic wall material to asphalt mixtures modified by epoxy resin
Rouge is coated, and compact structure, the excellent epoxy resin micro-capsule self-repair material of covering property are obtained；Using SiO2 as outer layer
Wall material solves the problems, such as the single organic wall material microcapsules self-repair material of tradition and cement-based material poor compatibility, secondly, outside
Layer SiO2 inorganic polymer wall material object has good chemical stability and thermal stability, with substrate medium (cement, concrete
Deng) there is better compatibility, so that microcapsules self-repair material is preferably compound in cement-based material.
Detailed description of the invention
Fig. 1-1 is the melamine-urea element-micro- glue of formaldehyde resin monoshell layer epoxy resin prepared in the embodiment of the present invention 1
Capsule self-repair material SEM photograph, prepare in Fig. 1-2 embodiment of the present invention 1 with melamine-urea element-formaldehyde resin hypostracum,
Inorganic SiO2 polymer is the double shell microcapsule self-repair material SEM photograph of outer shell；
Fig. 2-1 is the melamine-urea element-micro- glue of formaldehyde resin monoshell layer epoxy resin prepared in the embodiment of the present invention 2
Capsule self-repair material SEM photograph, prepare in Fig. 2-2 embodiment of the present invention 2 using melamine-urea element-formaldehyde resin as inner casing
Layer, inorganic SiO2 polymer are the double shell microcapsule self-repair material SEM photograph of outer shell；
Fig. 3-1 is the melamine-urea element-micro- glue of formaldehyde resin monoshell layer epoxy resin prepared in the embodiment of the present invention 3
Capsule self-repair material SEM photograph, prepare in Fig. 3-2 embodiment of the present invention 3 using melamine-urea element-formaldehyde resin as inner casing
Layer, inorganic SiO2 polymer are the double shell microcapsule self-repair material SEM photograph of outer shell；
Fig. 4-1 is the melamine-urea element-micro- glue of formaldehyde resin monoshell layer epoxy resin prepared in the embodiment of the present invention 4
Capsule self-repair material SEM photograph, the melamine-urea element-formaldehyde resin prepared in Fig. 4-2 embodiment of the present invention 4 are hypostracum,
Inorganic SiO2 polymer is the double shell microcapsule self-repair material SEM photograph of outer shell；
Fig. 5 is to prepare in present example 1 using epoxy resin as core material, melamine-urea element-formaldehyde resin single layer
Shell, inorganic SiO2 polymer outer double shell microcapsule self-repair material FTIR map.1469.1cm-1 and 1517.6cm-1
The characteristic peak at place is C on phenyl ring-it is the special vibration peak of epoxy group at C stretching vibration peak, 822.1cm-1 and 961.8cm-1,
Demonstrate the presence of epoxy resin；The peak occurred at 460.3cm-1 is the flexural vibrations peak of Si-O-Si, shows there is SiO2's
In the presence of；Peak within the scope of 2929.4~2963.2cm-1 is C-the symmetrical stretching vibration peak of H, very strong suction at 3429.4cm-1
Peak-the H and O-stretching vibration peak of H that is N is received, by the presence of proof melamine-formaldehyde-Lauxite.Thus ring is illustrated
Oxygen resin is good by melamine-formaldehyde-Lauxite and inorganic SiO2 polymer overmold, and foring has double shell structurres
Microcapsules self-repair material.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described.Based on the embodiment of the present invention, the common skill in this field
Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1：
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, comprises the following steps：
(1) by 30g bisphenol A type epoxy resin (E51), 4.5g butyl glycidyl ether and 15ml graphene oxide water dispersion
Liquid emulsifies shear agitation 30min with 3000r/min, instills 60ml deionized water in the process under 80 DEG C of bath temperatures,
Epoxy resin latex is formed, adjusting ph value of emulsion with the citric acid solution of 10% mass concentration is 3-4；
(2) by 4g melamine, after 8g urea, the mixing of 27g formalin, the magnetic agitation under 70 DEG C of bath temperatures is used
The sodium hydroxide solution of 10% mass concentration adjusts mixed solution system pH value 9-10, and 30ml deionized water is added, and stirring 1h is obtained
To clear viscous urea-formaldehyde performed polymer, low-molecular weight water-soluble prepolymer solution is generated；
(3) preparation of epoxy resin micro-capsule self-repair material, lotion is poured into three-necked flask, in 70 DEG C of bath temperatures
Under, prepolymer solution obtained is instilled in three-necked flask, after 1h is mixed, the hydrochloric acid solution tune of 10% mass concentration is added
Section system pH is 2-3, obtains microencapsulated phase change material suspension, after the washing of this suspension, filtering, drying, obtains trimerization
Cyanamide-urea element-formaldehyde resin is the monoshell layer epoxy resin micro-capsule self-repair material of wall material；
(4) by 10g tetraethyl orthosilicate, 40g deionized water, the mixing of 40ml dehydrated alcohol, addition epoxy radicals silicone hydride coupling
Agent KH560, which adjusts pH value, makes tetraethyl orthosilicate be fully hydrolyzed to form silicon to 10-11, magnetic agitation 30min at a temperature of 35 DEG C
Colloidal sol；By the monoshell layer epoxy resin micro-capsule self-repair material 40g and cetyltrimethylammonium bromide solution of above-mentioned preparation
120g is mixed 30min and forms microencapsulated phase change material dispersion liquid, and the silica solution of above-mentioned preparation is instilled in this dispersion liquid, is filled
Divide stirring for 24 hours, will obtain after the washing of obtained solid powder, filtering, drying using melamine-urea element-formaldehyde resin as internal layer
Wall material, inorganic polymer SiO2 are the double shell microcapsule self-repair material of outer layer wall material.
Embodiment 2：
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, comprises the following steps：
(1) by 20g bisphenol A type epoxy resin epoxy resin, ((E44), 2.4g butyl glycidyl ether and 15ml aoxidize stone
Black alkene aqueous dispersions emulsify shear agitation 30min with 2000r/min, instill 60ml in the process under 85 DEG C of bath temperatures
Deionized water forms epoxy resin latex, and adjusting ph value of emulsion with the hydrochloric acid of 10% mass concentration is 3-4；
(2) by 3g melamine, after 9g urea, the mixing of 27g formalin, the magnetic agitation under 70 DEG C of bath temperatures is used
10% triethanolamine solution adjusts mixed solution system pH value 9-10, and 30ml deionized water is added, and stirring 1h obtains sticky
Bright urea-formaldehyde performed polymer generates low-molecular weight water-soluble prepolymer solution；
(3) preparation of epoxy resin micro-capsule self-repair material, lotion is poured into three-necked flask, in 70 DEG C of bath temperatures
Under, prepolymer solution obtained is instilled in three-necked flask, after 1h is mixed, the acetum tune of 10% mass concentration is added
Section system pH is 2-3, obtains microencapsulated phase change material suspension, after the washing of this suspension, filtering, drying, obtains trimerization
Cyanamide-urea element-formaldehyde resin is the monoshell layer epoxy resin micro-capsule self-repair material of wall material；
(4) by 10g tetraethyl orthosilicate, 20g deionized water, the mixing of 20g dehydrated alcohol, addition ammonia spirit adjusting pH value
Tetraethyl orthosilicate is set to be fully hydrolyzed to form silica solution to 10-11, magnetic agitation 30min at a temperature of 35 DEG C；By above-mentioned preparation
Monoshell layer epoxy resin micro-capsule self-repair material 20g and cetyltrimethylammonium bromide solution 60g be mixed 30min
Microencapsulated phase change material dispersion liquid is formed, the silica solution of above-mentioned preparation is instilled in this dispersion liquid, is sufficiently stirred for 24 hours, will obtain
Solid powder washing, filtering, it is dry after obtain using melamine-urea element-formaldehyde resin as internal layer wall material, inorganic polymer
SiO2 is the double shell microcapsule self-repair material of outer layer wall material.
Embodiment 3：
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, comprises the following steps：
(1) by 10g bisphenol A type epoxy resin epoxy resin, ((E51), 1.5g butyl glycidyl ether and 15ml aoxidize stone
Black alkene aqueous dispersions emulsify shear agitation 30min with 4000r/min, instill 60ml in the process under 75 DEG C of bath temperatures
Deionized water forms epoxy resin latex, and adjusting ph value of emulsion with the citric acid solution solution of 10% mass concentration is 3-4；
(2) by 2g melamine, after 10g urea, the mixing of 27g formalin, the magnetic agitation under 70 DEG C of bath temperatures is used
10% sodium carbonate liquor adjusts mixed solution system pH value 9-10, and 30ml deionized water is added, and stirring 1h obtains clear viscous
Urea-formaldehyde performed polymer generates low-molecular weight water-soluble prepolymer solution；
(3) preparation of epoxy resin micro-capsule self-repair material, lotion is poured into three-necked flask, in 70 DEG C of bath temperatures
Under, prepolymer solution obtained is instilled in three-necked flask, after 1h is mixed, the hydrochloric acid solution tune of 10% mass concentration is added
Section system pH is 2-3, obtains microencapsulated phase change material suspension, after the washing of this suspension, filtering, drying, obtains trimerization
Cyanamide-urea element-formaldehyde resin is the monoshell layer epoxy resin micro-capsule self-repair material of wall material；
(4) by 10g tetraethyl orthosilicate, 10g deionized water, the mixing of 10g dehydrated alcohol, addition amido functional group silane idol
Connection agent KH550, which adjusts pH value, makes tetraethyl orthosilicate be fully hydrolyzed to be formed to 10-11, magnetic agitation 30min at a temperature of 35 DEG C
Silica solution；The monoshell layer epoxy resin micro-capsule self-repair material 10g and cetyltrimethylammonium bromide of above-mentioned preparation is molten
Liquid 30g is mixed 30min and forms microencapsulated phase change material dispersion liquid, and the silica solution of above-mentioned preparation is instilled in this dispersion liquid,
It is sufficiently stirred for 24 hours, will obtain with melamine-urea element-formaldehyde resin being interior after the washing of obtained solid powder, filtering, drying
Layer wall material, inorganic polymer SiO2 are the double shell microcapsule self-repair material of outer layer wall material.
Embodiment 4：
A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, comprises the following steps：
(1) by 5g bisphenol f type epoxy resin (NPEF-170), 0.5g butyl glycidyl ether and 15ml graphene oxide water
Dispersion liquid emulsifies shear agitation 30min with 3000r/min, instills 60ml deionization in the process under 75 DEG C of bath temperatures
Water forms epoxy resin latex, and adjusting ph value of emulsion with the citric acid solution of 10% mass concentration is 3-4；
(2) by 4g melamine, after 8g urea, the mixing of 27g formalin, the magnetic agitation under 70 DEG C of bath temperatures is used
The sodium hydroxide solution of 10% mass concentration adjusts mixed solution system pH value 9-10, and 30ml deionized water is added, and stirring 1h is obtained
To clear viscous urea-formaldehyde performed polymer, low-molecular weight water-soluble prepolymer solution is generated；
(3) preparation of epoxy resin micro-capsule self-repair material, lotion is poured into three-necked flask, in 70 DEG C of bath temperatures
Under, prepolymer solution obtained is instilled in three-necked flask, after 1h is mixed, the citric acid solution of 10% mass concentration is added
Regulation system pH value is 2-3, obtains microencapsulated phase change material suspension, after the washing of this suspension, filtering, drying, obtains three
Poly cyanamid-urea element-formaldehyde resin is the monoshell layer epoxy resin micro-capsule self-repair material of wall material；
(4) by 10g tetraethyl orthosilicate, 10g deionized water, the mixing of 10g dehydrated alcohol, addition vinyl trimethoxy silicon
Alkane coupling agent A171, which adjusts pH value, is fully hydrolyzed tetraethyl orthosilicate to 10-11, magnetic agitation 30min at a temperature of 35 DEG C
Form silica solution；By the monoshell layer epoxy resin micro-capsule self-repair material 2.5g and cetyl trimethyl bromination of above-mentioned preparation
Amine aqueous solution 7.5g is mixed 30min and forms microencapsulated phase change material dispersion liquid, and the silica solution of above-mentioned preparation is instilled this dispersion
In liquid, it is sufficiently stirred for 24 hours, will obtains after the washing of obtained solid powder, filtering, drying with melamine-urea element-formaldehyde resin
For internal layer wall material, inorganic polymer SiO2 is the double shell microcapsule self-repair material of outer layer wall material.
Above embodiments are only to illustrate the technical solution of type of the present invention, rather than its limitations；Although referring to aforementioned implementation
Type of the present invention is described in detail in example, those skilled in the art should understand that：It still can be to aforementioned each
Technical solution documented by embodiment is modified or equivalent replacement of some of the technical features；And these are modified
Or replacement, the spirit and scope for each embodiment technical solution of type of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof, which is characterized in that its preparation process packet
The preparation and double shell microcapsule self-repair material for including monoshell layer epoxy resin micro-capsule self-repair material prepare two stages,
Middle monoshell microcapsule self-repair material preparation process includes following three steps：
(1) graphene oxide emulsifier is mixed with epoxy resin and diluent, deionized water is added dropwise, 2000~
4000r/min is emulsified under shear agitation effect, is obtained uniform and stable epoxy resin latex, is adjusted lotion by acid regulator
PH value is 3-4；
(2) melamine, urea element, formaldehyde and deionized water are mixed evenly, it is molten obtains low-molecular weight water-soluble performed polymer
Liquid obtains aqueous solution prepolymer solution, and the pH value of mixed liquor is adjusted to 9-10 by alkaline conditioner；
(3) it by low-molecular weight water-soluble prepolymer solution, is slowly dropped in above-mentioned epoxy resin latex, after stirring 1-2 hours,
Acid regulator is slowly added dropwise, the pH of mixed solution is adjusted to 2-3, continues to stir 2h, obtains microencapsulated phase change material suspension,
After the washing of this suspension, filtering, drying, it is micro- to obtain the monoshell layer epoxy resin that melamine-urea element-formaldehyde resin is wall material
Capsule self-repair material.
2. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 1 and preparation method thereof, feature exists
In graphene oxide used is the graphene oxide aqueous dispersions prepared using Hummers method, and GO content is 7.4g/L, piece
The thickness of layer is about 1.027nm, and length and width is about 600nm.
3. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 1 and preparation method thereof, feature exists
In the epoxy resin latex is made of the raw material of following parts by weight：100 parts of epoxy resin, 8~15 parts of diluents, 10-
15 parts of graphene oxide water solutions, 150-300 parts of deionized waters, the low-molecular weight water-soluble prepolymer solution is by 15-60 parts
Melamine, 45-180 parts of urea elements, 125-500 parts of formalin compositions.
4. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 1 and preparation method thereof, feature exists
In the epoxy resin is by epoxy vinyl ester resin, glycidyl epoxies, bisphenol f type epoxy resin, bisphenol S type
Epoxy resin, bisphenol-A epoxy resin, multiple functional radical glycidyl ether resin, aminoepoxy resin, glycidyl ester type
One of epoxy resin, epoxidation of olefins, phenol formaldehyde epoxy vinyl ester resin or a variety of compositions.
5. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 1 and preparation method thereof, feature exists
In the diluent is by acetone, methyl ethyl ketone, cyclohexanone, benzene,toluene,xylene, n-butanol, styrene, butyl glycidyl
One of ether, glycol glycidyl ethers, diethylene glycol glycidol ether or a variety of compositions, incorporation are epoxy resin quality
8~15%.
6. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 1 and preparation method thereof, feature exists
In, the acid regulator be mass concentration be 10% hydrochloric acid solution, acetum, citric acid solution in it is any one
Kind.
7. -6 any bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof according to claim 1,
It is characterized in that, it is above-mentioned prepare monoshell microcapsule self-repair material on the basis of, prepare double shell microcapsule selfreparing material
Material, preparation process includes following two step：
(1) a certain amount of tetraethyl orthosilicate, deionized water and dehydrated alcohol are weighed, a certain amount of alkaline conditioner is added and adjusts
PH value is to 10, and being sufficiently stirred hydrolyzes tetraethyl orthosilicate, by the microcapsules self-repair material of above-mentioned preparation and quality point
Number is 2% cetyltrimethylammonium bromide aqueous solution according to mass ratio 1:3 after mixing, makes microcapsule granule in aqueous solution
In be uniformly dispersed；
(2) above-mentioned tetraethyl orthosilicate hydrolyzate is added in above-mentioned micro-capsule dispersion liquid, after being sufficiently stirred for 24 hours, will be obtained
Solid powder washing, filtering, it is dry after obtain using melamine-urea element-formaldehyde resin as internal layer wall material, inorganic polymer
SiO2For the double shell microcapsule self-repair material of outer layer wall material.
8. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 7 and preparation method thereof, feature exists
In the alkaline conditioner is any one in ammonia spirit or silane coupling agent.
9. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 7 and preparation method thereof, feature exists
In double shell microcapsule self-repair material includes the raw material composition of following parts by weight：100 parts of tetraethyl orthosilicates, 50-200
Part deionized water, 50-200 parts of dehydrated alcohols, 10-20 parts of alkaline conditioners, 30-100 parts of monoshell layer epoxy resin micro-capsule are certainly
Repair materials, 100-300 parts of cetyltrimethylammonium bromide aqueous solutions.
10. layer epoxy resin micro-capsule self-repair material in bivalve according to claim 8 and preparation method thereof, feature exists
In the silane coupling agent is vinyl silanes, amino silane, epoxy radicals silicone hydride, hydrosulphonyl silane and methacryloxy silicon
One of alkane is a variety of.
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