CN109627826A - A kind of compound shell material microcapsules and preparation method thereof with dual corrosion proof function - Google Patents
A kind of compound shell material microcapsules and preparation method thereof with dual corrosion proof function Download PDFInfo
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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Abstract
The invention discloses a kind of compound shell material microcapsules with dual corrosion proof function, the shell material of the microcapsules is by polyaniline, vinyl polymer, Nano-meter SiO_22Composition；The core material of the microcapsules is metal inhibitor；The capsule size is 5~100 μm, and the shell thickness of the microcapsules is 100nm~2 μm；The monomer of the vinyl polymer is the mixing of single functionality vinyl monomer and bifunctionality vinyl monomer；The metal inhibitor is one of benzotriazole, methyl benzotriazazole, nitro benzotriazole, hydroxy benzo triazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline or a variety of.The present invention loads corrosion proof function substance using the polyaniline with corrosion-resisting function and with the Shell Materials of the preferable vinyl polymer of matrix resin compatibility as microcapsules, is prepared for a kind of compound shell material microcapsules with dual corrosion proof function.
Description
Technical field
The present invention relates to high molecular materials and anticorrosion microcapsules technology field, have dual anti-corrosion more particularly, to one kind
Lose the compound shell material microcapsules and preparation method thereof of function.
Background technique
Microcapsules technology is most common function object carrying method, and advantage is that it is that a kind of effective substance is fixed
Molecule can be encapsulated by cyst wall and is isolated with external environment by change technology, and protection capsule-core property is not affected, while appropriate
Condition such as pressurization heats up or destroys cyst wall under radiating, or makes capsule-core material permeance cyst wall to external diffusion to realize controlled release.
Currently, the method for preparing microcapsules is numerous, such as template, interface polycondensation, situ aggregation method etc., wherein Pickering is newborn
Liquid template provides easy and effective preparation approach for the preparation of microcapsules, and Pickering lotion is i.e. with fine solid
The lotion that grain (such as silica, lignin, barium sulfate and kaolin) replaces conventional surfactant stable, with conventional emulsion
Compare, Pickering lotion have super stable, and foaming characteristic it is low, without molecular migration bring toxic problem.
It is a kind of effective anticorrosive metal means that addition, which has the microcapsules of anti-corrosion or corrosion inhibitive function, in the coating.Mainly
By loading some metal inhibitors in microcapsules, after microcapsules are with coating breaks down, loaded article and metal interaction or
Reaction forms barrier film, plays the function of passive metal.
It is micro- as shell material preparation anticorrosion that multiple polymers (such as polystyrene, polyurethane, polyureas) is had reported at present
Capsule, but most of shell materials mainly play coating function and provide mechanical support, but inhibiting effect is not present to corrosion itself, simultaneously
Microcapsules and matrix poor compatibility are also the previous main problem of mesh.Therefore it is badly in need of wanting developmental research shell that there are more function at present
There can be the anticorrosion microcapsules of superior compatibility to meet wider application requirement with coated substrate simultaneously.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of with dual corrosion proof function
Compound shell material microcapsules and preparation method thereof.The present invention with corrosion-resisting function polyaniline and with matrix resin compatibility compared with
Good vinyl polymer loads corrosion proof function substance as the Shell Materials of microcapsules, is prepared for a kind of with dual anticorrosion
The compound shell material microcapsules of function.
Technical scheme is as follows:
A kind of compound shell material microcapsules with dual corrosion proof function, the shell material of the microcapsules is by polyaniline, alkenes
Polymer, Nano-meter SiO_22Composition；The core material of the microcapsules is metal inhibitor；The capsule size is 5~100 μm, institute
The shell thickness for stating microcapsules is 100nm~2 μm；
The monomer of the vinyl polymer is the mixing of single functionality vinyl monomer and bifunctionality vinyl monomer；
The metal inhibitor is benzotriazole, methyl benzotriazazole, nitro benzotriazole, three nitrogen of hydroxy benzo
One of azoles, 2-mercaptobenzothiazole, 8-hydroxyquinoline are a variety of.
The single functionality vinyl monomer is (methyl) glycidyl acrylate, (methyl) acrylate second
Ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (first
Base) hydroxy-ethyl acrylate, (methyl) ethylhexyl acrylate, (methyl) acrylic acid, (methyl) tert-butyl acrylate, methoxyl group be poly-
Ethylene glycol acrylate, ethoxyethoxyethyl acrylate, styrene, n-isopropyl acrylamide, acrylamide, 2- fourth
One of acrylamide is a variety of.
The bifunctionality vinyl monomer be 1,6-HD acrylate, 1,6-hexylene glycols two (methyl) acrylate,
Tripropylene glycol double methacrylate, N,N methylene bis acrylamide, two (methyl) acrylic acid glycol esters, diethylene glycol dipropyl
Olefin(e) acid ester, neopentyl glycol diethoxy propene acid esters, diethylene glycol phthalate diacrylate, dipropylene glycol diacrylate
One of ester, divinylbenzene are a variety of.
A kind of preparation method of the compound shell material microcapsules with dual corrosion proof function, the preparation method include
Following steps:
(1) by Nano-meter SiO_22Be dispersed in ultrapure water as water phase, at the same by the monomer of vinyl polymer, aniline and
Photoinitiator is dissolved in organic solvent as oily phase, and water-oil phase is mixed, and forms stabilized oil-in-water under mulser effect
Type lotion；
(2) lotion prepared by step (1) is placed in 2~5min of illumination under ultraviolet light, is added dropwise causes containing aniline later
The aqueous solution of agent, static condition, under the conditions of 0~20 DEG C react 8~for 24 hours；Water and ethyl alcohol alternately washing and drying are used later,
Obtain compound shell material microcapsules；
(3) metal inhibitor is dissolved in solvent, microcapsules made from step (2) is immersed in corrosion inhibition for metal agent solution
1~5h of middle stirring removes unsupported object with water and ethanol washing later, obtains having the compound of dual corrosion proof function after dry
Shell material microcapsules.
Nano-meter SiO_2 described in step (1)2For commercially available gas phase nano SiO2, sol-gel method synthesis Nano-meter SiO_22, it is logical
Cross the gas phase nano SiO of silane coupling agent hydrophobically modified2One of；The Nano-meter SiO_22Partial size be 10~100nm.
The hydrophobically modified is dimethoxydiphenylsilane, (3- mercaptopropyi) trimethoxy silicon with silane coupling agent
Alkane, 3-aminopropyltriethoxysilane, 3- glycidyl ether oxypropyltrimethoxysilane, 3- methoxy acryloxy third
One of base trimethoxy silane is a variety of；The method of the hydrophobically modified are as follows: by commercially available gas phase nano SiO2It is scattered in second
In alcohol, addition accounts for SiO2The silane coupling agent of quality 2~10%, it is 8~10 that ammonium hydroxide, which adjusts pH, later, reacts 8 at 50~70 DEG C
The gas phase nano of silane coupling agent hydrophobically modified is made with the alternately washing, drying of ethyl alcohol and ultrapure water after reaction in~16h
SiO2。
Nano-meter SiO_2 described in step (1)2Concentration in ultrapure water is 3~5wt%；The aniline dosage accounts for the 5 of oily phase
~20vol%；In the monomer of the vinyl polymer volume ratio of bifunctionality monomer and alkenes monofunctional monomer be 1:1~
4,30~60vol% that total amount accounts for oily phase is added；The dosage of the photoinitiator is 2~5wt% of vinyl polymer monomer；Institute
Stating oily is mutually 1:1~4 with the volume ratio of water phase.
Organic solvent described in step (1) is benzene,toluene,xylene, chloroform, ether, white oil, hexane, N-Propyl Bromide, dichloro
One of ethane, chloroform, ethyl acetate, pentane, n-butanol are a variety of；The photoinitiator is photoinitiator
1173, photoinitiator 369, photoinitiator 2959, photoinitiator 184, photoinitiator 907, photoinitiator 651, photoinitiator
127, one of photoinitiator 819 or a variety of.
Aniline initiator described in step (2) is ammonium persulfate, potassium peroxydisulfate or ferric trichloride；The aniline initiator
Dosage and the molar ratio of aniline are 1:1~4.
The present invention is beneficial to be had the technical effect that
The present invention prepares microcapsules using Pickering emulsion template method, can be by changing particle emulsifying agents SiO2Dosage
The partial size of emulsion droplets is adjusted to control the size of gained microcapsules, while compared with conventional surfactant, particle emulsifying agents
Dosage is less, and the emulsion particle diameter of preparation is more uniformly spread, and stability is higher, can adjust its hydrophilic and hydrophobic as needed, with full
The mutually polar needs of foot difference grease.In addition it is simple to prepare microcapsules process for Pickering emulsion template method, economic and environment-friendly, subtracts
Pollution problem caused by the excessive use of surfactant is lacked.
Containing the polyaniline with corrosion proof function in microcapsules shell material of the present invention, while load has corrosion inhibiter in kernel,
It generates interaction with metal surface, is passivated metal and forms the film of barrier corrosion factor, metal can be effectively suppressed
Spot corrosion, after being impregnated 1 month in NaCl saturated solution by the coating that electrochemical impedance spectroscopy (EIS) characterizes discovery addition microcapsules
Low frequency range impedance modulus still with higher, it was demonstrated that the addition of microcapsules effectively increases the Corrosion Protection of coating.
Contain vinyl polymer in microcapsules shell material of the present invention, the compatibility of microcapsules in the coating can be effectively improved, together
When vinyl polymer the toughness and mechanical strength of microcapsules can be improved, make up that polyaniline is rigidly larger, the crisp disadvantage of matter.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the compound shell material microcapsules of dual anticorrosion effect that embodiment 1 synthesizes.
Fig. 2 is the SEM photograph of the compound shell material microcapsules of dual anticorrosion effect of embodiment 1-3 synthesis；In figure, A: real
Apply example 1；B: embodiment 2；C: embodiment 3.
Fig. 3 is answering for dual anticorrosion effect after the compound shell material microcapsules (A) that embodiment 1 synthesizes and load corrosion inhibiter
Close the infrared spectrogram of shell material microcapsules (B)；
Scheme A in, PANI HS be individually with polyaniline be shell material synthesis microcapsules；P (GMA-co-HDDA) HS is independent
It is the microcapsules of shell material with vinyl polymer；P (GMA-co-HDDA)-PANI HS is the micro- glue of compound shell material that the present invention synthesizes
Capsule；Scheme in B, P (GMA-co-HDDA)-PANI HS MBT is the Composite Shell for having loaded dual anticorrosion effect of corrosion inhibiter MBT
Material microcapsules.
Fig. 4 is that the compound shell material microcapsules of dual anticorrosion effect that embodiment 1 synthesizes disperse in epoxy coating
The super depth of field and digital photograph of situation.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
A kind of preparation method of the compound shell material microcapsules with dual anticorrosion effect, includes the following steps:
(1) Nano-meter SiO_2 of 6g is weighed first2(50nm) is scattered in 50mL etoh solvent, and the hexichol of 120mg is added later
Base dimethoxysilane, it is 10 that ammonium hydroxide, which is added, and adjusts pH, and in 50 DEG C of reaction 8h, with second alcohol and water, alternately washing is changed after reaction
Property Nano-meter SiO_22；
(2) SiO will be modified as ultrasound made from 180mg step (1)2It is dispersed in 6mL ultrapure water as water phase,
Simultaneously by 0.3mL aniline, 0.9mL glycidyl methacrylate (GMA), 0.9mL1,6- hexylene glycol acrylate (HDDA)
It is dissolved in 3.9mL oil phase toluene, while 36mg photoinitiator 369 is added as oily phase；Water-oil phase is mixed, is passed through
The mulser emulsification 2min of 8000rmp forms stabilized oil-in-water (O/W) type lotion；
(3) lotion made from step (2) is placed in illumination 3min in uv cure machine, polymerize vinyl monomer, illumination
The 2mL aqueous solution of ammonium persulfate containing 750mg, 50 μ L HCl (1M) is added dropwise afterwards, makes aniline polymerization, without any stirring 0
DEG C reaction 10h, is alternately washed with ultrapure water and ethyl alcohol and is dried to obtain compound shell material microcapsules；
(4) microcapsules after drying are placed in flask, the saturation ethyl alcohol that 2-mercaptobenzothiazole (MBT) is added later is molten
Liquid stirs 6h to increase load capacity, removes unsupported object with water and ethanol washing, obtain having dual anticorrosion effect after dry
Compound shell material microcapsules.
The SEM photograph of the compound shell material microcapsules of the present embodiment synthesis is as shown in Fig. 2, as can be seen from the figure microballoon is in rule
Then ball-type, from damaged portion it can be found that being hollow structure inside microballoon.
The infrared spectrogram of the compound shell material microcapsules of the present embodiment synthesis is as shown in Figure 3A, as seen from the figure, with list
Private polyaniline be shell material synthesis microcapsules (PANI HS) and individually with the microcapsules (P (GMA- that vinyl polymer is shell material
Co-HDDA) HS) it compares, the compound shell material microcapsules (P (GMA-co-HDDA)-PANI HS) that the present invention synthesizes have the above two
Characteristic absorption peak, it was demonstrated that it is successfully prepared, and the compound shell material of dual anticorrosion effect after having loaded corrosion inhibiter MBT is micro-
The infrared spectrogram of capsule is as shown in Figure 3B, loads the microcapsules P (GMA-co-HDDA)-after corrosion inhibiter as can be seen from Figure
There is the feature of corrosion inhibiter MBT compared to unsupported microcapsules (P (GMA-co-HDDA)-PANI HS) in PANI HS@MBT
Absorption peak illustrates the successful preparation of the compound shell material microcapsules of dual anticorrosion effect.
Compound shell material microcapsules dispersion in epoxy coating of dual anticorrosion effect of the present embodiment synthesis
The super depth of field and digital photograph as shown in figure 4, before epoxy resin cure, dual anticorrosion effect of resin quality 2% will be accounted for
Compound shell material microcapsules by being dispersed with stirring wherein, metal surface is coated on by way of roller coating, is heating and curing later
Form the epoxy coating for being dispersed with the compound shell material microcapsules of dual anticorrosion effect.Figure is the photo after resin solidification,
By figure it can be seen that microcapsules can be evenly dispersed in the coating, without significantly assembling situation.
Embodiment 2
A kind of preparation method of the compound shell material microcapsules with dual anticorrosion effect, includes the following steps:
(1) Nano-meter SiO_2 of 6g is weighed first2(100nm) is scattered in 50mL etoh solvent, and the 3- of 300mg is added later
Methoxy acryloyloxypropyltrimethoxysilane, be added ammonium hydroxide adjust pH to 8, in 60 DEG C of reaction 12h, after reaction with ethyl alcohol with
Alternately washing obtains product to water.
(2) as ultrasonic by modified Nano SiO made from (1) the step of 240mg2It is dispersed in 6mL ultrapure water, together
When by 0.3mL aniline, 0.75mL dimethylaminoethyl methacrylate (DMAEMA), 0.75mL divinylbenzene (DVB) dissolve
In 1.2mL oil phase ethyl acetate, while 54mg photoinitiator 1173 is added.Water-oil phase is mixed, passes through 10000rmp's
Mulser emulsifies 5min and forms stabilized oil-in-water (O/W) type lotion.
(3) lotion made from step (2) is placed in illumination 4min in uv cure machine, polymerize vinyl monomer.Illumination
The 2mL aqueous solution of ammonium persulfate containing 375mg, 100 μ L HCl (1M) is added dropwise afterwards, makes aniline polymerization, exists without any stirring
10 DEG C of reaction 16h are alternately washed with water and ethyl alcohol and are dried to obtain compound shell material microcapsules.
(4) microcapsules after drying are placed in flask, the saturation ethanol solution of benzotriazole (BTA) are added later,
And 12h is stirred to increase load capacity, unsupported object is removed with water and ethanol washing, obtains that there is dual anticorrosion effect after dry
Compound shell material microcapsules.The SEM photograph of the compound shell material microcapsules of the present embodiment synthesis is as shown in Fig. 2, can from figure
Microballoon is in regular ball-type out, from damaged portion it can be found that being hollow structure inside microballoon.
Embodiment 3
A kind of preparation method of the compound shell material microcapsules with dual anticorrosion effect, includes the following steps:
(1) gas phase SiO by ultrasound that 300mg is commercially available2(15nm) is dispersed in 6mL ultrapure water, simultaneously will
0.3mL aniline, 0.72mL styrene (St), 0.18mL dipropylene glycol diacrylate (DPGDA) are dissolved in 0.3mL oil phase dichloro
In ethane, while 41mg photoinitiator 907 is added.Water-oil phase is mixed, the emulsifier 10min shape of 12500rmp is passed through
At stabilized oil-in-water (O/W) type lotion.
(2) lotion made from step (1) is poured into and is placed in illumination 5min in uv cure machine, polymerize vinyl monomer,
The 2mL aqueous solution of ammonium persulfate containing 250mg, 50 μ L HCl (1M) is added dropwise after illumination, makes aniline polymerization, is not necessarily to any stirring
It is reacted at 20 DEG C for 24 hours, is alternately washed with water and ethyl alcohol and be dried to obtain compound shell material microcapsules.
(3) microcapsules after drying are placed in flask, the ethanol solution of 8-hydroxyquinoline (HQ) is added later, and stirred
For 24 hours to increase load capacity, unsupported object is removed with water and ethanol washing, obtains that there is the compound of dual anticorrosion effect after dry
Shell material microcapsules.The SEM photograph of the compound shell material microcapsules of the present embodiment synthesis is as shown in Fig. 2, as can be seen from the figure microballoon
In regular ball-type, from damaged portion it can be found that being hollow structure inside microballoon.
Claims (9)
1. a kind of compound shell material microcapsules with dual corrosion proof function, which is characterized in that the shell material of the microcapsules is by gathering
Aniline, vinyl polymer, Nano-meter SiO_22Composition；The core material of the microcapsules is metal inhibitor；The capsule size be 5~
100 μm, the shell thickness of the microcapsules is 100nm~2 μm；
The monomer of the vinyl polymer is the mixing of single functionality vinyl monomer and bifunctionality vinyl monomer；
The metal inhibitor be benzotriazole, methyl benzotriazazole, nitro benzotriazole, hydroxy benzo triazole,
One of 2-mercaptobenzothiazole, 8-hydroxyquinoline are a variety of.
2. according to right want 1 described in compound shell material microcapsules, which is characterized in that the single functionality vinyl monomer be (methyl)
Glycidyl acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate,
(methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) hydroxy-ethyl acrylate, (methyl) ethylhexyl acrylate,
(methyl) acrylic acid, (methyl) tert-butyl acrylate, methoxy polyethylene glycol acrylate, ethoxyethoxyethyl acrylic acid
One of ester, styrene, n-isopropyl acrylamide, acrylamide, 2- crotonamide are a variety of.
3. according to right want 1 described in compound shell material microcapsules, which is characterized in that the bifunctionality vinyl monomer be 1,6- oneself
Butanediol acrylate, 1,6-hexylene glycols two (methyl) acrylate, tripropylene glycol double methacrylate, N, N- methylene bisacrylamide
Amide, two (methyl) acrylic acid glycol esters, diethylene glycol diacrylate, neopentyl glycol diethoxy propene acid esters, adjacent benzene
One of dioctyl phthalate diethylene glycol diacrylate, dipropylene glycol diacrylate, divinylbenzene are a variety of.
4. a kind of preparation method of the compound shell material microcapsules described in claim 1 with dual corrosion proof function, feature exist
In the preparation method includes the following steps:
(1) by Nano-meter SiO_22It is dispersed in ultrapure water as water phase, while the monomer, aniline and light of vinyl polymer being drawn
Hair agent is dissolved in organic solvent as oily phase, and water-oil phase is mixed, and stabilised oil-in-water cream is formed under mulser effect
Liquid；
(2) lotion prepared by step (1) is placed in 2~5min of illumination under ultraviolet light, the initiator containing aniline is added dropwise later
Aqueous solution, static condition, under the conditions of 0~20 DEG C react 8~for 24 hours；Later using alternately washing and the drying of water and ethyl alcohol, obtain
Compound shell material microcapsules；
(3) metal inhibitor is dissolved in solvent, microcapsules made from step (2) is immersed in corrosion inhibition for metal agent solution and are stirred
1~5h is mixed, unsupported object is removed with water and ethanol washing later, obtains the compound shell material with dual corrosion proof function after dry
Microcapsules.
5. the preparation method according to claim 4, which is characterized in that Nano-meter SiO_2 described in step (1)2For commercially available gas phase
Nano-meter SiO_22, sol-gel method synthesis Nano-meter SiO_22, pass through the gas phase nano SiO of silane coupling agent hydrophobically modified2In one
Kind；The Nano-meter SiO_22Partial size be 10~100nm.
6. preparation method according to claim 5, which is characterized in that the hydrophobically modified is diphenyl with silane coupling agent
Dimethoxysilane, (3- mercaptopropyi) trimethoxy silane, 3-aminopropyltriethoxysilane, 3- glycidol ether oxygroup
One of propyl trimethoxy silicane, 3- methoxy acryloyloxypropyltrimethoxysilane are a variety of；The hydrophobically modified
Method are as follows: by commercially available gas phase nano SiO2It is scattered in ethyl alcohol, addition accounts for SiO2The silane coupling agent of quality 2~10%, later
It is 8~10 that ammonium hydroxide, which adjusts pH, in 50~70 DEG C of 8~16h of reaction, is alternately washed after reaction with ethyl alcohol and ultrapure water, is dry, be made
To the gas phase nano SiO of silane coupling agent hydrophobically modified2。
7. the preparation method according to claim 4, which is characterized in that Nano-meter SiO_2 described in step (1)2In ultrapure water
Concentration is 3~5wt%；The aniline dosage accounts for 5~20vol% of oily phase；Bifunctionality in the monomer of the vinyl polymer
The volume ratio of monomer and alkenes monofunctional monomer are 1:1~4, and 30~60vol% that total amount accounts for oily phase is added；It is described light-initiated
The dosage of agent is 2~5wt% of vinyl polymer monomer；The oil is mutually 1:1~4 with the volume ratio of water phase.
8. the preparation method according to claim 4, which is characterized in that organic solvent described in step (1) be benzene, toluene,
Dimethylbenzene, chloroform, ether, white oil, hexane, N-Propyl Bromide, dichloroethanes, chloroform, ethyl acetate, pentane, in n-butanol
It is one or more；The photoinitiator be photoinitiator 1173, photoinitiator 369, photoinitiator 2959, photoinitiator 184,
One of photoinitiator 907, photoinitiator 651, photoinitiator 127, photoinitiator 819 are a variety of.
9. the preparation method according to claim 4, which is characterized in that aniline initiator described in step (2) is persulfuric acid
Ammonium, potassium peroxydisulfate or ferric trichloride；The dosage of the aniline initiator and the molar ratio of aniline are 1:1~4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052230A (en) * | 2019-04-29 | 2019-07-26 | 东北石油大学 | A kind of self-repairing microcapsule and its preparation method and application |
| CN110433739A (en) * | 2019-08-26 | 2019-11-12 | 青岛农业大学 | A method of antifouling anti-rotten function microcapsules are prepared based on Pickering lotion |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903956A (en) * | 2006-07-28 | 2007-01-31 | 上海大学 | Preparation method of nano-SiO2/polyaniline anticorrosion paint |
| WO2008097741A1 (en) * | 2007-02-02 | 2008-08-14 | Solutia Incorporated | Multiple layer glass panels having adjustable tint |
| CN103205150A (en) * | 2013-03-25 | 2013-07-17 | 同济大学 | Anticorrosive coating with polyaniline covering gas-phase nano-silica and preparation method thereof |
| CN104010722A (en) * | 2011-12-01 | 2014-08-27 | Les创新材料公司 | Silica microcapsules, process of making the same and uses thereof |
| CN105440884A (en) * | 2015-12-12 | 2016-03-30 | 青岛农业大学 | Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof |
| CN106975376A (en) * | 2017-05-03 | 2017-07-25 | 上海益顿机电设备有限公司 | A kind of microbubble Physical generators |
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
-
2018
- 2018-11-29 CN CN201811440672.9A patent/CN109627826B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903956A (en) * | 2006-07-28 | 2007-01-31 | 上海大学 | Preparation method of nano-SiO2/polyaniline anticorrosion paint |
| WO2008097741A1 (en) * | 2007-02-02 | 2008-08-14 | Solutia Incorporated | Multiple layer glass panels having adjustable tint |
| CN104010722A (en) * | 2011-12-01 | 2014-08-27 | Les创新材料公司 | Silica microcapsules, process of making the same and uses thereof |
| CN103205150A (en) * | 2013-03-25 | 2013-07-17 | 同济大学 | Anticorrosive coating with polyaniline covering gas-phase nano-silica and preparation method thereof |
| CN105440884A (en) * | 2015-12-12 | 2016-03-30 | 青岛农业大学 | Preparation of waterborne epoxy resin self-repairing anticorrosion coating and application thereof |
| CN106975376A (en) * | 2017-05-03 | 2017-07-25 | 上海益顿机电设备有限公司 | A kind of microbubble Physical generators |
| CN107868161A (en) * | 2017-12-07 | 2018-04-03 | 张振 | A kind of preparation method of polymeric hollow microcapsules and its application |
Non-Patent Citations (2)
| Title |
|---|
| YUVARAJ HALDORAI ET AL: "Ultrasonically assisted in situ emulsion polymerization:a facile approach to prepare conducting copolymer/silica nonocomposites", 《POLYMERS ADVANCED TECHNOLOGIES》 * |
| 王冕等: "Pickering乳液聚合法制备pH敏感复合微胶囊及其缓释性能", 《北京化工大学学报(自然科学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052230A (en) * | 2019-04-29 | 2019-07-26 | 东北石油大学 | A kind of self-repairing microcapsule and its preparation method and application |
| CN110433739A (en) * | 2019-08-26 | 2019-11-12 | 青岛农业大学 | A method of antifouling anti-rotten function microcapsules are prepared based on Pickering lotion |
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