CN113559800A - Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof - Google Patents
Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof Download PDFInfo
- Publication number
- CN113559800A CN113559800A CN202110876857.XA CN202110876857A CN113559800A CN 113559800 A CN113559800 A CN 113559800A CN 202110876857 A CN202110876857 A CN 202110876857A CN 113559800 A CN113559800 A CN 113559800A
- Authority
- CN
- China
- Prior art keywords
- microcapsule
- solution
- percent
- functionalized
- wall
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 152
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229960001149 dopamine hydrochloride Drugs 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 19
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004568 cement Substances 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 93
- 238000003756 stirring Methods 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 24
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 239000002775 capsule Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- 229960003638 dopamine Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- CGXBXJAUUWZZOP-UHFFFAOYSA-N formaldehyde;phenol;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 CGXBXJAUUWZZOP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the technical field of cement-based material microcrack self-repair, and discloses a dopamine hydrochloride functional double-wall microcapsule, a preparation method and application thereof, wherein the dopamine hydrochloride functional double-wall microcapsule consists of a first component and a second component in percentage by mass; the first component consists of 3-5% of melamine, 16-19% of 37% of formaldehyde, 9-12% of phenol, 25-28% of epoxy resin, 5-7% of diluent, 3-5% of acidic pH regulator, 4-7% of alkaline pH regulator, 0.1-0.3% of emulsifier and the balance of water; the second component comprises 1-3% of single-wall microcapsule, 9-12% of tris (hydroxymethyl) aminomethane, 7-9% of hydrochloric acid, 0.4-0.6% of dopamine hydrochloride and 0.6-0.7% of nano TiO2Particles, 9-11% of triethanolamine, 20-22% of absolute ethyl alcohol and the balance of water. The microcapsule of the invention has good self-repairing function.
Description
Technical Field
The invention belongs to the technical field of cement-based material microcrack self-repair, and particularly relates to a dopamine hydrochloride functionalized double-wall microcapsule, a preparation method and application thereof.
Background
At present, cement-based materials are widely applied to various fields such as civil engineering, geothermal engineering, shipbuilding, mechanical industry, marine industry and the like due to excellent mechanical properties of the cement-based materials. Under the long-term service life, the cement-based material is influenced by the severe environment of the inside and the outside, cracks with different sizes are inevitably generated on the surface and the inside of the material, the mechanical property of the cement-based material is reduced, the durability of the structure is greatly reduced, and a series of safety problems are caused in serious conditions, so that the life safety of people is endangered. In the aspect of crack repair, the traditional single-wall microcapsule is selected in the existing cement-based microcapsule self-repairing technology, the microcapsules prepared by the method have poor compactness and unsatisfactory stability, and the traditional repairing method causes huge economic loss every year and needs to be further improved. Meanwhile, the thermal stability of the traditional microcapsule is 200-300 ℃, which is extremely unstable, and thus the application of the microcapsule under high temperature condition is hindered. Therefore, it is also important to improve the thermal stability of the microcapsules, and the problem of cracking of cement-based materials is a challenging problem to be solved.
The microcapsule self-repairing technology can form an intelligent bionic self-healing chemical system in a base material, and has great application value, so that the microcapsule self-healing technology is more and more concerned. In the aspect of crack repair of cement-based materials, urea formaldehyde/epoxy microcapsules, melamine/epoxy microcapsules, phenol formaldehyde/epoxy microcapsules and the like are researched more at present. Such microcapsules are of the break release type. The research on single-wall microcapsules prepared by selecting proper polymer or inorganic material to coat the repairing agent is very extensive. However, in the practical application process, the single-wall microcapsules have the defects of brittle and fragile capsule walls, poor temperature resistance and compactness and the like. Therefore, the development of multi-wall microcapsules with high repair efficiency, compactness and mechanical strength has become a hot research in the field.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the traditional single-wall microcapsule is selected in the existing cement-based microcapsule self-repairing technology, and the microcapsule prepared by the method has poor compactness and unsatisfactory stability, thereby causing huge economic loss every year.
(2) The heat stability of the traditional microcapsule is 200 ℃ to 300 ℃, which is extremely unstable, and the application of the microcapsule under high temperature condition is hindered.
(3) In the practical application process, the single-wall microcapsule has the defects of brittle and fragile capsule wall, poor temperature resistance and compactness and the like.
The difficulty in solving the above problems and defects is: how to form the double-wall microcapsule on the surface layer by layer of the single-wall microcapsule is a problem to be solved urgently. In the process, a secondary wall building mode is adopted, firstly, the single-wall microcapsule is prepared, then, the outer surface of the single-wall microcapsule is modified on the basis, so that the surface of the single-wall microcapsule is provided with active groups or positive and negative charges, and then, second-layer capsule walls with specific groups or opposite charges are alternately deposited on the surface of the single-wall microcapsule layer by layer through chemical bonds and electrostatic adsorption, so that the double-wall microcapsule is formed, the interface binding property of a second-layer wall material and a polymer matrix is improved, and the selection of materials is particularly important.
The significance of solving the problems and the defects is as follows: firstly, preparing a melamine phenol formaldehyde coated single-wall microcapsule by adopting an in-situ polymerization method, and then functionalizing the surface of the microcapsule through the oxidative autopolymerization of dopamine. Finally, depositing the nanometer titanium dioxide capsule wall on the surface of the functionalized single-wall microcapsule by a sol-gel method in a secondary wall-building mode, thereby preparing the double-wall microcapsule. By utilizing the adhesiveness of dopamine, the technology effectively solves the problem of interfacial bonding between the second layer wall material and the polymer matrix, thereby further improving the defects of brittle and fragile capsule wall, poor temperature resistance and compactness and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a dopamine hydrochloride functionalized double-wall microcapsule, a preparation method and application thereof, and particularly relates to a dopamine hydrochloride functionalized double-wall microcapsule with a self-repairing characteristic, a preparation method and application thereof.
The dopamine hydrochloride functional double-wall microcapsule is realized in the way that the dopamine hydrochloride functional double-wall microcapsule consists of a first component and a second component in percentage by mass; wherein, the first component consists of 3 to 5 percent of melamine, 16 to 19 percent of 37 percent of formaldehyde, 9 to 12 percent of phenol, 25 to 28 percent of epoxy resin, 5 to 7 percent of diluent, 3 to 5 percent of acidic pH regulator, 4 to 7 percent of alkaline pH regulator, 0.1 to 0.3 percent of emulsifier and the balance of water; the second component comprises 1 to 3 percent of single-wall microcapsule, 9 to 12 percent of trihydroxymethyl aminomethane, 7 to 9 percent of hydrochloric acid, 0.4 to 0.6 percent of dopamine hydrochloride and 0.6 to 0.7 percent of nano TiO2Particles, 9 to 11 percent of triethanolamine, 20 to 22 percent of absolute ethyl alcohol and the balance of water, and the balance is made up to 100 percent.
The single-wall microcapsules prepared by the first component of the invention use an in-situ polymerization method and are mainly divided into two stages. The first stage is that phenol, formaldehyde and melamine are subjected to ternary polymerization reaction in a reaction system under alkaline conditions to form a prepolymer with methylene combined between molecules. The second stage is the NH of the prepolymer in the reaction system under the acidic condition2A condensation reaction takes place. Finally forming the MPF three-dimensional net structure composite shell layer.
The second component of the invention is prepared into double-wall microcapsules by a dopamine hydrochloride modified sol-gel method. Dopamine hydrochloride is oxidized and polymerized on the surface of the single-pen microcapsule in an alkaline environment, nano TiO2 particles are adhered by utilizing the mussel bionics principle, and finally the double-wall microcapsule is formed by layer-by-layer self-assembly.
Further, the acidic pH regulator is one or more of diluted hydrochloric acid and citric acid, and the alkaline pH regulator is any one or more of triethanolamine and sodium hydroxide.
Further, the diluent is ethyl acetate, and the emulsifier is any one or a mixture of more of sodium dodecyl sulfate, polyvinyl alcohol and gelatin.
Further, the epoxy resin is any one of E-44 and E-51.
The invention also aims to provide a preparation method of the dopamine hydrochloride functionalized double-walled microcapsule by applying the dopamine hydrochloride functionalized double-walled microcapsule, which comprises the following steps:
feeding melamine, phenol and formaldehyde according to a mass ratio, adjusting the pH value of a solution by using a pH regulator, pouring the solution into a three-neck flask for reaction, and cooling to room temperature after reacting for 1 hour to form a prepolymer solution;
step two, uniformly mixing the prepolymer solution, the epoxy resin solution, the diluent and the emulsifier solution, and stirring to form a water-in-oil solution; adding a pH agent, adjusting to 3, reacting for 1-2h, and filtering and washing for 2-3 times by using distilled water; obtaining a free-flowing single-wall microcapsule sample by freeze-drying;
dispersing the single-wall microcapsules in a buffer solution, adding dopamine hydrochloride, stirring for 20min, mechanically stirring for 12h at 10 ℃ under an ice bath condition, filtering, washing, and freeze-drying to obtain functional microcapsules;
step four, adding the functionalized microcapsule into a solution containing triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring at 300 r/min; taking TiO2Slowly dripping the alcohol solution into the solution by using a rubber head dropper, and continuously reacting for 24 hours;
step five, after filtering, repeatedly washing the prepared product by using ethanol solutionVacuum drying at 60 deg.C for 5 hr for 3 times to obtain TiO2The nano particles are loaded on the surface of the functionalized microcapsule to prepare the double-wall microcapsule.
Further, in the step one, the prepolymer solution is obtained by adjusting the pH value to 8-9.
Further, in the first step, the reaction temperature of the water bath is set to be 70 ℃, and the stirring speed is 600 rmp.
Further, in step two, stirring was carried out at 800rmp for 30min to form a water-in-oil solution.
Further, in the third step, the buffer solution is 1M tris (hydroxymethyl) aminomethane-hydrochloric acid, and the pH is 8.5.
The pH, temperature, stirring speed, time and dosage set by the invention are optimized according to a single-factor test and are all optimal parameters. Therefore, the prepared microcapsule has the advantages of optimal particle size, best form and highest composite performance.
Another object of the present invention is to provide a method for cement-based self-healing using the dopamine hydrochloride functionalized double-walled microcapsules.
By combining all the technical schemes, the invention has the advantages and positive effects that: the dopamine hydrochloride functionalized double-wall microcapsule provided by the invention loads dopamine hydrochloride on the surface of a single-wall microcapsule, so that a multi-wall microcapsule with high-efficiency repair, high compactness and high mechanical strength can be obtained; with nano TiO2The particle modified single-wall microcapsule can effectively improve the composite performance of the microcapsule by utilizing the volume effect, small-size effect, surface effect and macroscopic quantum tunnel effect of the nano particles.
The functionalized double-wall microcapsule with the self-repairing effect is embedded by taking epoxy resin as a repairing agent. In-situ polymerization is adopted, phenolic resin is selected as a first layer of wall material, and melamine is adopted for modification to improve the mechanical property of the wall material. On the basis of forming single-wall microcapsules, the invention adopts a sol-gel method to carry out secondary wall building, selects dopamine hydrochloride to carry out functional modification on a single wall, thereby bonding nano TiO2The particles form double-walled microcapsules. At a certain placeTo the extent, the invention effectively improves the compactness, brittleness, temperature resistance and mechanical property of the single-wall microcapsule.
The functionalized double-wall microcapsule with the self-repairing effect, prepared by the invention, is characterized in that the surface of the microcapsule is functionalized through the oxidative autopolymerization of dopamine, and finally nano TiO is deposited on the surface of the functionalized microcapsule through a sol-gel method in a form of secondary wall building2Particles. The invention utilizes dopamine modification technology, dopamine is directly oxidized and polymerized under the conditions of oxygen, alkalinity and light shielding to form a polydopamine crosslinking layer which is attached to the surface of a material matrix, thereby improving the hydrophilicity and the adhesiveness of the single-wall microcapsule. The catechol, amino and other groups on the surface of the material have higher reactivity and can react with functional groups to form covalent bond connection; furthermore, it is also possible to use non-covalent forces such as: van der Waals force, hydrogen bond and the like act with the interface of the single-wall microcapsule to form a coating layer with strong adhesiveness. The invention selects the nanometer TiO2The particles utilize the volume effect, small-size effect, surface effect, macroscopic quantum tunneling effect and the like of the nano particles, the flame retardant property of the core material is improved on the basis of the self-repairing of the cement-based material, and the safety of the composite material is greatly improved; due to the introduction of the nano particles, the prepared functionalized double-wall microcapsule has the characteristics of small particle size, high dispersity and good mechanical property, and the flame retardant property of the cement-based material is improved while the cement-based material is effectively repaired.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of a preparation method of dopamine hydrochloride functionalized double-wall microcapsules provided by an embodiment of the invention.
Fig. 2 is a schematic diagram of a preparation method of a dopamine hydrochloride functionalized double-walled microcapsule provided by an embodiment of the invention.
Fig. 3 is a process diagram of the formation of wall material molecules of dopamine hydrochloride functionalized double-wall microcapsules provided by an embodiment of the invention.
Fig. 4 is an SEM image of dopamine hydrochloride functionalized double-walled microcapsules provided by the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a dopamine hydrochloride functionalized double-wall microcapsule, a preparation method and application thereof, and the invention is described in detail below with reference to the accompanying drawings.
According to the dopamine hydrochloride functional double-wall microcapsule with the self-repairing characteristic, 3% -5% of melamine, 16% -19% of 37% of formaldehyde, 9% -12% of phenol, 25% -28% of epoxy resin, 5% -7% of diluent, 3% -5% of acidic pH regulator, 4% -7% of alkaline pH regulator, 0.1% -0.3% of emulsifier and the balance of water are taken as a first component in percentage by mass; 1-3% of single-wall microcapsule, 9-12% of tris (hydroxymethyl) aminomethane, 7-9% of hydrochloric acid, 0.4-0.6% of dopamine hydrochloride, and 0.6-0.7% of nano TiO2Particles, 9-11% of triethanolamine, 20-22% of absolute ethyl alcohol and the balance of water, and the balance is the second component when the balance is up to 100%.
The acidic pH regulator provided by the embodiment of the invention is one or more of diluted hydrochloric acid and citric acid, and the alkaline pH regulator is any one or more of triethanolamine and sodium hydroxide.
The diluent provided by the embodiment of the invention is ethyl acetate, and the emulsifier is any one or a mixture of more of sodium dodecyl sulfate, polyvinyl alcohol and gelatin.
The epoxy resin provided by the embodiment of the invention is any one of E-44 and E-51.
As shown in fig. 1, the preparation method of the dopamine hydrochloride functionalized double-walled microcapsule provided by the embodiment of the invention comprises the following steps:
s101, feeding melamine, phenol and formaldehyde according to a mass ratio, adjusting the pH value of a solution by using a pH regulator, pouring the solution into a three-neck flask for reaction, and cooling to room temperature after reacting for 1 hour to form a prepolymer solution;
s102, uniformly mixing the prepolymer solution, the epoxy resin solution, the diluent and the emulsifier solution, and stirring to form a water-in-oil solution; adding a pH agent, adjusting to 3, reacting for 1-2h, and filtering and washing for 2-3 times by using distilled water; obtaining a free-flowing single-wall microcapsule sample by freeze-drying;
s103, dispersing the single-wall microcapsules in a buffer solution, adding dopamine hydrochloride, stirring for 20min, mechanically stirring for 12h at 10 ℃ under an ice bath condition, filtering, washing, and freeze-drying to obtain functionalized microcapsules;
s104, adding the functionalized microcapsule into a solution containing triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring at 300 r/min; taking TiO2Slowly dripping the alcohol solution into the solution by using a rubber head dropper, and continuously reacting for 24 hours;
s105, filtering, repeatedly washing the prepared product with ethanol solution for 3 times, and vacuum-drying at 60 ℃ for 5 hours to obtain TiO2The nano particles are loaded on the surface of the functionalized microcapsule to prepare the double-wall microcapsule.
The invention adjusts the pH value to 8-9 to obtain prepolymer solution, the buffer solution is 1M trihydroxymethyl aminomethane-hydrochloric acid, and the pH value is 8.5 to be optimal.
The invention sets the reaction temperature of the water bath kettle at 70 ℃ and the stirring speed at 600 rmp.
The invention is stirred for 30min at 800rmp to form water-in-oil solution.
The dopamine hydrochloride is loaded on the surface of the single-wall microcapsule, so that the multi-wall microcapsule with high-efficiency repair, high compactness and high mechanical strength is obtained.
The invention will use nano TiO2Particle modified single-wall microcapsules utilizing the volume effect, small size effect, surface effect and macroscopic quantum tunneling of nanoparticlesEffectively improves the composite performance of the microcapsule.
The preparation method of the functionalized double-walled microcapsule with the self-repairing characteristic provided by the invention can also be implemented by other steps by persons skilled in the art, and the preparation method of the functionalized double-walled microcapsule with the self-repairing characteristic provided by the invention in fig. 1 is only one specific example.
Fig. 2 is a schematic diagram of a method for preparing a dopamine hydrochloride functionalized double-walled microcapsule according to an embodiment of the present invention, fig. 3 is a diagram of a process for forming wall material molecules of the dopamine hydrochloride functionalized double-walled microcapsule according to the embodiment of the present invention, and fig. 4 is an SEM image of the dopamine hydrochloride functionalized double-walled microcapsule according to the embodiment of the present invention.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
The preparation method of the functionalized double-wall microcapsule with the characteristics of self-repair and flame retardance, provided by the invention, comprises the following steps: feeding melamine, phenol and formaldehyde according to 6g, 16g and 26.4g, adjusting the pH value of the solution to 8-9 by using triethanolamine, pouring the solution into a three-neck flask for reaction, setting the reaction temperature of a water bath kettle to be 70 ℃, the stirring rate to be 600rmp, reacting for 1h, and cooling to room temperature to form the MPF prepolymer for later use. Preparing 0.5 mass percent sodium dodecyl benzene sulfonate solution, and diluting 20g of epoxy resin with 8g of ethyl acetate. And (3) uniformly mixing the prepolymer solution, the core material solution and the emulsifier solution, and stirring for 30min at 800rmp to form an O/W solution. Adjusting the pH value of the solution to about 3 by using 2.0 percent dilute sulfuric acid, reacting for 3 hours, and filtering and washing for 2-3 times by using distilled water. Free-flowing single-wall microcapsule samples were obtained by freeze-drying. 2.0g of single-walled microcapsules were dispersed in 100ml of buffer 1M Tris-HCl, pH 8.5. After the subsequent addition of 0.2g DA and stirring for 20min, the solution turned tan, indicating that oxidative polymerization of DA began. And mechanically stirring for 12 hours at the temperature of 10 ℃ under an ice bath condition, and filtering, washing, freezing and drying to obtain the functionalized microcapsule. Adding 1.0g of the prepared functionalized microcapsule into 100mL of solution containing 10mL of triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring for 300 r/min); another 5ml of TiO2The alcoholic solution was slowly added dropwise to the above solution with a rubber dropper and reacted for 24 h. Filtering, repeatedly washing the obtained product with ethanol solution for 3 times, and vacuum drying at 60 deg.C for 5 hr to obtain TiO2The nanometer particle is loaded on the surface of the functional microcapsule to prepare E-51@ MPF/TiO2Double-walled microcapsules.
Example 2
The preparation method of the functionalized double-wall microcapsule with the characteristics of self-repair and flame retardance, provided by the invention, comprises the following steps: feeding melamine, phenol and formaldehyde according to 6g, 16g and 26.4g, adjusting the pH value of the solution to 8-9 by using triethanolamine, pouring the solution into a three-neck flask for reaction, setting the reaction temperature of a water bath kettle to be 70 ℃, the stirring rate to be 600rmp, reacting for 1h, and cooling to room temperature to form the MPF prepolymer for later use. Preparing 0.5 mass percent sodium dodecyl benzene sulfonate solution, and diluting 20g of epoxy resin with 8g of ethyl acetate. And (3) uniformly mixing the prepolymer solution, the core material solution and the emulsifier solution, and stirring for 30min at 800rmp to form an O/W solution. Adjusting the pH value of the solution to about 3 by using 2.0 percent dilute sulfuric acid, reacting for 3 hours, and filtering and washing for 2-3 times by using distilled water. Free-flowing single-wall microcapsule samples were obtained by freeze-drying. 2.0g of single-walled microcapsules were dispersed in 100ml of buffer 1M Tris-HCl, pH 8.5. After the subsequent addition of 0.4g DA and stirring for 20min, the solution turned tan, indicating that oxidative polymerization of DA began. And mechanically stirring for 12 hours at the temperature of 10 ℃ under an ice bath condition, and filtering, washing, freezing and drying to obtain the functionalized microcapsule. Adding 1.0g of the prepared functionalized microcapsule into 100mL of solution containing 10mL of triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring for 300 r/min); another 5ml of TiO was taken2The alcoholic solution was slowly added dropwise to the above solution with a rubber dropper and reacted for 24 h. Filtering, repeatedly washing the obtained product with ethanol solution for 3 times, and vacuum drying at 60 deg.C for 5 hr to obtain TiO2The nanometer particle is loaded on the surface of the functional microcapsule to prepare E-51@ MPF/TiO2Double-walled microcapsules.
Example 3
The invention provides a preparation method of a functionalized double-wall microcapsule with self-repairing and flame-retardant characteristicsThe method comprises the following steps: feeding melamine, phenol and formaldehyde according to 6g, 16g and 26.4g, adjusting the pH value of the solution to 8-9 by using triethanolamine, pouring the solution into a three-neck flask for reaction, setting the reaction temperature of a water bath kettle to be 70 ℃, the stirring rate to be 600rmp, reacting for 1h, and cooling to room temperature to form the MPF prepolymer for later use. Preparing 0.5 mass percent sodium dodecyl benzene sulfonate solution, and diluting 20g of epoxy resin with 8g of ethyl acetate. And (3) uniformly mixing the prepolymer solution, the core material solution and the emulsifier solution, and stirring for 30min at 800rmp to form an O/W solution. Adjusting the pH value of the solution to about 3 by using 2.0 percent dilute sulfuric acid, reacting for 3 hours, and filtering and washing for 2-3 times by using distilled water. Free-flowing single-wall microcapsule samples were obtained by freeze-drying. 2.0g of single-walled microcapsules were dispersed in 100ml of buffer 1M Tris-HCl, pH 8.5. After the subsequent addition of 0.2g DA and stirring for 20min, the solution turned tan, indicating that oxidative polymerization of DA began. And mechanically stirring for 12 hours at the temperature of 10 ℃ under an ice bath condition, and filtering, washing, freezing and drying to obtain the functionalized microcapsule. Adding 1.0g of the prepared functionalized microcapsule into 100mL of solution containing 10mL of triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring for 300 r/min); another 10ml of TiO was taken2The alcoholic solution was slowly added dropwise to the above solution with a rubber dropper and reacted for 24 h. Filtering, repeatedly washing the obtained product with ethanol solution for 3 times, and vacuum drying at 60 deg.C for 5 hr to obtain TiO2The nanometer particle is loaded on the surface of the functional microcapsule to prepare E-51@ MPF/TiO2Double-walled microcapsules.
Example 4
The preparation method of the functionalized double-wall microcapsule with the characteristics of self-repair and flame retardance, provided by the invention, comprises the following steps: feeding melamine, phenol and formaldehyde according to 6g, 16g and 26.4g, adjusting the pH value of the solution to 8-9 by using triethanolamine, pouring the solution into a three-neck flask for reaction, setting the reaction temperature of a water bath kettle to be 70 ℃, the stirring rate to be 600rmp, reacting for 1h, and cooling to room temperature to form the MPF prepolymer for later use. Preparing 0.5 mass percent sodium dodecyl benzene sulfonate solution, and diluting 20g of epoxy resin with 8g of ethyl acetate. Uniformly mixing the prepolymer solution, the core material solution and the emulsifier solution, and stirring at 800rmpStirring for 30min to form O/W solution. Adjusting the pH value of the solution to about 3 by using 2.0 percent dilute sulfuric acid, reacting for 3 hours, and filtering and washing for 2-3 times by using distilled water. Free-flowing single-wall microcapsule samples were obtained by freeze-drying. 2.0g of single-walled microcapsules were dispersed in 100ml of buffer 1M Tris-HCl, pH 8.5. After the subsequent addition of 0.4g DA and stirring for 20min, the solution turned tan, indicating that oxidative polymerization of DA began. And mechanically stirring for 12 hours at the temperature of 10 ℃ under an ice bath condition, and filtering, washing, freezing and drying to obtain the functionalized microcapsule. Adding 1.0g of the prepared functionalized microcapsule into 100mL of solution containing 10mL of triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring for 300 r/min); another 10ml of TiO was taken2The alcoholic solution was slowly added dropwise to the above solution with a rubber dropper and reacted for 24 h. Filtering, repeatedly washing the obtained product with ethanol solution for 3 times, and vacuum drying at 60 deg.C for 5 hr to obtain TiO2The nanometer particle is loaded on the surface of the functional microcapsule to prepare E-51@ MPF/TiO2Double-walled microcapsules.
The technical effects of the present invention will be described in detail with reference to the tests below.
The microcapsule samples of example 1, example 2, example 3 and example 4 were placed in a thermogravimetric and marvens instrument for thermal stability and particle size analysis, and the results are shown in table 1.
TABLE 1 thermal stability and particle size analysis results
The self-healing properties of the microcapsules were evaluated by uniaxial compression tests, as shown in table 2. The microcapsules in example 3 were added in amounts of 0%, 3%, 6% and 9%, and the test pieces were molded to dimensions of 70mm × 70mm × 70 mm.
TABLE 2 self-repair Performance evaluation of microcapsules
It can be found from table 1 that the thermal stability of the double-wall microcapsule can be effectively improved by introducing the nanoparticles, and the heat loss of the microcapsule is gradually reduced along with the addition of the nanoparticles. And the average particle diameter of the microcapsules is within the range of 89-95 μm. The minimum average particle size was 89.99. mu.m, and the maximum average particle size was 95.76. mu.m. The table 2 shows that the microcapsule prepared by the invention has good repairing effect, the repairing rate can reach 66.3% under the condition that the doping amount is 6%, and the repairing rate is effectively improved by 53.5%. The invention greatly prolongs the service life of the cement-based material, can effectively repair the microcracks in the cement-based material in time and avoids unnecessary loss. In addition, the invention can also effectively improve the thermal stability of the microcapsule and overcome the defects of the prior art.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The dopamine hydrochloride functional double-wall microcapsule is characterized by comprising a first component and a second component in percentage by mass;
the first component consists of 3 to 5 percent of melamine, 16 to 19 percent of 37 percent of formaldehyde, 9 to 12 percent of phenol, 25 to 28 percent of epoxy resin, 5 to 7 percent of diluent, 3 to 5 percent of acidic pH regulator, 4 to 7 percent of alkaline pH regulator, 0.1 to 0.3 percent of emulsifier and the balance of water;
the second component comprises 1 to 3 percent of single-wall microcapsule, 9 to 12 percent of trihydroxymethyl aminomethane, 7 to 9 percent of hydrochloric acid, 0.4 to 0.6 percent of dopamine hydrochloride and 0.6 to 0.7 percent of nano TiO2Particles, 9% -11% of triethanolamine, 20-22% of absolute ethyl alcohol and the balance of water, and the balance is made up to 100%.
2. The dopamine-hydrochloride-functionalized double-walled microcapsule according to claim 1, wherein the acidic pH modifier is one or more of diluted hydrochloric acid and citric acid, and the alkaline pH modifier is any one or more of triethanolamine and sodium hydroxide.
3. The dopamine-functionalized double-walled microcapsule according to claim 1, wherein the diluent is ethyl acetate, and the emulsifier is a mixture of one or more of sodium dodecyl sulfate, polyvinyl alcohol and gelatin.
4. The dopamine-functionalized double-walled microcapsule according to claim 1, wherein the epoxy resin is any one of E-44 and E-51.
5. A preparation method of the dopamine hydrochloride functionalized double-walled microcapsule applying the dopamine hydrochloride functionalized double-walled microcapsule as claimed in any one of claims 1 to 4, wherein the preparation method of the dopamine hydrochloride functionalized double-walled microcapsule comprises the following steps:
feeding melamine, phenol and formaldehyde according to a mass ratio, adjusting the pH value of a solution by using a pH regulator, pouring the solution into a three-neck flask for reaction, and cooling to room temperature after reacting for 1 hour to form a prepolymer solution;
step two, uniformly mixing the prepolymer solution, the epoxy resin solution, the diluent and the emulsifier solution, and stirring to form a water-in-oil solution; adding a pH agent, adjusting to 3, reacting for 1-2h, and filtering and washing for 2-3 times by using distilled water; obtaining a free-flowing single-wall microcapsule sample by freeze-drying;
dispersing the single-wall microcapsules in a buffer solution, adding dopamine hydrochloride, stirring for 20min, mechanically stirring for 12h at 10 ℃ under an ice bath condition, filtering, washing, and freeze-drying to obtain functional microcapsules;
step four, adding the functionalized microcapsule into a solution containing triethanolamine, and carrying out condensation reflux at 25 ℃ under the condition of mechanical stirring at 300 r/min; taking TiO2Slowly dripping the alcohol solution into the solution by using a rubber head dropper, and continuously reacting for 24 hours;
step five, after filtering, repeatedly washing the prepared product for 3 times by using ethanol solution, and drying the product for 5 hours in vacuum at the temperature of 60 ℃ to obtain TiO2The nano particles are loaded on the surface of the functionalized microcapsule to prepare the double-wall microcapsule.
6. The method for preparing dopamine-hydrochloride-functionalized double-walled microcapsules according to claim 5, wherein in the first step, the prepolymer solution is obtained by adjusting the pH value to 8-9.
7. The preparation method of dopamine hydrochloride functionalized double-walled microcapsules according to claim 5, wherein in the first step, the reaction temperature of a water bath is set to 70 ℃, and the stirring speed is 600 rmp.
8. The method for preparing dopamine-functionalized double-walled microcapsules according to claim 5, wherein in step two, the mixture is stirred at 800rmp for 30min to form an aqueous-in-oil solution.
9. The method for preparing dopamine hydrochloride functionalized double-walled microcapsules according to claim 5, wherein in step three, the buffer is 1M tris-hydroxymethyl aminomethane-hydrochloric acid and the pH is 8.5.
10. A method for cement-based self-repairing, which uses the dopamine hydrochloride functionalized double-wall microcapsule according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110876857.XA CN113559800A (en) | 2021-07-31 | 2021-07-31 | Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110876857.XA CN113559800A (en) | 2021-07-31 | 2021-07-31 | Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113559800A true CN113559800A (en) | 2021-10-29 |
Family
ID=78169744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110876857.XA Pending CN113559800A (en) | 2021-07-31 | 2021-07-31 | Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113559800A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286849A (en) * | 2022-08-04 | 2022-11-04 | 上海科邦医用乳胶器材有限公司 | Antibacterial and wear-resistant medical rubber gloves and preparation process thereof |
| CN117777548A (en) * | 2023-12-04 | 2024-03-29 | 科迈特新材料有限公司 | Modified flame retardant for high polymer material and preparation method thereof |
| CN117777548B (en) * | 2023-12-04 | 2024-05-31 | 科迈特新材料有限公司 | Modified flame retardant for high polymer material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205225A (en) * | 2011-06-02 | 2011-10-05 | 北京科技大学 | Method for preparing enhanced epoxy resin/curing agent double-wall microcapsule |
| CN108892407A (en) * | 2018-07-27 | 2018-11-27 | 安徽工业大学 | A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof |
| CN110983791A (en) * | 2019-12-10 | 2020-04-10 | 上海驰纺材料科技有限公司 | Microcapsule with integrated ultraviolet shielding function and preparation method thereof |
| CN112441769A (en) * | 2019-08-27 | 2021-03-05 | 滨州学院 | Microcapsule for performing damage self-repair at crack initiation stage of coal mine goaf sealing wall and preparation method thereof |
-
2021
- 2021-07-31 CN CN202110876857.XA patent/CN113559800A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205225A (en) * | 2011-06-02 | 2011-10-05 | 北京科技大学 | Method for preparing enhanced epoxy resin/curing agent double-wall microcapsule |
| CN108892407A (en) * | 2018-07-27 | 2018-11-27 | 安徽工业大学 | A kind of bivalve layer epoxy resin micro-capsule self-repair material and preparation method thereof |
| CN112441769A (en) * | 2019-08-27 | 2021-03-05 | 滨州学院 | Microcapsule for performing damage self-repair at crack initiation stage of coal mine goaf sealing wall and preparation method thereof |
| CN110983791A (en) * | 2019-12-10 | 2020-04-10 | 上海驰纺材料科技有限公司 | Microcapsule with integrated ultraviolet shielding function and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286849A (en) * | 2022-08-04 | 2022-11-04 | 上海科邦医用乳胶器材有限公司 | Antibacterial and wear-resistant medical rubber gloves and preparation process thereof |
| CN117777548A (en) * | 2023-12-04 | 2024-03-29 | 科迈特新材料有限公司 | Modified flame retardant for high polymer material and preparation method thereof |
| CN117777548B (en) * | 2023-12-04 | 2024-05-31 | 科迈特新材料有限公司 | Modified flame retardant for high polymer material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608985B (en) | Anticorrosive coating capable of being automatically repaired and preparation method thereof | |
| CN105623475A (en) | Method for preparing self-healing coating based on environment-friendly nanometer container | |
| CN114933441B (en) | Environment-responsive homogeneous expansion type self-repairing microcapsule for concrete and preparation method thereof | |
| CN109943169B (en) | Nano composite marine anticorrosive paint and preparation method thereof | |
| CN112745726A (en) | High-performance organic-inorganic composite heat-reflection waterproof coating, and preparation method and application thereof | |
| CN113559800A (en) | Dopamine hydrochloride functionalized double-wall microcapsule, preparation method and application thereof | |
| CN106433409A (en) | Intelligent anticorrosive and self-repairing coating and preparation method thereof | |
| CN109535652A (en) | The method for preparing hybrid material based on silicon/titanium complex sol modified epoxy | |
| CN111393592A (en) | Nano SiO2Super-hydrophobic material of toughened and modified epoxy resin and preparation method thereof | |
| CN112300608A (en) | Aqueous inorganic coating based on geopolymer and preparation method thereof | |
| CN115044279A (en) | Two-dimensional polydopamine-reinforced waterborne epoxy composite anticorrosive paint and preparation method and application thereof | |
| CN114656177A (en) | Silicate cement with chlorine ion permeation resistance and preparation method thereof | |
| Hettiarachchi et al. | Synthesis of calcium carbonate microcapsules as self-healing containers | |
| CN111825860B (en) | Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof | |
| CN110423542B (en) | Anticorrosive paint and preparation method and application thereof | |
| CN116640499A (en) | Polyurea waterproof composition and preparation method thereof | |
| CN116814157A (en) | Preparation method of epoxy organic coating based on nano material | |
| CN113088126B (en) | Microcapsule, microcapsule scale and/or fiber, and preparation method and application thereof | |
| CN115215683B (en) | Zirconia ceramic matrix with surface chain structure and preparation method and application thereof | |
| CN112852199B (en) | Preparation method of cement-based steel structure protective coating | |
| CN115196940A (en) | Composite fiber reinforced basic magnesium sulfate cement and preparation method thereof | |
| CN112812586A (en) | Boron nitride composite material and preparation method and application thereof | |
| CN111675518A (en) | Semi-rigid concrete pavement base material and preparation method and construction method thereof | |
| CN113121938A (en) | Silicon dioxide acrylic resin composite particle and preparation method thereof | |
| KR101076113B1 (en) | Composite beads with super water- and oil-repellent surface, and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |