CN110449094A - A kind of preparation method of self-repairing microcapsule and its application in super-hydrophobic coat - Google Patents
A kind of preparation method of self-repairing microcapsule and its application in super-hydrophobic coat Download PDFInfo
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- 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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- 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
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- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
Application the present invention relates to a kind of preparation method of self-repairing microcapsule and its in super-hydrophobic coat.Self-repairing microcapsule provided by the invention uses the porous nano particle of package low-surface-energy for Nang core, nanoscale porous granule structure can make microcapsules nano-particles filled crack when destroying by soda acid, play the role of selfreparing, porous structure can make the specific surface area of Nang core increase, surface can increase, and then adsorption ability is stronger, can be adsorbed on Nang wicking surface for low-surface energy substance is easier, microcapsules have preferable selfreparing effect when pH is 5-9；The cyst wall of microcapsules selects high molecular polymer, by the synergistic effect of Nang core and cyst wall, when the structure of cyst wall is by destroying, the surface of Nang core roughness still with higher, by the synergistic effect of cyst wall and Nang core, impaired super hydrophobic surface can be automatically repaired.
Description
Technical field
The invention belongs to super hydrophobic material technical fields, and in particular to a kind of preparation method of self-repairing microcapsule and its
Application in super-hydrophobic coat.
Background technique
Super hydrophobic surface (contact angle is greater than 150 ° with roll angle less than 10 °) is had excellent performance, therefore in many fields, such as certainly
The fields such as cleaning, anticorrosive, ice-covering-proof, drag reduction, antifouling are with a wide range of applications.However, artificial super hydrophobic surface is in reality
Durability is bad in the use process of border, is easy to lose ultra-hydrophobicity because the physical damages such as scraping, wearing, greatly limit super
Therefore the application of hydrophobic material, is assigned in addition, coating, when by acid-base solution erosion damage, also solution loses ultra-hydrophobicity
Give super hydrophobic material self-healing properties, in damage of material spontaneous starting reparation " program ", make up damage to material structure and group
Adverse effect caused by point repairs impaired ultra-hydrophobicity, can effectively extend the service life of material, leads to its application is expanded
Domain has a very important significance.
For these reasons, the present invention is specifically proposed.
Summary of the invention
In order to solve problem above of the existing technology, the present invention provides a kind of preparation methods of self-repairing microcapsule
And its application in super-hydrophobic coat, self-repairing microcapsule of the invention is when by acid-base solution erosion damage, microcapsules
It discharges low-surface energy substance in time in pH response range and porous nano particle can fill crack, reach the work of selfreparing
With.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of self-repairing microcapsule, includes the following steps:
(1) porous nano particle is prepared first；
(2) the porous nano particle of preparation is added in the mixed solution of deionized water and ethyl alcohol that volume ratio is 2:1
Low-surface energy substance is added thereto stirring 2-3h and forms mixed solution A, obtains Nang core by stirring and dissolving；
(3) polyglutamic acid and acrylic acid are dissolved in respectively in the phosphate buffer of 0.1mol/L, under stirring conditions
Initiator ammonium sulfate is added and stirs 25-35min, tetramethylethylenediamine is then added and is stirred for 1.8-2.2h formation mixed solution B,
Mixed solution A is added dropwise in mixed solution B and is stirred 2-3h, is cleaned, dry at 50-60 DEG C, grinding obtains described
Self-repairing microcapsule.
Further, porous nano particle described in step (1) is poriferous titanium dioxide nanoparticle, porous zinc bloom
One of nanoparticle, porous silicon dioxide nano particle are a variety of.
Further, the poriferous titanium dioxide nanoparticle is prepared by the following method: ethyl alcohol, positive metatitanic acid
Four butyl esters, diethanol amine, glacial acetic acid are added sequentially to jar agitation 2-3h according to volume ratio 1:0.5:0.05:0.8, are formed milky white
It is aged 12h after color suspension, outwells supernatant and with 3 removing foreign ions of acetone eccentric cleaning, the dry 12h at 60 DEG C,
Grinding obtains powdered titanium dioxide, and powdered titanium dioxide is calcined 3-4h at 300-400 DEG C, obtains poriferous titanium dioxide
Nanoparticle；
Further, the porous zinc bloom nanoparticle is prepared by the following method: 2.2g zinc acetate is molten
The mixed solution of deionized water and ethyl alcohol that volume ratio is 1:1-3 is added in 15-25ml ethanol amine in solution, is stirred 25-
35min, then the isothermal reaction 4-8h at 170-180 DEG C, eccentric cleaning to neutrality, dry 12h at 60 DEG C, in 300- after grinding
3-4h is calcined at 400 DEG C, obtains porous zinc bloom nanoparticle；
Further, the porous silicon dioxide nano particle is prepared by the following method: 0.5g polyethylene
Pyrrolidones is dissolved in 40ml ethyl alcohol and the mixed solution of 60ml deionized water, and 1g lauryl amine is dissolved in 5ml dehydrated alcohol and is added
Enter wherein, 5ml ethyl orthosilicate is added after stirring 50-70min, and stirs 5-7h at 30-50 DEG C and form white colloidal, centrifugation
After cleaning, dry 12h, after grinding, calcines 3.5-4.5h at 550-650 DEG C, obtains porous silicon dioxide nano at 100 DEG C
Particle.
Further, in step (2) according to parts by weight, porous nano particle 15-30 parts by weight, deionized water and ethyl alcohol
Mixed solution 20-30 parts by weight, low-surface energy substance 1-4 parts by weight.
Further, low-surface energy substance described in step (2) be ten trifluoro zinc-base triethoxysilanes, 1H, 1H,
2H, 2H- perfluoro capryl trimethoxy silane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane and octadecane
One of base trimethoxy silane is a variety of.
Further, polyglutamic acid in step (3), acrylic acid, ammonium sulfate, tetramethylethylenediamine mass ratio be 3:7:
The mass volume ratio of 0.55:0.043, polyglutamic acid and phosphate buffer is 0.03g:5ml.
Application of the self-repairing microcapsule of method preparation described in a kind of in super-hydrophobic coat.
Further, the sensitive range 5-9 of the super-hydrophobic coat pH.
Namely in pH between 5-9, super-hydrophobic coat prepared by the present invention has preferable selfreparing effect, hydrophobicity
It can be with endurance quality lasting stability.
Further, the super-hydrophobic coat is according to parts by weight, including the following raw material: acrylic resin 15-20 weight
Part, solvent 15-30 parts by weight, microcapsules 5-20 parts by weight, surfactant 1-3 parts by weight, lyophobic dust 10-20 weight
Part, defoaming agent 1-5 parts by weight, levelling agent 1-5 parts by weight and curing agent 2-8 parts by weight.
Further, the solvent be one of toluene, dimethylbenzene, acetone, polyamide, tetrahydrofuran or a variety of,
The surfactant is polyvinylpyrrolidone or cetyl trimethylammonium bromide, and the lyophobic dust is stone
Wax, talcum powder, bentonite, ten trifluoro zinc-base triethoxysilanes, 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane, 12
One of alkyl trimethoxysilane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane are a variety of, described
Defoaming agent be dimethyl silicone polymer or poly- third ethylene glycol-alkylene oxide polymer, the levelling agent be polyether-modified poly- silicon
Oxygen alkane, the curing agent are benzoyl peroxide, cumyl hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, mistake
One of peroxyester is a variety of.
Further, the preparation method of super-hydrophobic coat includes the following steps:
(a) substrate pre-processes: selecting silica glass as matrix, matrix leaching is cleaned by ultrasonic 15- in ethanol
20min, ultrapure water clean three times, and drying is encased spare with preservative film；
(b) super-hydrophobic coat is prepared by the following method: the weight according to each raw material, acrylic resin is dissolved in molten
In agent, microcapsules, surfactant, lyophobic dust, defoaming agent, levelling agent and curing agent are sequentially added, ultrasonic agitation is uniform
It is coated on spare substrate, solidifies at 100-110 DEG C afterwards.
The super-hydrophobic coating of preparation of the invention can be used for the fields such as outdoor building, glass, metal and textile.
Compared with prior art, the invention has the benefit that
(1) self-repairing microcapsule provided by the invention uses the porous nano particle of package low-surface-energy for Nang core, nanometer
The porous granule structure of grade can make microcapsules nano-particles filled crack when destroying by soda acid, play the work of selfreparing
With porous structure can make the specific surface area of Nang core increase, and surface can increase, and then adsorption ability is stronger, can incite somebody to action
Low-surface energy substance is easier to be adsorbed on Nang wicking surface, and microcapsules have preferable selfreparing effect when pH is 5-9；It is micro-
The cyst wall of capsule selects high molecular polymer, and high molecular polymer contains the group of the pH response characteristic of weak acid or weak base, such as carboxylic
Base, amino etc., as pH value, the variation of ionic strength, weak acid or weak base group can ionize, hydrogen bond dissociation causes to polymerize
Swelling, by the synergistic effect of Nang core and cyst wall, when the structure of cyst wall is by destroying, the surface of Nang core is still with higher
Roughness can be automatically repaired impaired super hydrophobic surface by the synergistic effect of cyst wall and Nang core；
(2) super-hydrophobic coat of preparation of the invention can timely be discharged in pH sensitive range low-surface energy substance with
And porous nano particle can fill crack, achieve the effect that selfreparing, so that the hydrophobic performance of the super-hydrophobic coating and resistance to
Long consistency of performance is stablized, and coating of the invention can be using the fields such as building, glass, metal and textile outdoors.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the transmission electron microscope picture of poriferous titanium dioxide nanoparticle prepared by embodiment 1；
Fig. 2 is the contact angle of super-hydrophobic coat prepared by embodiment 4；
Fig. 3 is acid solution treated the contact angle that super-hydrophobic coat prepared by embodiment 4 is 5 with pH；
Fig. 4 is the contact angle after the alkaline solution treatment that super-hydrophobic coat prepared by embodiment 4 is 9 with pH.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
A kind of preparation method of self-repairing microcapsule of the present embodiment, includes the following steps:
(1) prepare poriferous titanium dioxide nanoparticle first: poriferous titanium dioxide nanoparticle is prepared as follows
It forms: ethyl alcohol, tetrabutyl titanate, diethanol amine, glacial acetic acid is added sequentially to burn according to volume ratio 1:0.5:0.05:0.8
Cup stirring 2h, is aged 12h after forming milk-white coloured suspension, outwells supernatant and with 3 removing foreign ions of acetone eccentric cleaning,
Dry 12h, grinding obtain powdered titanium dioxide, powdered titanium dioxide are calcined 3h at 300 DEG C, is obtained more at 60 DEG C
Porous titanium dioxide nanoparticle；
(2) the poriferous titanium dioxide nanoparticle of preparation is added to volume ratio as the deionized water of 2:1 and mixing for ethyl alcohol
Stirring and dissolving in solution is closed, low-surface energy substance is added thereto stirring 2.5h and forms mixed solution A, obtains Nang core, wherein more
The mixed solution 20g of porous titanium dioxide nanoparticle 15g, deionized water and ethyl alcohol, low-surface energy substance 1g, low-surface energy substance
For ten trifluoro zinc-base triethoxysilanes；
(3) it by the phosphate buffer of polyglutamic acid 3g and acrylic acid the 7g 0.1mol/L for being dissolved in 500ml respectively, is stirring
Initiator ammonium sulfate 0.55g is added under conditions of mixing and stirs 30min, tetramethylethylenediamine 0.043g is then added and is stirred for 2h shape
At mixed solution B, mixed solution A is added dropwise in mixed solution B and is stirred 2.5h, is cleaned with deionized water, at 55 DEG C
Dry, grinding obtains the self-repairing microcapsule.
The transmission electron microscope picture of poriferous titanium dioxide nanoparticle manufactured in the present embodiment is as shown in Figure 1.
The aperture of the micropore of poriferous titanium dioxide nanoparticle is as the raising of calcination temperature can reduce, specific surface area subtracts
Less, the crystallinity of crystal grain increases, and the average grain diameter of nano particle increases, as shown in Figure 1, porous silica manufactured in the present embodiment
Titanium nanoparticle, the micropore size that calcination temperature is formed at 300 DEG C is smaller, aperture in 1-2nm, grain diameter in 10-12nm,
Varying aperture is unobvious.The applicant has found by a large number of experiments when calcination temperature increases to 400 DEG C, forms Detitanium-ore-type
Titanium dioxide.But calcination temperature it is excessively high when, porous structure can shrink or collapse, and specific surface area greatly reduces, under specific surface energy
Drop, and then the adsorbance of low surface mass is influenced, the hydrophobic effect of coating is deteriorated.
Embodiment 2
A kind of preparation method of self-repairing microcapsule of the present embodiment, includes the following steps:
(1) prepare porous zinc bloom nanoparticle first: porous zinc bloom nanoparticle is prepared by the following method:
2.2g zinc acetate is dissolved in 20ml ethanol amine, and the mixed solution of deionized water and ethyl alcohol that volume ratio is 1:2 is added
10ml is stirred 30min, then the isothermal reaction 6h at 175 DEG C, eccentric cleaning to neutrality, dry 12h, grinding at 60 DEG C
3.5h is calcined at 350 DEG C afterwards, obtains porous zinc bloom nanoparticle；
(2) the porous zinc bloom nanoparticle of preparation is added to the mixing of deionized water and ethyl alcohol that volume ratio is 2:1
Low-surface energy substance is added thereto stirring 2h and forms mixed solution A, obtains Nang core, wherein porous oxygen by stirring and dissolving in solution
Change zinc nanoparticle 22g, the mixed solution 25g of deionized water and ethyl alcohol, low-surface energy substance 2.5g, low-surface energy substance ten
Dialkyl group trimethoxy silane；
(3) it by the phosphate buffer of polyglutamic acid 3g and acrylic acid the 7g 0.1mol/L for being dissolved in 500ml respectively, is stirring
Initiator ammonium sulfate 0.55g is added under conditions of mixing and stirs 30min, tetramethylethylenediamine 0.043g is then added and is stirred for 1.8h
Mixed solution B is formed, mixed solution A is added dropwise in mixed solution B and is stirred 2h, is cleaned with deionized water, at 50 DEG C
Dry, grinding obtains the self-repairing microcapsule.
Embodiment 3
A kind of preparation method of self-repairing microcapsule of the present embodiment, includes the following steps:
(1) prepare porous silicon dioxide nano particle first: porous silicon dioxide nano particle is prepared as follows
It forms: 0.5g polyvinylpyrrolidone is dissolved in 40ml ethyl alcohol and the mixed solution of 60ml deionized water, 1g lauryl amine is molten
It is added thereto in 5ml dehydrated alcohol, 5ml ethyl orthosilicate is added after stirring 60min, and stirred 6h at 40 DEG C and form white
Colloid, after eccentric cleaning, dry 12h, after grinding, calcines 4h at 600 DEG C, obtains porous silicon dioxide nano at 100 DEG C
Particle；
(2) the porous silicon dioxide nano particle of preparation is added to volume ratio as the deionized water of 2:1 and mixing for ethyl alcohol
Stirring and dissolving in solution is closed, low-surface energy substance is added thereto stirring 2h and forms mixed solution A, obtains Nang core, wherein porous
The mixed solution 30g of Nano particles of silicon dioxide 30g, deionized water and ethyl alcohol, low-surface energy substance 4g, low-surface energy substance are
1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane；
(3) by the phosphate buffer of polyglutamic acid 1.5g and acrylic acid the 3.5g 0.1mol/L for being dissolved in 250ml respectively,
Initiator ammonium sulfate 0.275g is added under stirring conditions and stirs 30min, tetramethylethylenediamine 0.0215g is then added and stirs again
It mixes 2.2h and forms mixed solution B, mixed solution A is added dropwise in mixed solution B and is stirred 3h, is cleaned with deionized water,
Dry at 60 DEG C, grinding obtains the self-repairing microcapsule.
Embodiment 4
The present embodiment is application of the self-repairing microcapsule of the preparation of embodiment 1 in super-hydrophobic coat, prepares super-hydrophobic painting
The raw material of layer includes the following: acrylic resin 15g, solvent 15g, the microcapsules 5g of the preparation of embodiment 1, surfactant 1g, dredges
Aqueous substance 10g, defoaming agent 1g, levelling agent 1g and curing agent 2g；Wherein, solvent is toluene, and surfactant is polyethylene pyrrole
Pyrrolidone, lyophobic dust are ten trifluoro zinc-base triethoxysilanes, and defoaming agent is dimethyl silicone polymer, and levelling agent is polyethers
Modified polyorganosiloxane (Hubei xinsihai Chemical Co., Ltd., manufacturer), curing agent is benzoyl peroxide；
The preparation method of super-hydrophobic coat includes the following steps:
(a) substrate pre-processes: it selects silica glass as matrix, matrix leaching is cleaned by ultrasonic 15min in ethanol,
Ultrapure water cleans three times, and drying is encased spare with preservative film；
(b) super-hydrophobic coat, which is prepared by the following method:, is dissolved in acrylic resin in solvent, sequentially adds micro- glue
Capsule, surfactant, lyophobic dust, defoaming agent, levelling agent and curing agent are coated in spare substrate after being stirred by ultrasonic uniformly
On, solidify at 100 DEG C.
Embodiment 5
The present embodiment is application of the self-repairing microcapsule of the preparation of embodiment 2 in super-hydrophobic coat, prepares super-hydrophobic painting
The raw material of layer includes the following: acrylic resin 17.5g, solvent 22.5g, the microcapsules 12.5g of the preparation of embodiment 2, surface-active
Agent 2g, lyophobic dust 15g, defoaming agent 3g, levelling agent 3g and curing agent 5g；Wherein, solvent is tetrahydrofuran, surfactant
For cetyl trimethylammonium bromide, lyophobic dust is dodecyltrimethoxysilane, and defoaming agent is poly- third ethylene glycol-ring
Oxygen alkane polymer, levelling agent are Siloxane-Oxyalkylene Copolymers (Hubei xinsihai Chemical Co., Ltd., manufacturer), solidification
Agent is cumyl hydroperoxide；
The preparation method of super-hydrophobic coat includes the following steps:
(a) substrate pre-processes: selecting silica glass as matrix, matrix leaching is cleaned by ultrasonic in ethanol
17.5min, ultrapure water clean three times, and drying is encased spare with preservative film；
(b) super-hydrophobic coat, which is prepared by the following method:, is dissolved in acrylic resin in solvent, sequentially adds micro- glue
Capsule, surfactant, lyophobic dust, defoaming agent, levelling agent and curing agent are coated in spare substrate after being stirred by ultrasonic uniformly
On, solidify at 105 DEG C.
Embodiment 6
The present embodiment is application of the self-repairing microcapsule of the preparation of embodiment 3 in super-hydrophobic coat, prepares super-hydrophobic painting
The raw material of layer includes the following: acrylic resin 20g, solvent 30g, the microcapsules 20g of the preparation of embodiment 3, surfactant 3g, dredges
Aqueous substance 20g, defoaming agent 5g, levelling agent 5g and curing agent 8g；Wherein, solvent is acetone, and surfactant is cetyl
Trimethylammonium bromide, lyophobic dust 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane, defoaming agent are poly- third ethylene glycol-
Alkylene oxide polymer, levelling agent are Siloxane-Oxyalkylene Copolymers (Hubei xinsihai Chemical Co., Ltd., manufacturer), Gu
Agent is benzoyl peroxide；
The preparation method of super-hydrophobic coat includes the following steps:
(a) substrate pre-processes: it selects silica glass as matrix, matrix leaching is cleaned by ultrasonic 20min in ethanol,
Ultrapure water cleans three times, and drying is encased spare with preservative film；
(b) super-hydrophobic coat, which is prepared by the following method:, is dissolved in acrylic resin in solvent, sequentially adds micro- glue
Capsule, surfactant, lyophobic dust, defoaming agent, levelling agent and curing agent are coated in spare substrate after being stirred by ultrasonic uniformly
On, solidify at 110 DEG C.
Comparative example 1
The super-hydrophobic coat of this comparative example preparation is same as Example 4, the difference is that, poriferous titanium dioxide nanoparticle
Son does not use calcination processing during the preparation process, directly grinds.
Test example 1
Self-healing properties of the super-hydrophobic coating of the method preparation of testing example 4 under acid-base condition.
Hydrophobicity test method: with contact angle tester measurement water droplet in film surface contact angle, contact angle values by 5 with
Seat in the plane is set after measurement is averaged and is obtained, and static contact angle is using drop method (sessile drop) measurement of lying, and super hydrophobic surface is (i.e.
Static contact angle is greater than 150 ° of surface) measurement when, when measurement, uniformly uses 5 μ L water droplets.
1, the contact angle of the super-hydrophobic coat prepared according to above-mentioned hydrophobicity test method, testing example 4 is
159.12 °, contact angle is as shown in Figure 2.
2, the acid solution that pH is 4,5 and 6 is respectively configured with hydrochloric acid, the aqueous slkali for being 8,9 and 10 with sodium hydroxide configuration pH.
6 groups of sample coatings are prepared respectively according to the method for embodiment 4 to carry out testing super-hydrophobic coating under different acid-base property
Self-healing properties, test method is as follows: respectively immersing sample coatings in the solution of different pH for 24 hours, then removes coating
And the acid-base solution on surface is removed, contact angle is measured, painting is then placed on 80 DEG C of environment remediation 2h, measures the contact of coating
Angle the results are shown in Table 1.
Table 1
| The pH value of solution of processing | Contact angle (°) after acid or alkaline solution treatment | Contact angle (°) after reparation |
| 4 | 132.14 | 138.95 |
| 5 | 153.26 | 158.16 |
| 6 | 154.49 | 158.87 |
| 8 | 153.62 | 158.71 |
| 9 | 154.03 | 158.83 |
| 10 | 134.62 | 139.82 |
As it can be seen from table 1 the repairing performance of coating is preferable when pH is 5-9, pH repairs effect less than 5 or when being greater than 9
Fruit is poor, illustrates that super-hydrophobic coat of the invention has preferable selfreparing effect when pH is 5-9, when of the invention super-hydrophobic
When coating is destroyed by the solution that pH is 5-9, stable hydrophobic performance can be kept.
Wherein, the contact angle of super-hydrophobic coat is as shown in figure 3, the alkaline solution treatment that pH is 9 after the acid solution processing that pH is 5
The contact angle of super-hydrophobic coat afterwards is as shown in Figure 4.
The present inventor has also done above-mentioned test to the super-hydrophobic coat of other embodiments preparation, as a result almost the same, due to
Length is limited, will not enumerate.
Test example 2
This test example tests the self-healing properties under acid-base condition, test side to super-hydrophobic coat prepared by comparative example 1
Method is identical as test example 1, and measurement result is shown in Table 2.
1, the contact angle of super-hydrophobic coat prepared by comparative example 1 is 153.12 °.
Table 2
| The pH value of solution of processing | Contact angle (°) after acid or alkaline solution treatment | Contact angle (°) after reparation |
| 4 | 123.45 | 127.56 |
| 5 | 146.32 | 148.28 |
| 6 | 147.56 | 147.98 |
| 8 | 145.85 | 146.13 |
| 9 | 146.38 | 148.23 |
| 10 | 114.62 | 123.87 |
As can be seen that not using the hydrophobic coating self-healing properties ratio of the nano-titanium dioxide of calcination processing from table 1 and 2
Selfreparing effect using the hydrophobic coating of calcination processing is poor, and contact angle is small, i.e., hydrophobicity also reduces, this is because at calcining
The hole that reason increases porous nano particle surface increases surface area, and the absorption property of low-surface energy substance is stronger, selfreparing
Effect is more preferable, and hydrophobic performance is more preferable.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of preparation method of self-repairing microcapsule, which comprises the steps of:
(1) porous nano particle is prepared first；
(2) the porous nano particle of preparation is added in the mixed solution of deionized water and ethyl alcohol that volume ratio is 2:1 and is stirred
Low-surface energy substance is added thereto stirring 2-3h and forms mixed solution A, obtains Nang core by dissolution；
(3) polyglutamic acid and acrylic acid are dissolved in the phosphate buffer of 0.1mol/L respectively, are added under stirring conditions
Initiator ammonium sulfate stirs 25-35min, and tetramethylethylenediamine is then added and is stirred for 1.8-2.2h formation mixed solution B, will mix
It closes solution A and is added dropwise in mixed solution B and stirs 2-3h, clean, dry at 50-60 DEG C, grinding obtains described review one's lessons by oneself
Multiple microcapsules.
2. the preparation method of self-repairing microcapsule according to claim 1, which is characterized in that more described in step (1)
Hole nanoparticle is poriferous titanium dioxide nanoparticle, in porous zinc bloom nanoparticle, porous silicon dioxide nano particle
It is one or more.
3. the preparation method of self-repairing microcapsule according to claim 2, which is characterized in that the poriferous titanium dioxide
Nanoparticle is prepared by the following method: ethyl alcohol, tetrabutyl titanate, diethanol amine, glacial acetic acid according to volume ratio 1:
0.5:0.05:0.8 is added sequentially to jar agitation 2-3h, is aged 12h after forming milk-white coloured suspension, outwells supernatant and with third
3 removing foreign ions of ketone eccentric cleaning, the dry 12h at 60 DEG C, grinding obtains powdered titanium dioxide, by powdered dioxy
Change titanium and calcine 3-4h at 300-400 DEG C, obtains poriferous titanium dioxide nanoparticle；
Preferably, the porous zinc bloom nanoparticle, which is prepared by the following method:, is dissolved in 15- for 2.2g zinc acetate
In 25ml ethanol amine, and the mixed solution of deionized water and ethyl alcohol that volume ratio is 1:1-3 is added, is stirred 25-35min,
Then the isothermal reaction 4-8h at 170-180 DEG C, eccentric cleaning to neutrality, dry 12h at 60 DEG C, at 300-400 DEG C after grinding
Lower calcining 3-4h, obtains porous zinc bloom nanoparticle；
Further preferably, the porous silicon dioxide nano particle is prepared by the following method: 0.5g polyvinyl pyrrole
Alkanone is dissolved in 40ml ethyl alcohol and the mixed solution of 60ml deionized water, 1g lauryl amine is dissolved in 5ml dehydrated alcohol, it is added
In, 5ml ethyl orthosilicate is added after stirring 50-70min, and stir 5-7h at 30-50 DEG C and form white colloidal, eccentric cleaning
Afterwards, the dry 12h at 100 DEG C, after grinding, calcines 3.5-4.5h at 550-650 DEG C, obtains porous silicon dioxide nano grain
Son.
4. the preparation method of self-repairing microcapsule according to claim 1, which is characterized in that according to weight in step (2)
Part, porous nano particle 15-30 parts by weight, the mixed solution 20-30 parts by weight of deionized water and ethyl alcohol, low-surface energy substance 1-
4 parts by weight.
5. the preparation method of self-repairing microcapsule according to claim 1 or 4, which is characterized in that described in step (2)
Low-surface energy substance is ten trifluoro zinc-base triethoxysilanes, 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane, dodecane
One of base trimethoxy silane, hexadecyl trimethoxy silane and octadecyl trimethoxysilane are a variety of.
6. the preparation method of self-repairing microcapsule according to claim 1, which is characterized in that polyglutamic acid in step (3),
Acrylic acid, ammonium sulfate, tetramethylethylenediamine mass ratio be 3:7:0.55:0.043, the matter of polyglutamic acid and phosphate buffer
Amount volume ratio is 0.03g:5ml.
7. a kind of self-repairing microcapsule answering in super-hydrophobic coat of method preparation as claimed in any one of claims 1 to 6
With.
8. application of the self-repairing microcapsule according to claim 7 in super-hydrophobic coat, which is characterized in that its feature exists
In the super-hydrophobic coat is according to parts by weight, including the following raw material: acrylic resin 15-20 parts by weight, solvent 15-30 weight
Measure part, microcapsules 5-20 parts by weight, surfactant 1-3 parts by weight, lyophobic dust 10-20 parts by weight, defoaming agent 1-5 weight
Part, levelling agent 1-5 parts by weight and curing agent 2-8 parts by weight.
9. application of the self-repairing microcapsule according to claim 8 in super-hydrophobic coat, which is characterized in that described is molten
Agent is one of toluene, dimethylbenzene, acetone, polyamide, tetrahydrofuran or a variety of, and the surfactant is polyethylene pyrrole
Pyrrolidone or cetyl trimethylammonium bromide, the lyophobic dust are paraffin, talcum powder, bentonite, ten trifluoro zinc-bases
Triethoxysilane, 1H, 1H, 2H, 2H- perfluoro capryl trimethoxy silane, dodecyltrimethoxysilane, cetyl three
One of methoxy silane, octadecyl trimethoxysilane are a variety of, the defoaming agent be dimethyl silicone polymer or
Poly- third ethylene glycol-alkylene oxide polymer, the levelling agent are Siloxane-Oxyalkylene Copolymers, and the curing agent is benzoyl peroxide
One of formyl, cumyl hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide are a variety of.
10. being existed according to application of the self-repairing microcapsule in super-hydrophobic coat, feature described in claim 7-9 any one
In the preparation method of super-hydrophobic coat includes the following steps:
(a) substrate pre-processes: it selects silica glass as matrix, matrix leaching is cleaned by ultrasonic 15-20min in ethanol,
Ultrapure water cleans three times, and drying is encased spare with preservative film；
(b) super-hydrophobic coat is prepared by the following method: the weight according to each raw material, and acrylic resin is dissolved in solvent
In, microcapsules, surfactant, lyophobic dust, defoaming agent, levelling agent and curing agent are sequentially added, after ultrasonic agitation is uniform
Coated on spare substrate, solidify at 100-110 DEG C.
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