CN110465251A - A kind of long-acting repairing type bilayered microcapsule - Google Patents
A kind of long-acting repairing type bilayered microcapsule Download PDFInfo
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- CN110465251A CN110465251A CN201910856494.6A CN201910856494A CN110465251A CN 110465251 A CN110465251 A CN 110465251A CN 201910856494 A CN201910856494 A CN 201910856494A CN 110465251 A CN110465251 A CN 110465251A
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention discloses a kind of long-acting repairing type bilayered microcapsule preparation methods, the following steps are included: (1) prepares SDB nanosphere: taking azo-initiator, it is added in the mixture of styrene, divinylbenzene and anionic surfactant, oil-in-water pickering emulsion is made；Under nitrogen protection, pickering emulsion is heated and is reacted, obtain white solid SDB nanosphere；(2) SDB/PMMA Nano composite granules are prepared: PMMA being taken to be added to the water, SDB nanosphere is added, enter SDB particle to PMMA swelling；Oxidant is added, inorganic acid is added dropwise, so that the abundant polymerization reaction of PMMA, obtains SDB/PMMA Nano composite granules；(3) ZIF-8/PMMA hollow microsphere: SDB/PMMA Nano composite granules, 2-methylimidazole is prepared, anhydrous methanol is added, zinc nitrate is added, reaction obtains ZIF-8/SDB/PMMA compound particle；It is added in organic solvent, removes SDB template, obtain ZIF-8/PMMA hollow microsphere；(4) renovation agent or corrosion inhibiter are loaded: by ZIF-8/PMMA hollow microsphere, being added in repair liquid and impregnates, obtains ZIF-8/PMMA/ repairing liquid microcapsule.
Description
Technical field
The present invention relates to a kind of microcapsules, in particular to a kind of long-acting type bilayered microcapsule preparation method belongs to coating skill
Art field.
Background technique
Coating is a kind of composite material of polymer matrix, has polymeric long-chain-segment complete characteristic.Coating is being applied
After the completion of work, gradually cross-linked polymeric solidifies, and reaches maximum intensity performance for a period of time after being fully cured.With coating application
The time of completion increases, and the internal cross-linked structure of coating can gradually be damaged, and causes the mechanical performance of coating to reduce, if ring
There is temperature difference fluctuation in border, and coating surface is very easy to cracked.Crackle initially only exists in the inside of coating, it is difficult to send out
It is existing, it is also difficult to it repairs, as the gradually crosslinking of crackle merges, forms the macroscopic large fracture of macroscopic view, it is at this time if right
Coating, which is repaired, just becomes extremely difficult.
The coating of self-repair function is the preferred plan for solving coating and effectively adapting to various environmental nuisances after the completion of construction.
The key of repair function, which is that, timely provides substance supplement to coating microfissure, is filled out fine crack by supplementation material
Fill it is full, prevent minute crack growth expand form macrocrack.
The self-healing coatings of built-in type are by adding microcapsules, and when so that crackle being diffused at microcapsules, microcapsules are broken
Release renovation agent is split, renovation agent fills up crackle and crosslinks reaction solidification with the coating matrix of crackle two sides, so that crackle is not
Regrowth.The renovation agent of built-in type has good universality, but the cross-linked polymeric characteristic of the renovation agent of built-in type is induced
It is more difficult to control, if the cross-linking reaction quality of built-in type renovation agent cannot be controlled well, repair it is not only ineffective, also
It will lead to surface topography deterioration after coating is repaired.
The core materials that existing microcapsule product wraps up mostly are all more strongly active reparation core materials, this leads to microcapsules
Product in application process, often can not long-time storage, after storage after a period of time, microcapsules capsule-core is gradually lost
It is living.In addition, the cyst wall structure of microcapsules is more weak, also cause a large amount of microcapsules it is real play repair effect before just
Because various internal causes, it is outer thus the effect of failing, causing final microcapsule product that can not play expected design.
Summary of the invention
It is an object of the invention to overcome the microcapsules storage in the presence of the prior art gradually to inactivate in the process, and micro- glue
Capsule cyst wall structural weak leads to microcapsules because a variety of causes fails, can not play the problem of repairing effect, provides a kind of long-acting
Repairing type bilayered microcapsule preparation method and its microcapsule product of preparation.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes:
A kind of long-acting repairing type bilayered microcapsule preparation method, comprising the following steps:
(1) SDB nanosphere is prepared
Azo-initiator is taken, is added in the mixture of styrene, divinylbenzene and anionic surfactant, is mixed to form
Oily phase.It is added in deionized water, mixing, homogeneous obtains oil-in-water pickering emulsion；
Under nitrogen protection, pickering emulsion is heated to 70-80 DEG C of reaction 10-20h, after reaction, centrifuge washing 2-5
Secondary, vacuum drying obtains white solid SDB nanosphere (polystyrene nanospheres).
(2) SDB/PMMA Nano composite granules are prepared
PMMA is taken to be added to the water, ultrasonic disperse；Then, the SDB nanosphere of step (1) preparation, ultrasound, stirring, to PMMA is added
Swelling enters SDB particle；Oxidant is added, stirs evenly, inorganic acid is added dropwise and stirs, 0-5 DEG C of reaction 2-8h is then heated to
15-35 DEG C of room temperature, polymerization reaction 14-28h, so that PMMA sufficiently polymerize；After the reaction was completed, be centrifuged, washing, until supernatant without
Color, vacuum drying, obtains SDB/PMMA Nano composite granules.
(3) ZIF-8/PMMA hollow microsphere is prepared
SDB/PMMA Nano composite granules, 2-methylimidazole obtained by step (2) are taken, anhydrous methanol is added, is uniformly dispersed；Nitre is added
Sour zinc, is stirred to react 2-8h, and centrifuge washing obtains ZIF-8/SDB/PMMA compound particle；
Gained ZIF-8/SDB/PMMA compound particle is added in organic solvent, SDB template is removed, is filtered, it is dry, obtain ZIF-
8/PMMA hollow microsphere.
(4) renovation agent or corrosion inhibiter are loaded
By ZIF-8/PMMA hollow microsphere, it is added in repair liquid and impregnates, be stirred to react, so that repair liquid enters in ZIF-8/PMMA
Empty microballoon；Filtering is washed, and is centrifuged, vacuum drying, obtains ZIF-8/PMMA/ repairing liquid microcapsule.
The microcapsules of preparation method design of the present invention are long-acting repairing type MOF/PMMA/ bilayered microcapsules, have " metal-
Organic frame (metal-organic framework) " structure (MOF).Microcapsule core is formed centrally pickering emulsion
(Pickering emulsion) is that solia particle is adsorbed onto two-phase interface composition stabilized emulsion.Solids are integrated to boundary
The surface in face and prevent drop coalescence, thus make emulsion stablize, emulsifier is low, and environmental-friendly, stability is strong, not vulnerable to
The influence of the factors such as system pH, salinity, temperature and oily phase composition, has long-acting advantage.Then, microcapsules use nucleocapsid packet
Structure is wrapped up in, there is bilayer core@shell design feature, the property feature for sufficiently combining different core-shell structures can play
Outstanding composite strengthening facilitation.Multi-layer core-shell structure load reparation liquid hold-up is higher, and release diffusion property is more various, repairs
Multiple excellent.Microcapsules shell of the present invention has ZIF-8 structure (Zeolitic Imidazolate Frameworks, zeolite
Imidazate frame structure material), it is porous crystalline material, can be good at that microcapsules slow release is helped to play efficacy effect,
With outstanding permanent repair efficacy effect.
The SDB/PMMA Nano composite granules first in preparation method of the present invention, penetrate into SDB nanometers using PMMA
In microballoon, the nanoparticle of SDB shell, PMMA core is prepared.Wherein, expression form SDB/PMMA, ZIF-8/PMMA/ is repaired
Fluid infusion microcapsules etc. are to refer to component A package B component ingredient or be constituted shell core micro-sphere structure, such as " SDB/PMMA " refers to SDB
The nanosphere structure of PMMA is wrapped up, " ZIF-8/PMMA/ repairs liquid microcapsule " refers to that ZIF-8 is located at outermost layer, inside package
PMMA, repair liquid ingredient load wherein.
Further, step (1) described azo-initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile
(ABVN), the one or more of azo-bis-isobutyrate hydrochloride (AIBA), two isobutyl imidazoline hydrochloride (AIBI) of azo etc..
Preferably, the azo-initiator is AIBN.Azodiisobutyronitrile, decomposition reaction is more steady, only generates a kind
Free radical does not occur induction and reduces side reaction.
Preferably, the dosage of azo-initiator is the 0.1-6% of the first polymer raw quality, first polymer raw
Including styrene and divinylbenzene.
Further, in step (1), the anionic surfactant refers to C12-C16 sodium alkyl sulfate, C12-C16 alkane
At least one of base sodium sulfonate.Preferably, the anionic surfactant is lauryl sodium sulfate.Wherein C12-C16
Sodium alkyl sulfate is the sodium sulphate of the alkyl connection containing 12-16 carbon atom, such as lauryl sodium sulfate, myristyl sulphur
Sour sodium.
Preferably, the dosage of the anionic surfactant is 0.5-2 times of the first polymer raw quality, described first
Polymer raw includes styrene and divinylbenzene.Such as 0.7,0.9,1,1.1,1.3,1.5 times etc..
Further, step (1) described divinylbenzene is divinylbenzene, DVB, purity 80%, isomer mixture,
The 4 tert-butyl catechol inhibitor comprising concentration less than 0.1%.
Preferably, the weight ratio of the divinylbenzene and styrene is styrene: divinylbenzene=1:0.5-2.
Further, after step (1) water phase and oil mix, using high speed homogenization device homogenization.Preferably, homogenizer
Revolving speed >=12000r/min.Preferably, homogenization 2-5min.Wherein, deionized water is as water phase.
Further, pickering emulsion is heated to 72-88 DEG C of reaction by step (1).Preferably, using heating water bath.Water-bath
Heating and temperature control is accurate, and fluctuation is less.
Further, step (1) centrifuge washing process, centrifugal rotational speed 2000-18000r/min.
Further, step (1) centrifuge washing process, is washed using C1-C6 low mass molecule alcohol.The C1-C6 low molecule
Alcohol is at least one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol.Preferably dehydrated alcohol.
Further, step (1) vacuum drying temperature≤50 DEG C.Preferably, vacuum drying temperature≤45 DEG C, such as 40 DEG C.
Vacuum drying temperature control is no more than 50 DEG C, keeps microcapsule core shell structure integrally indeformable, structure is more compact.
Further, step (2) described PMMA is polymethyl methacrylate, and molecular weight ranges are 60,000-30 ten thousand.
Further, in step (2), the weight ratio that SDB nanosphere and PMMA raw material is added is SDB nanosphere: PMMA=1:
40-1:2.Such as 1:20,1:15,1:10,1:8,1:5 etc..
Further, in step (2), after SDB nanosphere is added, mass concentration of the SDB nanosphere in mixed solution is
2-10%。
Further, in step (2), the oxidant be one of potassium peroxydisulfate, ammonium persulfate, peroxide oxidant or
Two kinds.The peroxide oxidant includes benzoyl peroxide etc..Preferably, the oxidant is potassium peroxydisulfate.
Preferably, the molar ratio of oxidant and PMMA are 1:0.8-1.2, preferably 1:1.The mole and PMMA of oxidant
Molar ratio is conducive to the subsequent swollen-state polymerization reaction of PMMA close to 1:1, the good ratio of both control.
Further, in step (2), the inorganic acid is one or more of hydrochloric acid, sulfuric acid, perchloric acid, nitric acid etc..It is excellent
It is selected as hydrochloric acid.
Preferably, the molar ratio of inorganic acid and PMMA are 1:0.7-1.2.The mole and PMMA mole of inorganic acid are close
1:1 cooperates the polymerization reaction for realizing composite particles as oxidant.The addition mole of inorganic acid is reaction equivalent calculating,
Ensure that polymerization reaction sufficiently carries out.
Further, step (2) takes PMMA to be added to the water, at 0-5 DEG C, ultrasonic disperse.First under cryogenic by PMMA
Ultrasonic disperse is carried out, uniformity is promoted, inhibits ultrasound fever, avoids unexpected polymerization reaction.
Further, SDB nanosphere is added in step (2), keeps 0-5 DEG C of temperature of mixed liquor.
Further, step (2) is swollen PMMA sufficiently into SDB nanosphere.To PMMA under the observation of optical microscopy
Drop fades away, and shows that PMMA is sufficiently swollen and enters in SDB nanosphere.
Further, it is the aqueous solution that oxidant is added that oxidant, which is added, in step (2).Such as persulfate aqueous solution.By oxygen
Agent (such as potassium peroxydisulfate) is soluble in water to be configured to oxidant use, and material mixing is more uniform.
Further, SDB emulsion solid content is maintained at that 4wt.% is constant by step (2), the weight of PMMA raw material and seed emulsion
Than for 1:40 ~ 1:2.
Further, step (3) takes SDB/PMMA Nano composite granules, 2-methylimidazole, and anhydrous methanol, ultrasonic disperse is added
Uniformly.The mutual dispersion mixing done using anhydrous methanol as solvent, dissolution cooperation Nano composite granules and 2- methyl miaow, is promoted
Shell reacts the uniformity.
Further, in step (3), the mass ratio of SDB/PMMA Nano composite granules and 2-methylimidazole is SDB/PMMA
Nano composite granules: 2-methylimidazole mass ratio=1:0.5-5.
Further, the zinc nitrate is zinc nitrate hexahydrate.
Further, it is 25:1-2 that 2-methylimidazole and the weight ratio of zinc nitrate hexahydrate, which is added, in step (3).
Further, step (3) ZIF-8/SDB/PMMA compound particle is added in organic solvent, removes SDB template.It is preferred that
, the organic solvent is polar aprotic solvent.Preferably, the organic solvent is any one in DMF, DMAC.It is described
DMF refers to n,N-Dimethylformamide, and DMAC is n,N-dimethylacetamide, both polar aprotic solvent, and dissolubility is good,
It does not react, it is good that dissolution removes SDB template effect.
Further, in step (4), the repair liquid is the one of the unsaturated fats such as tung oil, linseed oil, sodium alginate oil
Kind is several.Such as can be single tung oil, be also possible to tung oil+linseed oil mixing repair liquid, can also be tung oil,
The compound repair liquid such as linseed oil, sodium alginate.Preferably one or both of tung oil, linseed oil mixture.
Further, step (4) ZIF-8/PMMA hollow microsphere is added in repair liquid and impregnates 4-20h；Then, it is heated to 30-
40 DEG C, continue to stir 4-12h, so that repair liquid enters ZIF-8/PMMA hollow microsphere.Repair liquid leaching first is added in hollow microsphere
It is bubble a period of time, then micro- to heat and continue to impregnate, rate and quality that repair liquid penetrates into hollow microsphere are promoted, height is obtained
Quality microcapsules.
Further, it after step (4) filtering, is washed 2-5 times with ultrapure water and/or C1-C6 low mass molecule alcohol, preferably 3 times.It is preferred that
It is alternately washed for water and ethyl alcohol, water and ethyl alcohol wash 3 times respectively.
Further, after the completion of step (4) washing, centrifuge separation is dried in vacuo 5-10h, preferably 6-8h.Preferably, very
Empty drying temperature≤45 DEG C.Preferably, centrifugal rotational speed 2000-18000r/min, preferably 6000-8000r/min.
Compared with prior art, beneficial effects of the present invention:
1. long-acting type bilayered microcapsule of the invention includes with repair liquid (corrosion inhibiter by MOF/PMMA bilayered microcapsule structure
Or linseed oil) cooperation made of capsule-core.MOF outer shell is hollow microsphere, coats capsule-core, and PMMA is inner layer cyst wall, bilayer vesicles
Hollow layer between wall is also filled by capsule-core.The overall load capsule-core lotion total amount of microcapsules is higher, has preferable active table
It is existing, multiple repair can be played, microcapsules load reparation tung oil component content is higher, and repairing effect is more preferably lasting.
2. long-acting type bilayered microcapsule of the invention, bilayered microcapsule cladding repairs liquid (repair liquid) or corrosion inhibiter, has
The effect of long-acting reparation, repairs liquid exudation and is repaired, repaired when first time after MOf porous layer is punctured by crackle, between cyst wall
Ineffective crack propagation punctures second layer MOf porous layer, and inner layer capsule-core, which overflows, carries out second of reparation；Such as imitated when first time
Fruit is ideal, and remaining inner layer microcapsules will be produced from repairing effect after second of corrosion cracks, while can also increase
The service life of selfreparing.
3. the long-acting repairing type MOF/PMMA/ bilayered microcapsule of the present invention can be seeped using MOf as porous structure by hole
It is repaired out with fracture breaks two ways, repair mode multiplicity.Reparation liquid tung oil inside microcapsules, which has, preferably to be held
Long stability is able to maintain good activity in prolonged storage, avoids the problem that microcapsules fail.
Detailed description of the invention:
Fig. 1 is ZIF-8/PMMA/ linseed oil microcapsules.
Fig. 2 is the resistance variations situation that microcapsules impregnate different time coating.
Specific embodiment
Below with reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
It is all that this is belonged to based on the technology that the content of present invention is realized for the scope of the above subject matter of the present invention is limited to the following embodiments
The range of invention.
<Embodiment 1 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
0.0078g azodiisobutyronitrile is taken, 1.4g styrene is added, (DVB, 80%, isomers is mixed for 2.1gDVB(divinylbenzene
Close object, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and the mixture of 4g lauryl sodium sulfate in,
It is uniformly mixed to form oily phase.50mL deionized water is added, is uniformly mixed, with high speed homogenization device with the revolving speed of 15000r/min
Homogeneous 2min obtains stable oil-in-water pickering emulsion.Gained lotion is added in 100mL neck round bottom flask, leads to after cooling
Nitrogen 20min displaced air, then by lotion under the conditions of 75 DEG C heating water bath 16h.6000r/min is centrifuged 2min after reaction,
It collects product and is washed with 10mL dehydrated alcohol, repeated centrifugation is washed 3 times.It is solid that white is obtained after 40 DEG C of vacuum drying 2h
Body SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
0.5 gram of PMMA is added in 50mL water, ultrasound 15 minutes at 0 DEG C.Then, be added 4 grams of SDB nanospheres, mixture after
It is stirred by ultrasonic 30 minutes at 0 DEG C continuous, is swollen PMMA sufficiently into SDB particle, to PMMA drop under the observation of optical microscopy
After fading away.Then, the PMMA SDB particle being swollen is transferred in a three neck round bottom in ice bath.By 0.05g
Potassium persulfate solution is dissolved in 1L deionized water and obtains oxidizing agent solution, takes the 10mL oxidizing agent solution, is then added at one time point
In granular media.Then 0.5mL hydrochloric acid (0.5mol/L) is added, is instilled by syringe.5h is kept at a temperature of 0 DEG C, in room temperature 26
It polymerize again at DEG C 18 hours, polymerize PMMA sufficiently.Resulting green SDB/PMMA compound particle is centrifuged through 6000r/min
2min, with 10mL ethanol washing, repeated centrifugation is washed 3 times, until supernatant is colourless.Finally, being done in 40 DEG C of vacuum drying ovens of product
It is dry in 48h.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 11.3 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses magnetic agitation 30min after 3min.The methanol solution containing 0.59g zinc nitrate hexahydrate is added later, continues to stir 3h,
6000r/min is centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtains ZIF-8/SDB/PMMA compound particle.Add
Enter and impregnate 3h in the DMF of 50mL, remove SDB template, filtering, 10mL dehydrated alcohol washs 3 times, and 45 DEG C of vacuum drying 2h are obtained
Prepare ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
Dry ZIF-8/PMMA hollow microsphere being added in 20mL linseed oil, 25 DEG C of room temperature are impregnated and are stirred 12 hours,
Then heating and magnetic agitation reaction 12h in 35 DEG C of water-baths.Filtering is alternately washed with 10mL ultrapure water and 10mL dehydrated alcohol
It washs, repeats above-mentioned carrying out washing treatment three times, then be centrifugated 3min with centrifuge 6000r/min, finally by the load of washes clean
The microcapsules of linseed oil are put into 60 DEG C of vacuum drying 8h in vacuum oven, obtain ZIF-8/PMMA/ linseed oil microcapsules.
<test>
Microcapsules prepared by embodiment 1 carry out scratch testing impedance, and test method is as follows:
Control group: taking 50g bisphenol A epoxide resin E-44, and 9.2g diethylenetriamine is added, and two drop dispersing agents are added dropwise, and two drips are flat
Agent is uniformly mixed.Then it brushes and is rinsed on clean iron plate by derusting and with dehydrated alcohol.Iron plate is horizontal positioned,
It is to be coated to spontaneously dry overnight.After film is done solid work, with blade scratch.Film coated surface, control patch are pasted onto using patch electrode
Distance 10cm between plate electrode, two patch electrode being equidistant apart from scratch, tests the resistance variations situation of patch electrode
Test group: taking 50g bisphenol A epoxide resin E-44, and 9.2g diethylenetriamine is added, and two drop dispersing agents are added dropwise, and two drips are flat
Agent is uniformly mixed.Then 4g microcapsules are added, stir evenly, then brush by derusting and being rinsed with dehydrated alcohol
On clean iron plate.Iron plate is horizontal positioned, to be coated to spontaneously dry overnight.After film is done solid work, with blade scratch.Using patch
Attachment of electrodes controls distance 10cm between patch electrode in film coated surface, and two patch electrode being equidistant apart from scratch are surveyed
Try the resistance variations situation of patch electrode.
As a result as shown in Figure 2.Wherein, curve 2a is variation of the common microencapsulation coating impedance with scratch time to rupture；
Curve 2b is addition ZIF-8/PMMA/ linseed oil microencapsulation coating with the variation with scratch time to rupture.Figure middle impedance is applying
For layer during 0-1 hours, impedance is lower, and impedance increases after 1 hour, this is because selfreparing has occurred in coating；It is general after 10 hours
The impedance of logical coating declines always, and the impedance of bilayered microcapsule is replied during 10-20 hours, this is micro- second
The process of capsule reparation, when scratching first time, some microcapsules have only punctured first layer, and subsequent microcapsules continue release repairing
Liquid realizes the repair for coating, so resistance persistently changes.
<Embodiment 2 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
Take 0.0078g azodiisobutyronitrile, be added 1.5g styrene, 2.2g DVB(divinylbenzene (DVB, 80%, isomers
Mixture, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and 4.3g lauryl sodium sulfate mixture
In, it is uniformly mixed to form oily phase.50mL deionized water is added, is uniformly mixed, with high speed homogenization device with 12000r/min's
Revolving speed homogeneous 3min obtains stable oil-in-water pickering emulsion.Gained lotion is transferred in 100mL neck round bottom flask, cold
But lead to nitrogen 25min afterwards, then for 24 hours, 6000r/min is centrifuged 2min to heating water bath after reaction under the conditions of 73 DEG C by lotion, receives
Collection product is simultaneously washed with 10mL mixed alcohol (dehydrated alcohol: methanol=1:1 mixed alcohol), and repeated centrifugation is washed 3 times.Through 45
DEG C vacuum drying 2h after obtain white solid SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
SDB/PMMA Nano composite granules are prepared by swelling-diffusion-interface-polymerization.Firstly, 0.5 gram of PMMA is added to
In 50mL water, ultrasonic disperse 20 minutes at 0 DEG C.Then, 4 grams of SDB nanospheres are added, mixture is kept for 0 DEG C, is continued ultrasound and is stirred
It mixes 35 minutes, makes the abundant swelling of PMMA into SDB particle, under the observation of optical microscopy after PMMA drop fades away；It will
The SDB particle of PMMA swelling is transferred in a three neck round bottom in ice bath.1 step 2 of 10mL embodiment is taken to prepare
Oxidizing agent solution is added at one time in dispersion, and 0.5mL sulfuric acid (0.3mol/L) then is added, is instilled by syringe.0
6h is kept at a temperature of DEG C, is polymerize 16 hours again under room temperature (28 DEG C), is polymerize PMMA sufficiently.Resulting green SDB/PMMA is multiple
It closes particle and is centrifuged 2min through 6000r/min, then use 10mL ethanol washing, repeated centrifugation is washed 3 times, until supernatant is colourless.
Finally, drying in 45 DEG C of vacuum drying ovens for 24 hours.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 11.5 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses magnetic agitation 45min after 3min.The methanol solution containing 0.62g zinc nitrate hexahydrate is added later, continues to stir 5h,
6000r/min is centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtains ZIF-8/SDB/PMMA compound particle.Add
Enter and impregnate 3h in the DMF of 50mL, remove SDB template, filtering, 10mL dehydrated alcohol washs 3 times, and 45 DEG C of vacuum drying 2h are obtained
Prepare ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
Dry ZIF-8/PMMA microcapsules are put into 20mL tung oil, stir 10 hours.Then, add in 36 DEG C of water-baths
Heat, magnetic agitation 14h, later with 10mL ultrapure water and 10mL dehydrated alcohol alternately washing three times, then with centrifuge 6000r/min
It is centrifugated 3min, the negative microcapsules of washes clean are finally put into 58 DEG C of vacuum drying 8h in vacuum oven, obtain ZIF-
8/PMMA/ repairs liquid microcapsule.
<comparative example 1>
Microcapsule product is prepared using with the identical mode of embodiment 2, only step (2) does not use note during sulfuric acid is added
Emitter is added dropwise, and sulfuric acid solution needed for being added at one time reaction is uniformly mixed.Remaining preparation section and embodiment 2 are kept
Unanimously.
<Embodiment 3 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
0.008g azodiisobutyronitrile is taken, 1.5g styrene is added, (DVB, 80%, isomers is mixed for 2.1gDVB(divinylbenzene
Close object, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and 4.1g sodium tetradecyl sulfate mixing, stir
It mixes to be uniformly mixed and forms oily phase.50mL deionized water is added, is uniformly mixed, it is equal with the revolving speed of 15000r/min with high speed homogenization device
Matter 4min obtains stable oil-in-water pickering emulsion.Gained lotion is added in 100mL neck round bottom flask, leads to nitrogen after cooling
Gas 15min displaced air, then by lotion under the conditions of 79 DEG C heating water bath 12h.6000r/min is centrifuged 2min after reaction, receives
Collection product is simultaneously washed with 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times.White solid is obtained after 40 DEG C of vacuum drying 2h
SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
0.5 gram of PMMA is added in 50mL water, ultrasonic disperse 20 minutes at 0 DEG C.Then, 4 grams of SDB nanospheres are added, mix
Object continue 0 DEG C at be stirred by ultrasonic 35 minutes, be swollen PMMA sufficiently into SDB particle, under the observation of optical microscopy to
After PMMA drop fades away.Then, the PMMA SDB particle being swollen is transferred in a three neck round bottom in ice bath.
The oxidizing agent solution for taking 1 step 2 of 10mL embodiment to prepare, is added at one time in dispersion.Then 0.5mL hydrochloric acid (1mol/ is added
L), instilled by syringe.5h is kept at a temperature of 0 DEG C, polymerize again at room temperature 18 hours, polymerize PMMA sufficiently.Gained
Green SDB/PMMA compound particle be centrifuged 2min through 6000r/min, then use 10mL ethanol washing, repeated centrifugation wash 3 times,
Until supernatant is colourless.Finally, drying in 50 DEG C of vacuum drying ovens of products obtained therefrom for 24 hours.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 11.5 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses magnetic agitation 50min after 3min.The methanol solution containing 0.59g zinc nitrate hexahydrate is added later, continues to stir 3h,
6000r/min is centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtains ZIF-8/SDB/PMMA compound particle.Add
Enter and impregnate 3h in the DMF of 50mL, remove SDB template, filtering, 10mL dehydrated alcohol washs 3 times, and 45 DEG C of vacuum drying 2h are obtained
Prepare ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
By dry ZIF-8/PMMA hollow microsphere, it puts into 20mL tung oil, impregnates and stir 6 hours.Then, 35 are transferred to
It is heated in DEG C water-bath, magnetic agitation reacts 12h.Filtering is alternately washed three times with 10mL ultrapure water and 10mL dehydrated alcohol, then
It is centrifugated 3min with centrifuge 6000r/min, the microcapsules of the load tung oil of washes clean are finally put into vacuum oven
In 55 DEG C of vacuum drying 12h, obtain ZIF-8/PMMA/ tung oil microcapsules.
<comparative example 2>
Microcapsule product is prepared using with the identical mode of embodiment 3, omits step 2, SDB nanosphere prepared by step 1 is straight
It scoops out for step 3, ZIF-8/SDB compound particle will be prepared into, do not use DMF to impregnate and remove SDB template.It is finally that this is compound
Particle is added in tung oil and impregnates according to the technique of step 4, obtains the ZIF-8/SDB composite particles of load tung oil.
<Embodiment 4 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
0.0078g azobisisoheptonitrile is taken, 1.5g styrene is added, (DVB, 80%, isomers is mixed for 2.1g DVB(divinylbenzene
Close object, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and 4.1g lauryl sodium sulfate mixture,
It is uniformly mixed to form oily phase.50mL deionized water is added, is uniformly mixed, with high speed homogenization device with the revolving speed of 12000r/min
Homogeneous 4min obtains stable oil-in-water pickering emulsion.Gained lotion is added in 100mL neck round bottom flask, leads to after cooling
Nitrogen 23min displaced air, then by lotion under the conditions of 75 DEG C heating water bath 17h.6000r/min is centrifuged 2min after reaction,
It collects product and is washed with 10mL dehydrated alcohol, repeated centrifugation is washed 3 times.It is solid that white is obtained after 42 DEG C of vacuum drying 2h
Body SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
0.5 gram of PMMA is added in 50mL water, is kept for 2-3 DEG C of solution temperature, ultrasonic disperse 25 minutes.Then, 4 grams of SDB are added
Nanosphere, mixture continue to keep to be stirred by ultrasonic 30 minutes at 1-3 DEG C of feed liquid temperature, are swollen PMMA sufficiently into SDB particle,
Under the observation of optical microscopy after PMMA drop fades away.Then, the PMMA SDB particle being swollen is transferred to one in ice
In three neck round bottom in bath.The oxidizing agent solution for taking 1 step 2 of 10mL embodiment to prepare, is added at one time in dispersion, so
0.5mL hydrochloric acid (0.5mol/L) is added afterwards, is equally to be instilled relative to the equimolar amount of PMMA by syringe.In 0 DEG C of temperature
Degree is lower to keep 6h, polymerize 20 hours again at room temperature, polymerize PMMA sufficiently.Resulting green SDB/PMMA compound particle warp
6000r/min is centrifuged 2min, then uses 10mL ethanol washing, repeated centrifugation is washed 3 times, until supernatant is colourless.Finally, product
It dries in 40 DEG C of vacuum drying ovens in 48h.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 11.5 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses magnetic agitation 30min after 3min.The methanol solution containing 0.59g zinc nitrate hexahydrate is added later, continues to stir 3h,
6000r/min is centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtains ZIF-8/SDB/PMMA compound particle.Add
Enter and impregnate 3h in the DMF of 50mL, remove SDB template, filtering, 10mL dehydrated alcohol washs 2 times, and 45 DEG C of vacuum drying 2h are obtained
Prepare ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
It is added to dry ZIF-8/PMMA hollow microsphere in the solvent of tung oil, impregnates and stirs 7 hours.Then, it is transferred to
In 35 DEG C of water-baths, magnetic agitation reacts 11h.Filtering, three times, then with centrifuge is separated, finally with ultrapure water and ethanol washing
The microcapsules of the load tung oil of washes clean are put into 60 DEG C of vacuum drying 8h in vacuum oven, obtain ZIF-8/PMMA/ paulownia
Oil microcapsule.
<comparative example 3>
Prepare microcapsule product using with the identical mode of embodiment 4, only step 2 be prepared SDB/PMMA compound particle with
Afterwards, using hot-air oven, 65 DEG C of progress drying and processings, remaining step of preparation process is remained unchanged.Microcapsules part is bonded in one
It rises, loses original discrete particles state, it is difficult to keep original dispersing morphology of microcapsules.
<Comparative example 4 >
Microcapsule product is prepared using with the identical mode of embodiment 4, only the microcapsules of load tung oil are prepared in step 4,
Using hot-air oven, 70 DEG C of progress drying and processings, remaining step of preparation process is remained unchanged.Microcapsules part bonds together,
And part microcapsules rupture, internal tung oil outflow, microcapsules integral adhesive is together.
<Comparative example 5 >
Microcapsule product is prepared using with the identical mode of embodiment 4, only the microcapsules of load tung oil are prepared in step 4,
Using vacuum drying, 80 DEG C of drying temperature, remaining step of preparation process is remained unchanged.Microcapsules rupture, internal tung oil outflow are micro-
Capsule integral adhesive is together.
<Embodiment 5 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
0.008g azobisisoheptonitrile is taken, 2g styrene is added, (DVB, 80%, isomers mixes 2.5gDVB(divinylbenzene
Object, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and the mixture of 4.5g lauryl sodium sulfate in,
It is uniformly mixed to form oily phase.50mL deionized water is added, is uniformly mixed, with high speed homogenization device with the revolving speed of 15000r/min
Homogeneous 2min obtains stable oil-in-water pickering emulsion.Gained lotion is added in 100mL neck round bottom flask, leads to after cooling
Nitrogen 20min displaced air, then by lotion under the conditions of 78 DEG C heating water bath 16h.6000r/min is centrifuged 2min after reaction,
It collects product and is washed with 10mL dehydrated alcohol, repeated centrifugation is washed 3 times.It is solid that white is obtained after 40 DEG C of vacuum drying 2h
Body SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
0.6 gram of PMMA is added in 50mL water, ultrasound 22 minutes at 0 DEG C.Then, be added 5 grams of SDB nanospheres, mixture after
It is stirred by ultrasonic 30 minutes at 0 DEG C continuous, is swollen PMMA sufficiently into SDB particle, to PMMA drop under the observation of optical microscopy
After fading away.Then, the PMMA SDB particle being swollen is transferred in a three neck round bottom in ice bath.Take 10mL
The oxidizing agent solution that 1 step 2 of embodiment is prepared, is added at one time in dispersion, and 0.5mL hydrochloric acid (0.5mol/L) then is added,
It is equally to be instilled relative to the equimolar amount of PMMA by syringe.6.5h is kept at a temperature of 0 DEG C, is polymerize again at room temperature
16.5 hours, it polymerize PMMA sufficiently.Resulting green SDB/PMMA compound particle is centrifuged 2min through 6000r/min, then uses
10mL ethanol washing, repeated centrifugation is washed 3 times, until supernatant is colourless.Finally, dry 36h in 40 DEG C of vacuum drying ovens of product.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 12.1 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses 2min, magnetic agitation 25min.The methanol solution containing 0.63g zinc nitrate hexahydrate is added later, continues to stir 4h,
6000r/min is centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtains ZIF-8/SDB/PMMA compound particle.Add
Enter and impregnate 3h in the DMF of 50mL, remove SDB template, filtering, 10mL dehydrated alcohol washs 3 times, and 45 DEG C of vacuum drying 2h are obtained
Prepare ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
By dry ZIF-8/PMMA hollow microsphere, puts into the solvent of 20mL tung oil, impregnate and stir 10 hours, then 35
Magnetic agitation reacts 14h in DEG C water-bath.Filtering, with 10mL ultrapure water and 10mL mixed alcohol (methanol: ethyl alcohol=2:8, volume ratio)
Washing three times, then with centrifuge 6000r/min is centrifugated 3min, is finally put into the microcapsules of the load tung oil of washes clean
60 DEG C of vacuum drying 8h, obtain ZIF-8/PMMA/ tung oil microcapsules in vacuum oven.
<Comparative example 6 >
Prepare microcapsule product using with the identical mode of embodiment 5, only step 2, PMMA and SDB nanosphere in the solution,
Magnetic agitation dispersion, does not use ultrasonic wave added.Compare the influence that ultrasonic treatment combines SDB nanosphere and PMMA.It is testing
The speed of discovery PMMA swelling into SDB nanosphere is extremely slow in the process, and the structure and morphology for influencing microcapsules is realized.
<Comparative example 7 >
Microcapsule product is prepared using with the identical mode of embodiment 5, only during step 4 load, is in advance added tung oil
Then heat puts into ZIF-8/PMMA hollow microsphere to 35 DEG C, magnetic agitation reacts 14h, and more different immersion load process is right
In the influence of load efficiency.Tung oil temperature is higher, and the speed for penetrating into microcapsules is not accelerated but, and mainly temperature raising is led
Surface of microcapsule ZIF-8 and the mutual polymerization reaction of tung oil are caused, the duct of microcapsules is enclosed, the microcapsules vacuum of front and back will be impregnated
It carries out weighing after drying and compares weight, the weight of microcapsules, which increases, is reduced to 6.8% by increasing by 46.7%, and weight increases significant drop
Low, the total amount for showing that tung oil enters inside microcapsules is reduced.
<Test >
Microcapsules prepared by embodiment 5 and comparative example 6-7 are subjected to scratch test, test method is as follows:
Firstly, preparing varnish: it takes 50g bisphenol A epoxide resin E-44,9.2g diethylenetriamine is added, be added dropwise two drop dispersing agents, two
Levelling agent is dripped, is uniformly mixed.Then 4g microcapsules are added, stir evenly, then brush by derusting and with anhydrous second
Alcohol rinses on clean iron plate.Iron plate is horizontal positioned, to be coated to spontaneously dry overnight.After film is done solid work, with blade scratch, draw
From fine to coarse, iron plate is transferred to humidity 100%, in 35 DEG C of temperature of baking oven after scratch, dried trace width by most thick scratch about 1mm
Roasting 4h, takes out the situation of change of each scratch of observation.
Addition Application Example 5 prepares the varnish of microcapsules, and coating produces at scratch without iron rust after scratch experiment
It is raw.And it also obtains sufficient infiltration at maximum scratch to repair, scratch destroys minimum.
The varnish of microcapsules prepared by Comparison study example 6 is added, brushing iron plate has certain reparation for fine scratches later
Effect, iron rust is less, but the scratch for being greater than 0.5mm, and tung oil flows the ineffective of filling, there is slight rusty stain.Point
Analysis reason is primarily due to lack necessary auxiliary, lead to PMMA micro-capsule wall during PMMA is dispersed into SDB nanosphere
Structure it is partially thin, structural strength is bad, it is subsequent package ZIF-8 structure and morphology low strength, load the poor quality of tung oil, repair
It acts on again on the weak side.
Microcapsules prepared by comparative example 7 are added in varnish, and coating scratch experiment result has apparent differentiation, for
The lesser situation of scratch, repair is preferable, and repair ability is obviously insufficient in the case of scratch is more serious, and analysis reason is main
It is to load temperature during tung oil, so that the efficiency that tung oil enters microcapsules reduces, influences the practical maximum reparation of microcapsules
Ability.
<Embodiment 6 >
Prepare long-acting type bilayered microcapsule
Prepare SDB nanosphere
0.008g azobisisoheptonitrile is taken, 1.5g styrene is added, (DVB, 80%, isomers mixes 2.0gDVB(divinylbenzene
Object, the 4- tert-butyl catechol inhibitor comprising concentration less than 0.1%) and the mixture of 0.5g lauryl sodium sulfate in,
It is uniformly mixed to form oily phase.50mL deionized water is added, is uniformly mixed, with high speed homogenization device with the revolving speed of 15000r/min
Homogeneous 2min obtains stable oil-in-water pickering emulsion.Gained lotion is added in 100mL neck round bottom flask, leads to after cooling
Nitrogen 18min displaced air, then by lotion under the conditions of 78 DEG C heating water bath 16h.6000r/min is centrifuged 2min after reaction,
It collects product and is washed with 10mL dehydrated alcohol, repeated centrifugation is washed 2 times.It is solid that white is obtained after 40 DEG C of vacuum drying 2h
Body SDB nanosphere.
Prepare SDB/PMMA Nano composite granules
0.5 gram of PMMA is added in 50mL water, ultrasound 22 minutes at 0 DEG C.Then, be added 4 grams of SDB nanospheres, mixture after
It is stirred by ultrasonic 30 minutes at 0 DEG C continuous, is swollen PMMA sufficiently into SDB particle, to PMMA drop under the observation of optical microscopy
After fading away.Then, the PMMA SDB particle being swollen is transferred in a three neck round bottom in ice bath.Take 10mL
The oxidizing agent solution that 1 step 2 of embodiment is prepared, is added at one time in dispersion, and 0.5mL hydrochloric acid (0.8mol/L) then is added,
It is instilled by syringe.6.5h is kept at a temperature of 0 DEG C, polymerize again at room temperature 16.5 hours, polymerize PMMA sufficiently.Gained
Green SDB/PMMA compound particle be centrifuged 2min through 6000r/min, then use 10mL ethanol washing, repeated centrifugation wash 3 times,
Until supernatant is colourless.Finally, dry 36h in 40 DEG C of vacuum drying ovens of product.
Prepare ZIF-8/PMMA hollow microsphere
1 gram of SDB/PMMA solid powder and 13.2 grams of 2-methylimidazoles are weighed in single-necked flask, 50mL anhydrous methanol is added, is surpassed
Sound disperses 2.5min, magnetic agitation 25min.The methanol solution containing 0.63g zinc nitrate hexahydrate is added later, continues to stir
4h, 6000r/min are centrifuged 3min, 10mL dehydrated alcohol, and repeated centrifugation is washed 3 times, obtain ZIF-8/SDB/PMMA compound particle.
It is added in the DMF of 50mL and impregnates 3h, remove SDB template, filtering, 10mL dehydrated alcohol washs 3 times, and 45 DEG C of vacuum drying 2h are obtained
To preparation ZIF-8/PMMA hollow microsphere.
Load renovation agent or corrosion inhibiter
It is added to dry ZIF-8/PMMA hollow microsphere in the solution of 20mL sodium alginate, impregnates and stirs 14 hours, so
Magnetic agitation reacts 14h in 35 DEG C of water-baths afterwards.Filtering, with 10mL ultrapure water and 10mL mixed alcohol (n-butanol: ethyl alcohol=1:
9, volume ratio) it washs three times, then it is centrifugated 3min with centrifuge 6000r/min, finally by the load alginic acid of washes clean
The microcapsules of sodium are put into 60 DEG C of vacuum drying 8h in vacuum oven, obtain ZIF-8/PMMA/ sodium alginate micro gel capsule.
Claims (10)
1. a kind of long-acting repairing type bilayered microcapsule preparation method, which comprises the following steps:
(1) SDB nanosphere is prepared
Azo-initiator is taken, is added in the mixture of styrene, divinylbenzene and anionic surfactant, is mixed to form
Oily phase；It is added in deionized water, mixing, homogeneous obtains oil-in-water pickering emulsion；
Under nitrogen protection, pickering emulsion is heated to 70-80 DEG C of reaction 10-20h, after reaction, centrifuge washing 2-5
Secondary, vacuum drying obtains white solid SDB nanosphere；
(2) SDB/PMMA Nano composite granules are prepared
PMMA is taken to be added to the water, ultrasonic disperse；Then, the SDB nanosphere of step (1) preparation, ultrasound, stirring, to PMMA is added
Swelling enters SDB nanosphere；
Oxidant is added, stirs evenly, inorganic acid is added dropwise and stirs, 0-5 DEG C of reaction 2-8h then heats to 15-35 DEG C of room temperature,
Polymerization reaction 14-28h, so that PMMA sufficiently polymerize；After the reaction was completed, it is centrifuged, washing, until supernatant is colourless, vacuum drying,
Obtain SDB/PMMA Nano composite granules；
(3) ZIF-8/PMMA hollow microsphere is prepared
SDB/PMMA Nano composite granules, 2-methylimidazole obtained by step (2) are taken, anhydrous methanol is added, is uniformly dispersed；Nitre is added
Sour zinc, is stirred to react 2-8h, and centrifuge washing obtains ZIF-8/SDB/PMMA compound particle；
Gained ZIF-8/SDB/PMMA compound particle is added in organic solvent, SDB template is removed, is filtered, it is dry, obtain ZIF-
8/PMMA hollow microsphere；
(4) renovation agent or corrosion inhibiter are loaded
By ZIF-8/PMMA hollow microsphere, it is added in repair liquid and impregnates, be stirred to react, so that repair liquid enters in ZIF-8/PMMA
Empty microballoon；Filtering is washed, and is centrifuged, vacuum drying, obtains ZIF-8/PMMA/ repairing liquid microcapsule.
2. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that step (1) described azo
Class initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-isobutyrate hydrochloride, two isobutyl imidazoline hydrochloride of azo
One or more of.
3. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that in step (1), the yin
Ionic surface active agent refers at least one of C12-C16 sodium alkyl sulfate, C12-C16 sodium alkyl sulfonate.
4. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that step (2) described PMMA
It is polymethyl methacrylate, molecular weight ranges are 60,000-30 ten thousand.
5. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that in step (2), the oxygen
Agent is one or both of potassium peroxydisulfate, ammonium persulfate, peroxide oxidant.
6. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that step (2) fills PMMA
Divide and is swollen into SDB nanosphere；It fades away under the observation of optical microscopy to PMMA drop, shows that PMMA is sufficiently swollen entrance
In SDB nanosphere.
7. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that in step (3), SDB/
The mass ratio of PMMA Nano composite granules and 2-methylimidazole is SDB/PMMA Nano composite granules: 2-methylimidazole mass ratio
=1:0.5-5.
8. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that 2- first is added in step (3)
The weight ratio of base imidazoles and zinc nitrate hexahydrate is 25:1-2.
9. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that step (3) ZIF-8/
SDB/PMMA compound particle is added in organic solvent, removes SDB template, the organic solvent is polar aprotic solvent.
10. long-acting repairing type bilayered microcapsule preparation method as described in claim 1, which is characterized in that described in step (4)
Repair liquid is one or more of tung oil, linseed oil, sodium alginate.
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