CN116814111A - Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof - Google Patents
Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof Download PDFInfo
- Publication number
- CN116814111A CN116814111A CN202310810995.7A CN202310810995A CN116814111A CN 116814111 A CN116814111 A CN 116814111A CN 202310810995 A CN202310810995 A CN 202310810995A CN 116814111 A CN116814111 A CN 116814111A
- Authority
- CN
- China
- Prior art keywords
- self
- epoxy resin
- microcapsule
- modified epoxy
- stirring
- 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 87
- 239000004593 Epoxy Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 phenyl compound Chemical class 0.000 claims abstract description 16
- 239000011162 core material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 claims description 9
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 229920006334 epoxy coating Polymers 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- 238000009849 vacuum degassing Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 13
- 125000003700 epoxy group Chemical group 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000012634 fragment Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000002775 capsule Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 210000004088 microvessel Anatomy 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a surface-modified epoxy self-repairing microcapsule, and a preparation method and application thereof. First SiO is made of 2 Adding the particles into ethanol solution, stirring at room temperature, performing ultrasonic dispersion to obtain uniform liquid, adding KH560 and KH570 under stirring, heating and maintaining the temperature for reaction, drying, and grinding to obtain white powder; adding the white powder into deionized water, stirring and performing ultrasonic treatment to obtain a water phase; mixing and dissolving phenyl compound, glycidyl dimethacrylate and dibenzoyl peroxide with a mixed solution of o-toluene glycidyl ether and epoxy resin as a core material, and mixing with the core material to obtain an oil phase; mixing the oil phase with the water phase, stirring and homogenizing, adding a reducing agent under stirring, reacting for 2-8 h at 40 ℃, washing, filtering to obtain powder, and drying to obtain the surface modified epoxy groupSelf-repairing microcapsule. The epoxy resin coating prepared by embedding the self-repairing microcapsule has self-repairing performance and has good application prospect.
Description
Technical Field
The invention belongs to the field of self-repairing microcapsules, and particularly relates to a surface-modified epoxy self-repairing microcapsule, and a preparation method and application thereof.
Background
The organic coating is cracked in the use process due to mechanical damage such as scratches, cutting and the like, so that the coating loses the protective performance, the service life of the coating is reduced, and the self-repairing material can repair the cracks automatically after the coating is mechanically damaged, so that the service life of the coating is prolonged. The main preparation means of the self-repairing polymer materials reported at present comprise embedding microcapsules, micro-vessels, hollow fibers and other external-assistance self-repairing agents, or utilizing reversible dynamic bonding, supermolecular action and the like, wherein the microcapsules with core-shell structures and embedded with the repairing agents are an economic, convenient and effective method, so that the microcapsule self-repairing strategy is widely applied to epoxy resin coatings. However, the compatibility between the microcapsule surface and the coating substrate is poor due to the polarity difference of the components, and the initial mechanical property of the coating is often reduced after the microcapsule is embedded, so that the coating is more easily damaged mechanically, and therefore, more and more attention is paid to how to improve the initial mechanical property of the self-repairing coating after the microcapsule is added.
The compatibility of the microcapsule and a coating substrate can be improved by modifying specific functional groups on the surface of the microcapsule, and the preparation method of the self-repairing microcapsule comprises in-situ polymerization, interfacial polymerization, permeation after polymerization and the like, but the types of the functional groups introduced on the surface of the microcapsule by the method are limited, the surface modification concentration is limited, and the initial mechanical property of the self-repairing coating of the microcapsule cannot be improved. Pickering particles are solid particles with moderate hydrophilicity and lipophilicity and sizes ranging from tens of nanometers to several micrometers, and prevent the aggregation of dispersed phases through irreversible adsorption at an oil-water interface. Compared with the traditional small molecular surfactant, siO 2 The Pickering particles have low cost, low toxicity, easy surface modification and strong emulsion stability, and can participate in the shell forming reaction of the microcapsule without the influence of molecular residues.
Disclosure of Invention
Aiming at overcoming the defects of the prior art, the invention aims to provide a surface modified epoxy group self-repairing microcapsule, and a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme:
a preparation method of a surface modified epoxy self-repairing microcapsule comprises the following steps:
(1) First SiO is made of 2 Adding particles into ethanol water solution, stirring at room temperature, performing ultrasonic dispersion to obtain uniform liquid with blue fluorescence, adding KH560 (gamma-glycidoxypropyl trimethoxysilane) and KH570 (gamma-methacryloxypropyl trimethoxysilane) under stirring, heating to 60 ℃, performing heat preservation reaction for 3-10 h, performing rotary evaporation concentration on the reaction liquid, drying at 60-80 ℃ for 48-72 h, grinding to obtain white powder, and recording as KH560-KH570-SiO 2 Pickering particles;
(2) KH560-KH570-SiO 2 Adding Pickering particles into water, stirring and performing ultrasonic treatment to obtain a water phase; mixing and dissolving phenyl compound, glycidyl dimethacrylate and dibenzoyl peroxide by using mixed liquid of o-toluene glycidyl ether and epoxy resin as a core material, and then mixing with the core material to obtain an oil phase;
(3) Mixing the oil phase with the water phase, stirring and homogenizing, adding a reducing agent under stirring, reacting for 2-8 hours at 40 ℃, drying, washing with acetone, and grinding to obtain the surface-modified epoxy self-repairing microcapsule powder.
Preferably, the total mass of KH560 and KH570 in step (1) is SiO 2 3.2 to 22.2wt% of the particles, more preferably 12.7wt%, 15.9wt%, 19.0wt% and 22.2wt%.
Preferably, the KH560 and KH570 in step (1) are present in a volume ratio of 1:1.
Preferably, the ethanol solution in the step (1) is obtained by mixing water and absolute ethanol according to a volume ratio of 1:1.
Preferably, the SiO of step (1) 2 The amount of the particles added to the ethanol aqueous solution was 0.03g/mL.
Preferably, step (2) said KH560-KH570-SiO 2 The addition amount of Pickering particles in water is 0.01-0.02 g/mL.
Preferably, the mass ratio of the o-toluene glycidyl ether to the epoxy resin in the step (2) is 1:4-1.
Preferably, the epoxy resin in the step (2) is at least one of epoxy resins E-51 and E-44.
Preferably, the mass ratio of the phenyl compound to the glycerol dimethacrylate in the step (2) is 1-4:1; the dibenzoyl peroxide represents 3wt% of the total amount of phenyl compound and glycerol dimethacrylate.
Preferably, the mass ratio of the total amount of the phenyl compound and the glycerol dimethacrylate in the step (2) to the core material is 4:6.
preferably, the phenyl compound in the step (2) is at least one of styrene and divinylbenzene.
Preferably, the mass ratio of the oil phase to the water phase in the step (3) is 2-4: 10.
preferably, the reducing agent in the step (3) is at least one of N, N-dimethyl-p-toluidine and N, N-dimethylaniline.
Preferably, the reducing agent in the step (3) is added in an amount of 50 to 100wt% of dibenzoyl peroxide.
The surface-modified epoxy self-repairing microcapsule is prepared by the preparation method of the surface-modified epoxy self-repairing microcapsule.
The application of the surface modified epoxy self-repairing microcapsule in preparing an epoxy resin coating.
Preferably, the application comprises the steps of: firstly heating epoxy resin at 40-60 ℃, then adding surface modified epoxy self-repairing microcapsules and a latent curing agent, stirring and mixing uniformly, then vacuum degassing, adding triethylene tetramine after degassing, stirring uniformly, vacuum degassing again, finally curing for 24-48 hours at room temperature, and then reacting for 3-6 hours at 60-80 ℃ to complete the reaction, thus obtaining the epoxy resin coating.
Preferably, the epoxy resin is epoxy resin E-51.
Preferably, the mass ratio of the epoxy resin to the surface modified epoxy self-repairing microcapsule is 100: 15-30.
Preferably, the latent curing agent is added in an amount of 1 to 3wt% of the epoxy resin coating.
Preferably, the latent curing agent is at least one of 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine and methyltetrahydrophthalic anhydride.
Preferably, the molar ratio of triethylene tetramine to epoxy resin is 2-1:1.
The principle or mechanism involved in the invention is as follows:
(1) The invention is designed on SiO by molecules 2 The Pickering particle surface is grafted and modified with C=C double bonds and epoxy groups, so that a chemical bonding transition layer is constructed, on one hand, the grafted carbon-carbon double bonds are utilized to participate in the composition of the microcapsule shell layer, and on the other hand, the grafted epoxy groups are utilized to chemically bond with the epoxy resin substrate, and the self-repairing process of the substrate is participated in through the curing reaction, so that the problem of the initial performance reduction of the embedded self-repairing microcapsule epoxy coating is obviously improved.
(2) Two silane coupling agents, gamma-glycidyl ether oxypropyl trimethoxy silane (KH 560) and gamma-methacryloxypropyl trimethoxy silane (KH 570) are adopted to compound and modify hydrophilic SiO 2 Particle surface, siO is regulated by controlling the feeding ratio of the silane coupling agent 2 Wettability of particle surfaces Pickering particles with good emulsifying property are prepared. Then taking the Pickering particles as a solid particle emulsifier, taking epoxy resin E-51 and o-toluene glycidyl ether as capsule core materials, taking polystyrene-glycerol dimethacrylate P (St-Bis-GMA) as wall materials, and adopting a redox initiation system to prepare the microcapsule with the surface modified epoxy groups at 40 ℃. Microcapsules with the surface modified epoxy groups and a latent curing agent 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl group]The 1,3, 5-thiazine is added into the epoxy resin base material according to a certain proportion to prepare the epoxy resin self-repairing coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention prepares the composite modified SiO by a one-step method 2 The Pickering particles have the diameter of about 10-15 nm, have an underwater oil contact angle of 108 degrees, and can be used for emulsifying high-viscosity epoxy resin to form stable oil-in-water epoxy resin Pickering emulsion.
(2) The self-repairing microcapsule with the surface modified epoxy group is prepared by Pickering emulsion polymerization, and the diameter ratio of the capsule core to the self-repairing microcapsule is 2:1-1:2. The wall material is composed of polystyrene-glycerol dimethacrylate copolymer, and the mass ratio of the polystyrene to the glycerol dimethacrylate is 8:2-5:5. The microcapsule has good normal temperature barrier property, long storage period, high repair speed and high reaction activity, and can be used for repairing a work window with the temperature of more than 120 ℃. The breaking strength of the epoxy resin coating embedded with the surface modified epoxy microcapsule is improved from 21.9MPa to 28.5MPa relative to that of the epoxy resin coating embedded with the surface unmodified epoxy microcapsule, the initial breaking strength of the epoxy resin coating is improved by 30.1%, the breaking elongation is improved from 5.9% to 6.8%, and the breaking elongation is improved by 15.3%.
Drawings
FIG. 1 is an unmodified SiO 2 Particles and modified KH560-KH570-SiO 2 Infrared spectrogram of Pickering particles, a corresponds to unmodified SiO 2 The particle, b corresponds to KH560-KH570-SiO 2 Pickering particles.
FIG. 2 shows KH560-KH570-SiO prepared in example 1 2 SEM images of Pickering particles, wherein the inner inset is an underwater oil contact angle image of the particles.
Fig. 3 is an optical micrograph and an SEM image of the surface-modified epoxy-based self-repairing microcapsule prepared in example 1.
Fig. 4 is an SEM image of capsule fragments of the surface-modified epoxy self-repairing microcapsule prepared in example 1 after grinding and washing with acetone.
FIG. 5 shows the epoxy resin self-healing microcapsule fragments (curve a in FIG. 5) and KH560-KH570-SiO after milling/acetone extraction treatment in example 1 2 Infrared signature of Pickering particles (curve b in FIG. 5).
FIG. 6 is an optical microscope image of an epoxy coating with embedded self-healing microcapsules and an epoxy coating without embedded self-healing microcapsules before and after a self-healing process, with a scale of 100 μm.
Fig. 7 is a stress-strain graph of the microcapsule-embedded epoxy resin coating prepared in example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Examples of SiO 2 The particle size of the particles is 10-15 nm.
Example 1
A preparation method of a surface modified epoxy self-repairing microcapsule comprises the following steps:
(1) First 1.5g of SiO 2 Adding the particles into 50mL of deionized water/absolute ethyl alcohol (1/1, V/V) mixed solution, magnetically stirring at room temperature for 1min (the speed is 500 rpm), and performing ultrasonic dispersion for 20min to obtain a uniform solution with blue fluorescence; 0.141g KH560 and 0.144g KH570 (V) were added with magnetic stirring at 220rpm KH570 /V KH560 =1/1), the reaction was incubated at an elevated temperature of 60℃for 5h. Drying at 60deg.C for 48 hr, and grinding to obtain white powder (KH 560-KH 570-SiO) 2 Pickering particles.
(2) 1g of KH560-KH570-SiO 2 Pickering particles were added to 50mL of deionized water, stirred at 500rpm for 15min, and sonicated for 20min to prepare the aqueous phase. 1g of o-toluene glycidyl ether (CGE) and 3g of epoxy resin E-51 were stirred and mixed uniformly as an epoxy core material, 3g of styrene (St) and 1g of glycerol dimethacrylate (Bis-GMA) and 0.12g of dibenzoyl peroxide (BPO) were stirred and mixed at 500rpm for 15min, and then mixed with 6g of the core material to prepare an oil phase. Mixing the oil phase and the water phase, homogenizing at 6000rpm for 5min, adding 70.27mg of N, N-dimethyl-p-toluidine (DMT) at a stirring rate of 200rpm, stirring for 2min, reacting at 40 ℃ for 5.5h, washing, and drying to obtain microcapsule powder with the surface modified epoxy groups.
Preparation of microcapsule-embedded epoxy resin coating
10. 10g E-51 g of the surface-modified epoxy-based microcapsule powder prepared in example 1 and 0.125g of 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine as latent curing agents were heated at 40℃and stirred and mixed uniformly, and vacuum deaerated in a vacuum box. Then adding 2.48g of triethylene tetramine at room temperature, uniformly stirring, uniformly coating on a polytetrafluoroethylene plate, vacuum degassing at the thickness of 3-5 mm, curing at room temperature for 24 hours, and reacting at 60 ℃ for 3 hours to complete the reaction.
Comparative example 1
The preparation method of the surface unmodified epoxy self-repairing microcapsule comprises the following steps:
(1) First 1.5g of SiO 2 Adding the particles into 50mL of deionized water/absolute ethyl alcohol (1/1, V/V) mixed solution, magnetically stirring at room temperature for 1min (the speed is 500 rpm), and performing ultrasonic dispersion for 20min to obtain a uniform solution with blue fluorescence; 0.095g KH570 was added under magnetic stirring at 220rpm, and the reaction was allowed to proceed at 60℃for 5h. Drying at 60deg.C for 48 hr, and grinding to obtain white powder (KH 570-SiO) 2 Pickering particles.
(2) 1g of KH570-SiO 2 Pickering was added to 50mL of deionized water, stirred at 500rpm for 15min, and sonicated for 20min to prepare the aqueous phase. 1g of o-toluene glycidyl ether (CGE) and 3g of epoxy resin E-51 were stirred and mixed uniformly as an epoxy core material, 3g of styrene (St) and 1g of glycerol dimethacrylate (Bis-GMA) and 0.12g of dibenzoyl peroxide (BPO) were stirred and mixed at 500rpm for 15min, and then mixed with 6g of the core material to prepare an oil phase. Mixing the oil phase and the water phase, homogenizing at 6000rpm for 5min, adding 70.27mg of N, N-dimethyl-p-toluidine (DMT) at a stirring rate of 200rpm, stirring for 2min, reacting at 40 ℃ for 5.5h, and finally drying to obtain the microcapsule powder with the surface modified epoxy groups.
Preparation of microcapsule-embedded epoxy resin coating
The preparation method was the same as in example 1 except that "1.87 g of the surface-modified epoxy-based microcapsule powder prepared in example 1 was added" was replaced with "1.87 g of the surface-unmodified epoxy-based microcapsule powder prepared in comparative example 1".
Test characterization of epoxy coating embedding self-healing microcapsules
The epoxy resin coating of example 1 and the coating without embedded microcapsules was scratched with a No. 11 scalpel with a crack width of 40 to 50 μm, then self-repaired at 120℃for 120min, and observed with an optical microscope. The epoxy coating without embedded microcapsules was used as a blank. The observation is seen in fig. 6, from which fig. 6 we can see: after 120min of self-repairing treatment, the scratch of the epoxy resin coating without the self-repairing microcapsule is not obviously changed, which indicates that the epoxy resin coating has no self-repairing effect. And the epoxy resin coating embedded with the self-repairing microcapsule is filled and repaired after self-repairing, which shows that the microcapsule has the self-repairing effect.
Mechanical property test of microcapsule-embedded epoxy resin coating
The microcapsule-embedded epoxy resin coatings prepared in example 1 and comparative example 1 were drawn at a speed of 10mm/min until they were broken, to obtain the breaking strength of the self-repairing coating. The test was performed using a 68TM-10 high and low temperature materials tester (Instron, USA). The test results are shown in fig. 7, and can be seen from fig. 7: after the surface-modified epoxy group microcapsules and the surface-unmodified epoxy group microcapsules are embedded in the coating substrate, the breaking strength is 28.5MPa and 21.9MPa respectively, the initial breaking strength of the epoxy resin coating is improved by 30.1%, the breaking elongation is improved from 5.9% to 6.8%, and the breaking elongation is improved by 15.3%. The surface of the microcapsule is modified with the epoxy functional groups, so that the surface of the microcapsule participates in the epoxy resin curing reaction, and the surface of the microcapsule is chemically bonded with the epoxy resin base material, so that the interfacial compatibility of the microcapsule and the epoxy resin coating is increased, and the initial mechanical property of the epoxy resin coating is improved.
To verify whether the silane coupling agent was successfully grafted on SiO 2 Particle surface, modified SiO by FT-IR technique 2 Particles and modified KH560-KH570-SiO 2 Qualitative analysis was performed on Pickering particle chemistry. The analysis results are shown in fig. 1, and it can be seen from fig. 1: unmodified SiO 2 Particles and KH560-KH570-SiO 2 The particle is 1100cm -1 All have strong peaksThis is the peak of Si-O-Si absorption of antisymmetric stretching vibration, and furthermore, at 3400cm -1 1640cm -1 Obvious peaks appear, hydroxyl and water peaks due to SiO 2 The particle surface has a large amount of silicon hydroxyl groups, and free water in the air is adsorbed, so that hydroxyl groups and water peaks appear. Relative to unmodified SiO 2 Particles, KH560-KH570-SiO 2 Particles at 1715cm -1 The stretching vibration characteristic peak of the c=o group (shown by the arrow in the figure) appears, which is the carbonyl peak on the methacrylate on KH570, indicating that KH570 grafting was successful. But the characteristic absorption peak of the epoxy group is masked by the Si-O-Si strong absorption peak.
FIG. 2 shows KH560-KH570-SiO prepared in example 1 2 TEM images of Pickering particles, with the inner inset being the underwater oil contact angle image of the particles. As can be seen from fig. 2: KH560-KH570-SiO 2 The Pickering particles have regular spherical microcosmic morphology, and the size of the particles is mainly distributed at 10-15 nm. The Pickering particles have a contact angle of 108 degrees and relatively balanced hydrophilicity and lipophilicity, so that the Pickering particles can be preferentially distributed on an oil-water interface, the contact angle is slightly more than 90 degrees, and the Pickering particles are relatively hydrophilic, thereby being beneficial to the formation of oil-in-water emulsion.
Fig. 3 is an optical micrograph and an SEM image of the surface-modified epoxy-based self-repairing microcapsule prepared in example 1. As can be seen from fig. 3: the optical microscope photograph of the microcapsule shows that the morphology of the microcapsule is a transparent regular microsphere with a core-shell structure, and the regular microsphere morphology shows KH560-KH570-SiO 2 The Pickering particle emulsion has strong stability, so that oil drops can keep good morphology in the reaction process; the transparent appearance of the center indicates that the microsphere has liquid inside, and indicates that the microsphere has a microcapsule core-shell structure. Regular spherical particles were also observed in the scanning electron micrograph of the microcapsules and the surface was dense and crack free, but the presence of small particle aggregates resulted in a slightly rough surface, from the Pickering particles involved in the polymerization.
Fig. 4 is an SEM image of capsule fragments of the surface-modified epoxy self-repairing microcapsule prepared in example 1 after grinding and washing with acetone. To verify the core-shell structure of the microcapsules, after grinding the microcapsules and washing the epoxy core material thoroughly with acetone, fragments of the microcapsules were observed by scanning electron microscopy (shown by the arrows in fig. 4). As can be seen from fig. 4: the shell fragments of the microcapsules have the characteristic of rough outer surface and smooth inner surface, and the thickness of the shell is about 10 μm.
To verify successful grafting of Pickering particles onto the microcapsule shell, the epoxy resin self-repairing microcapsule fragments (curve a in FIG. 5) and KH560-KH570-SiO after grinding/acetone extraction treatment were subjected to 2 The Pickering particles (curve b in FIG. 5) were infrared characterized. As shown in FIG. 5, curve a shows an infrared spectrum of 1730cm for the microcapsule shell -1 There appears a strong c=o characteristic peak of stretching vibration, 3420cm -1 A spike appears at this point, which is the-OH characteristic absorption peak, which is the characteristic absorption peak of the functional group on poly Bis-GMA; at 2930cm -1 、3020cm -1 700cm -1 The characteristic absorption peak of benzene ring appears at this point, which is the characteristic absorption peak of polystyrene. At the same time, curve a is at 1100cm -1 An antisymmetric telescopic vibration characteristic absorption peak of Si-O-Si also appears, which indicates the modified SiO 2 Pickering particles were successfully grafted onto the microcapsule shells.
Example 2
A preparation method of a surface modified epoxy self-repairing microcapsule comprises the following steps:
the procedure of example 1 was repeated except that the styrene in the monomer composition was replaced with divinylbenzene.
Example 3
A preparation method of a surface modified epoxy self-repairing microcapsule comprises the following steps:
the procedure of example 1 was repeated except that N, N-dimethylaniline was used instead of N, N-dimethylaniline in the reducing agent.
The backup microcapsules prepared in the embodiment 2 and the embodiment 3 are prepared into epoxy resin coatings, and the self-repairing property, the breaking strength and the breaking elongation of the epoxy resin coatings can achieve the similar effects as those of the embodiment 1, and cracks can disappear after self-repairing.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any of various other corresponding changes and modifications made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the surface modified epoxy self-repairing microcapsule is characterized by comprising the following steps of:
(1) First SiO is made of 2 Adding the particles into ethanol solution, stirring at room temperature, performing ultrasonic dispersion to obtain uniform liquid, adding silane coupling agents KH560 and KH570 under stirring, heating to 60 ℃, performing heat preservation reaction for 3-10 h, performing rotary evaporation concentration on the reaction liquid, drying at 60-80 ℃ for 48-72 h, grinding to obtain white powder, and recording as KH560-KH570-SiO 2 Pickering particles;
(2) KH560-KH570-SiO 2 Adding Pickering particles into deionized water, stirring and performing ultrasonic treatment to obtain a water phase; mixing and dissolving phenyl compound, glycidyl dimethacrylate and dibenzoyl peroxide by using mixed liquid of o-toluene glycidyl ether and epoxy resin as a core material, and then mixing with the core material to obtain an oil phase;
(3) Mixing the oil phase and the water phase, stirring and homogenizing, adding a reducing agent under stirring, reacting for 2-8 hours at 40 ℃, washing, filtering and drying the obtained powder to obtain the surface modified epoxy self-repairing microcapsule.
2. The method for preparing a surface-modified epoxy self-healing microcapsule according to claim 1, wherein the total mass of KH560 and KH570 in step (1) is SiO 2 3.2 to 22.2 weight percent of particles;
the SiO of step (1) 2 The amount of the particles added to the ethanol aqueous solution was 0.03g/mL.
3. The method for preparing a surface-modified epoxy self-healing microcapsule according to claim 1 or 2, wherein the volume ratio of KH560 to KH570 in step (1) is 1:1;
step (2) KH560-KH570-SiO 2 Pickering granuleThe adding amount of seeds in water is 0.01-0.02 g/mL;
the mass ratio of the o-toluene glycidyl ether to the epoxy resin in the step (2) is 1:4-1;
the mass ratio of the phenyl compound to the glycerol dimethacrylate in the step (2) is 1-4:1; the dibenzoyl peroxide represents 3wt% of the total amount of phenyl compound and glycerol dimethacrylate.
4. The method for preparing the surface-modified epoxy self-repairing microcapsule according to claim 1 or 2, wherein the mass ratio of the total amount of the phenyl compound and the glycerol dimethacrylate to the core material in the step (2) is 4:6, preparing a base material;
the ethanol solution in the step (1) is obtained by mixing water and absolute ethanol according to the volume ratio of 1:1;
the mass ratio of the oil phase to the water phase in the step (3) is 2-4: 10;
the addition amount of the reducing agent in the step (3) accounts for 50-100 wt% of the dibenzoyl peroxide.
5. The method for preparing a surface-modified epoxy self-healing microcapsule according to claim 1, wherein the phenyl compound in the step (2) is at least one of styrene and divinylbenzene;
the reducing agent in the step (3) is at least one of N, N-dimethyl-p-toluidine and N, N-dimethylaniline;
the epoxy resin in the step (2) is at least one of epoxy resins E-51 and E-44.
6. The surface-modified epoxy self-repairing microcapsule according to any one of claims 1 to 5.
7. The use of the surface-modified epoxy-based self-healing microcapsule of claim 6 in the preparation of an epoxy coating.
8. The use according to claim 7, characterized by the steps of: firstly heating epoxy resin at 40-60 ℃, then adding surface modified epoxy self-repairing microcapsules and a latent curing agent, stirring and mixing uniformly, then vacuum degassing, adding triethylene tetramine after degassing, stirring uniformly, vacuum degassing again, finally curing for 24-48 hours at room temperature, and then reacting for 3-6 hours at 60-80 ℃ to complete the reaction, thus obtaining the epoxy resin coating.
9. The use according to claim 8, wherein the mass ratio of the epoxy resin to the surface modified epoxy-based self-healing microcapsules is 100: 15-30;
the addition amount of the latent curing agent accounts for 1-3wt% of the epoxy resin coating;
the molar ratio of triethylene tetramine to epoxy resin is 2-1:1.
10. Use according to claim 8 or 9, wherein the epoxy resin is epoxy resin E-51;
the latent curing agent is at least one of 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-thiazine and methyl tetrahydrophthalic anhydride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310810995.7A CN116814111A (en) | 2023-07-03 | 2023-07-03 | Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310810995.7A CN116814111A (en) | 2023-07-03 | 2023-07-03 | Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116814111A true CN116814111A (en) | 2023-09-29 |
Family
ID=88121823
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310810995.7A Pending CN116814111A (en) | 2023-07-03 | 2023-07-03 | Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116814111A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117417680A (en) * | 2023-11-17 | 2024-01-19 | 中山虹丽美新材料科技有限公司 | Self-repairing coating and preparation method and application thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101215408A (en) * | 2008-01-18 | 2008-07-09 | 中山大学 | High temperature self-restoring epoxy resin material and preparation method thereof |
CN101319055A (en) * | 2007-11-27 | 2008-12-10 | 中山大学 | Epoxy resin micro-capsule and its preparation method |
CN101508823A (en) * | 2009-03-12 | 2009-08-19 | 中山大学 | Quick self-repair type polymer composite material at room temperature |
CN105833811A (en) * | 2016-03-27 | 2016-08-10 | 华南理工大学 | Double-capsule self-repairing epoxy coating and preparation method thereof |
CN106118367A (en) * | 2016-07-26 | 2016-11-16 | 中国工程物理研究院材料研究所 | There is the microcapsule of damage hint repair function and the application in epoxy coating thereof |
CN109929093A (en) * | 2019-04-16 | 2019-06-25 | 江南大学 | A kind of microcapsule-type On The Latent Accelerator For Epoxy Resin and its methods for making and using same |
CN110819071A (en) * | 2019-10-18 | 2020-02-21 | 中国船舶重工集团公司第七二五研究所 | Normal-temperature self-repairing type solid buoyancy material for ocean development equipment and preparation method thereof |
CN111117574A (en) * | 2019-12-30 | 2020-05-08 | 北京中海前沿材料技术有限公司 | Phase-change microcapsule and preparation method thereof |
US20220152574A1 (en) * | 2019-03-28 | 2022-05-19 | 3M Innovative Properties Company | Epoxide microcapsules with pickering emulsifiers |
CN115975617A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | High-interfacial-tension high-interfacial-modulus composite emulsion and preparation method and application thereof |
CN116042070A (en) * | 2023-03-01 | 2023-05-02 | 山东卓高新材料有限公司 | Self-repairing polyaspartic acid ester polyurea waterproof coating and preparation method thereof |
-
2023
- 2023-07-03 CN CN202310810995.7A patent/CN116814111A/en active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101319055A (en) * | 2007-11-27 | 2008-12-10 | 中山大学 | Epoxy resin micro-capsule and its preparation method |
CN101215408A (en) * | 2008-01-18 | 2008-07-09 | 中山大学 | High temperature self-restoring epoxy resin material and preparation method thereof |
CN101508823A (en) * | 2009-03-12 | 2009-08-19 | 中山大学 | Quick self-repair type polymer composite material at room temperature |
CN105833811A (en) * | 2016-03-27 | 2016-08-10 | 华南理工大学 | Double-capsule self-repairing epoxy coating and preparation method thereof |
CN106118367A (en) * | 2016-07-26 | 2016-11-16 | 中国工程物理研究院材料研究所 | There is the microcapsule of damage hint repair function and the application in epoxy coating thereof |
US20220152574A1 (en) * | 2019-03-28 | 2022-05-19 | 3M Innovative Properties Company | Epoxide microcapsules with pickering emulsifiers |
CN109929093A (en) * | 2019-04-16 | 2019-06-25 | 江南大学 | A kind of microcapsule-type On The Latent Accelerator For Epoxy Resin and its methods for making and using same |
CN110819071A (en) * | 2019-10-18 | 2020-02-21 | 中国船舶重工集团公司第七二五研究所 | Normal-temperature self-repairing type solid buoyancy material for ocean development equipment and preparation method thereof |
CN111117574A (en) * | 2019-12-30 | 2020-05-08 | 北京中海前沿材料技术有限公司 | Phase-change microcapsule and preparation method thereof |
CN115975617A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | High-interfacial-tension high-interfacial-modulus composite emulsion and preparation method and application thereof |
CN116042070A (en) * | 2023-03-01 | 2023-05-02 | 山东卓高新材料有限公司 | Self-repairing polyaspartic acid ester polyurea waterproof coating and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
刘昊哲: "改性SiO2皮克林粒子及其乳液稳定性的研究", 《胶体与聚合物》, vol. 41, no. 1, 14 March 2023 (2023-03-14), pages 29 - 32 * |
陈琳琳;范梦雨;孙冠卿;刘仁;: "Pickering乳液法制备复合壳层微胶囊及其在涂料中的应用", 涂料工业, no. 08 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117417680A (en) * | 2023-11-17 | 2024-01-19 | 中山虹丽美新材料科技有限公司 | Self-repairing coating and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN116814111A (en) | Surface-modified epoxy self-repairing microcapsule and preparation method and application thereof | |
CN105833811B (en) | A kind of double-capsule selfreparing epoxy coating and preparation method thereof | |
KR101378645B1 (en) | Novel nanoparticles | |
CN1509298A (en) | Multifunctional autonomically healing composite material | |
CN1654489A (en) | Process for preparing nano silicon dioxide-acrylate composite emulsion | |
JP5374343B2 (en) | Core-shell particle and method for producing core-shell particle | |
CN111303676A (en) | Graphene dispersion liquid, preparation method thereof and anticorrosive paint applying graphene dispersion liquid | |
JP2006193700A (en) | Organic and inorganic hybrid particle | |
WO2020213637A1 (en) | Heat insulating material, engine comprising heat insulating material, nanoparticle dispersion liquid, and production method for heat insulating material | |
JP4780710B2 (en) | Core-shell type polymer gel fine particles and method for producing the same | |
JP2024504563A (en) | Method for preparing graphene oxide modified styrene-acrylic Pickering emulsion and composite emulsion, and method for preventing corrosion of cementitious materials | |
JP5054920B2 (en) | Method for producing non-aqueous fine particle dispersion and antireflection plate or antireflection film using the dispersion | |
JP5279065B2 (en) | Surface-coated porous oxide particles and surface coating method of porous oxide particles | |
CN111116896A (en) | Dehydrorosin polyether surfactant, Pickering high internal phase emulsion and preparation method thereof | |
Cai et al. | Effects of surface modification on the properties of microcapsules for self-healing | |
JP5660481B2 (en) | Hydrophobic treatment method of inorganic oxide fine particles and method of producing dispersion, and inorganic oxide fine particles and dispersion thereof, resin composition and use | |
JP2007216072A (en) | Asbestos treatment agent | |
CN107262056A (en) | A kind of epoxy resin-silica is combined single hole Janus hollow microspheres and preparation method thereof | |
CN112029439A (en) | Shading heat-insulating glass film | |
JP5609109B2 (en) | Method for producing reflection enhancement film, reflection enhancement film, and coating material for forming reflection enhancement film | |
CN112059172B (en) | SiO is carried out to micron order granule2Method of coating | |
CN113861329B (en) | Low-cost W/C reversed-phase micelle and preparation method of reversed-phase Pickering emulsion polymerization thereof | |
CN106317425B (en) | A method of organic inorganic hybridization hollow nanospheres are prepared by ultrasound | |
WO2014038033A1 (en) | Production method for curing agent and/or curing accelerant complex particles, curing agent and/or curing accelerant complex particles, and heat-curable resin composition | |
CN114456292B (en) | polystyrene-SiO with surface wrinkles 2 Core-shell nano composite particle and preparation method thereof |
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 |