CN105949861A - Self-repairing super-hydrophobic composite material, preparation method and application thereof - Google Patents
Self-repairing super-hydrophobic composite material, preparation method and application thereof Download PDFInfo
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- 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
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- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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Abstract
The invention discloses a self-repairing super-hydrophobic composite material, a preparation method and application thereof. The composite material has a structural general formula of: APA/M-PD/APA@HMS, wherein, APA is alkyl primary amine having a long carbon chain with C greater than or equal to 12, PD is polydopamine, HMS is hollow mesoporous SiO2 microsphere, APA@HMS refers to HMS loaded with APA, and the M refers to an antifouling able to stick on PD. The preparation method provided by the invention has the advantages of simple operation, and rich raw material sources, and is suitable for mass production. The prepared APA/M-PD/APA@HMS can be used as a paint additive, can endow a coating with super-hydrophobicity, antifouling property, self-repairability, and durability, and can be used for protective coatings of marine materials.
Description
Technical field
The present invention relates to a kind of super-hydrophobic composite, it particularly relates to a kind of the energy super-hydrophobic composite of selfreparing, Preparation Method And The Use.
Background technology
Marine organisms adhere tos and have a strong impact on the global problem of marine facility military service performance with corroding to have become relating to sea material.As the one risen the in recent years super-hydrophobic bionic coating of antifouling concept, it it is a class the most active in novel environmental friendly nonpolluting coating research field, it can substitute the environmentally harmful tradition antifouling paint that application at present is more, its application can be made to be extended significantly, and development prospect is boundless.This type coating is typically by the simulation animals and plants such as Folium Nelumbinis, sharkskin surface, hydrophobic material is utilized to build surface micronano level coarse structure or modify low-surface energy substance at rough porous material surface, to change physical arrangement and the chemical property of material surface, make material have super-hydrophobic characteristic, reach to suppress the purpose of fouling organism attachment.
Although super hydrophobic material presents the character of excellence and huge application prospect in antifouling field, but it is limited by very large in actual application aspect, its main cause, first consist in routine micro-nano classification rough surface construction method (as, the methods such as chemical etching, Cement Composite Treated by Plasma, vapour deposition and electrochemical process deposition), excessively complicated, technological requirement is the highest, is unfavorable for large-scale production；Secondly, super hydrophobic surface coarse structure due to these modifications in actual applications, self-regeneration function is not mostly had when being worn or destroy, its shaggy micro-nano hierarchy is when being rubbed, its local sharp protrusion structure is more easily damaged, and causes micro-nano hierarchy to disappear and be difficult to maintain good mechanical stability；Furthermore, if in the marine environment of geo-stationary, simple dependence coating ultra-hydrophobicity is also not enough to reach to completely inhibit the purpose of biological attachment, also needs collaborative other technologies.Therefore, study a kind of have be persistency, can the super hydrophobic material of the feature such as self-repairability and applicable large-scale production significant.
Summary of the invention
The technical problem to be solved is to provide a kind of super-hydrophobic composite, its can selfreparing, there is soil resistance, super-hydrophobicity and persistency, be suitable for large-scale production, marine environment can be used for.
For reaching above-mentioned purpose, the invention provides a kind of energy super-hydrophobic composite of selfreparing, the super-hydrophobic composite of Preparation Method And The Use a kind of energy selfreparing, the general structure of this composite is: APA/
M-PD/APA@HMS, wherein, APA is the kiber alkyl amine of the Long carbon chain being more than or equal to 12 with C, and PD is poly-dopamine, and HMS is the mesoporous SiO of hollow2Microsphere, APA@HMS refers to that HMS is loaded with APA, described M and refers to stick to the anti-fouling agent on PD.
Above-mentioned can the super-hydrophobic composite of selfreparing, wherein, this composite is to form poly-dopamine film on the HMS of load APA, then loads anti-fouling agent M, then is mixed to form the polymeric film of band alkyl hydrophobic chain with APA and prepares.
The super-hydrophobic composite of above-mentioned energy selfreparing, wherein, in this composite, anti-fouling agent M and APA@HMS mass ratio are 0.4% ~ 1%.
The super-hydrophobic composite of above-mentioned energy selfreparing, wherein, described APA selects any one or any two or more mixing in lauryl amine, tetradecy lamine, cetylamine or 18-amine..
The super-hydrophobic composite of above-mentioned energy selfreparing, wherein, described SiO2Nano-level sphere granule selected by microsphere, and its particle diameter is 200 nm ~ 500 nm.
The super-hydrophobic composite of above-mentioned energy selfreparing, wherein, described SiO2Micron-size spherical particles selected by microsphere, and its particle diameter is 2 μm ~ 5 μm.
The super-hydrophobic composite of above-mentioned energy selfreparing, wherein, described anti-fouling agent refers to any one or any two or more mixture in nano-Ag particles, nano cuprous oxide, nano titanium oxide and graphene oxide.
Present invention also offers the preparation method of a kind of super-hydrophobic composite according to above-mentioned energy selfreparing, the method includes the steps of:
Step 1, loads APA: HMS with APA, conventional organic solvent are mixed, and is dried, and obtains loading the HMS microsphere powder APA@HMS of APA；
Step 2, loads anti-fouling agent, and it comprises:
Step 2.1, mixes with dopamine in the basic conditions by APA@HMS so that it is microsphere surface forms poly-dopamine thin film, obtains PD/APA@HMS；
Step 2.2, adds anti-fouling agent M in PD/APA@HMS, and stirring forms the APA@HMS microsphere M-PD/APA@HMS carrying M poly-dopamine film coated；
Step 3, mixes M-PD/APA@HMS with APA so that it is Surface Creation is with the polymeric film of alkyl hydrophobic chain, and obtain carrying anti-fouling agent can self-repairing super hydrophobic microsphere APA/
M-PD/APA@HMS；
Wherein, APA is the kiber alkyl amine of the Long carbon chain being more than or equal to 12 with C, and PD is poly-dopamine, and HMS is the mesoporous SiO of hollow2Microsphere, APA@HMS refers to that HMS is loaded with APA, described M and refers to stick to the anti-fouling agent on PD.
The preparation method of the super-hydrophobic composite of above-mentioned energy selfreparing, wherein, described HMS is the mesoporous SiO of hollow2Microsphere, described SiO2Microsphere selects nano-level sphere granule or micron-size spherical particles；Described APA selects any one or any two or more mixing in lauryl amine, tetradecy lamine, cetylamine or 18-amine.；Described M refers to any one or any two or more mixture in nano-Ag particles, nano cuprous oxide, nano titanium oxide and graphene oxide；M Yu APA@HMS mass ratio is 0.4% ~ 1%.
Present invention also offers the purposes of the super-hydrophobic composite of a kind of above-mentioned energy selfreparing, wherein, this composite A PA/
M-PD/APA@HMS can serve as the super-hydrophobic bionic coating of selfreparing.
Above-mentioned purposes, wherein, the preparation method of the super-hydrophobic bionic coating of described selfreparing is: is mixed with quality 1:1 with micron order microsphere by APA/ M-PD/APA@HMS nanoscale microsphere, then mixes with oil paint, through covering with paint, lacquer, colour wash, etc. the super-hydrophobic bionic coating forming selfreparing.The purpose of above-mentioned mixing is to make coating surface form multiple dimensioned coarse structure, to realize ultra-hydrophobicity, through the ratio 1:1 the most by quality ratio of experiment mixing.
Super-hydrophobic composite prepared by the present invention is used as coating additive, coating can be made to have super-hydrophobicity, soil resistance, self-repairability, and have persistency, can be used for relating to the protective coating of sea material.
Accompanying drawing explanation
Fig. 1 is the reaction principle figure of the super-hydrophobic composite material and preparation method thereof of a kind of energy selfreparing of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, by specific embodiment, the invention will be further described, and these embodiments are merely to illustrate the present invention, are not limiting the scope of the invention.
The present invention provide a kind of can the super-hydrophobic composite of selfreparing, it is loaded with nano antifouling agent, and have can the super hydrophobic surface of self-repair function.The general structure of this composite is: APA/
M-PD/APA@HMS, wherein, APA is the kiber alkyl amine of the Long carbon chain being more than or equal to 12 with C, and PD is poly-dopamine, and HMS is the mesoporous SiO of hollow2Microsphere, APA@HMS refers to that HMS is loaded with APA, described M and refers to stick to the anti-fouling agent on PD；APA content in APA@HMS depends on the size of HMS inner hollow space；M Yu APA@HMS mass ratio is preferably 0.4% ~ 1%.This composite A PA/
M-PD/APA@HMS is to form poly-dopamine film on the HMS of load APA, then loads anti-fouling agent M, then is mixed to form the polymeric film of band alkyl hydrophobic chain with APA and prepares.
Being illustrated in figure 1 the preparation principle of the super-hydrophobic composite of the present invention, the preparation process of this super-hydrophobic composite is as follows:
Step 1: the preparation of environmental type nano antifouling agent.Every green is the additive that environmental protection inorganic nano antifouling agent can serve as in this method, as medium in nano-Ag particles, nano cuprous oxide, nano titanium oxide and graphene oxide, and application is in the method.Present case is as a example by nanometer silver, and its preparation process is with AgNO3For presoma, caseinhydrolysate is reducing agent, prepares the nano-Ag particles that a collection of particle diameter is 10 ~ 20nm in the basic conditions.
Step 2, the mesoporous SiO of hollow2The preparation of microsphere (HMS).Buy size and be respectively 200 nm ~ 500 nm and the 2 μm ~ 5 solid SiO of μm spherical monodisperse nano-particle2Microsphere is template, with cetyl trimethylammonium bromide (CTAB) as surfactant, in the basic conditions, with TEOS(tetraethyl orthosilicate) it is silicon source shape shell, then surfactant templates, the most in addition solid SiO of sodium carbonate selective etch are removed in calcining2, forming the HMS with aerial configurations, its size is by the solid SiO added2Determine.
Step 3, carrying silver can prepare by self-repairing super hydrophobic microsphere.First take the HMS of above-mentioned synthesis, load the kiber alkyl amine (APA, such as 18-amine. etc.) with Long carbon chain, obtain loading the HMS microsphere (APA HMS) of APA；Secondly, above-mentioned microsphere is mixed under alkalescence condition (pH=8.5) with dopamine, its microsphere surface is made to form poly-dopamine thin film, then under conditions of magnetic agitation, add Silver Nanoparticles, to form the APA@HMS microsphere carrying silver-colored poly-dopamine film coated, finally it is mixed with APA again, making its Surface Creation with the polymeric film of alkyl hydrophobic chain, carrying silver with realization can self-repairing super hydrophobic microsphere (APA/
Ag-PD/APA@HMS) nanoscale or micron-sized preparation.
Step 4, the nanoscale that obtained by above-mentioned synthetic method is carried silver can self-repairing super hydrophobic microsphere and micron order carry silver can self-repairing super hydrophobic microsphere, mix according to quality 1:1, it is then added in oil paint, finally by spraying, just can obtain carrying silver at matrix surface can self-repairing super hydrophobic bionic coating.
The preparation method of the super-hydrophobic composite of the present invention is illustrated below in conjunction with embodiment.
Embodiment 1
1. the preparation of nanometer silver
By 45 mg caseinhydrolysates and 10 mg
Sodium hydroxide is dissolved in 45 mL deionized waters, then instills 5 mL silver nitrate (20 mM) solution.By above-mentioned mixed solution after magnetic agitation heats 3 h at 60 DEG C, mixed with ethanol 1:4 it is incorporated in high speed centrifugation under 20000 × g, finally precipitate with deionized water is cleaned final vacuum and is dried to obtain nanometer silver (Ag NPs) granule.
2. prepared by nanoscale hollow mesoporous silicon oxide (HMS)
First, in 1 L deionized water, nanoscale (200 nm ~ 500 nm) the solid SiO of spherical monodisperse nano-particle that 5 g buy is added2Microsphere, and ultrasonic disperse formed white SiO2Emulsion；The CTAB of 5:1:1 mixing the most by volume, ethanol and deionized water, and by ammonia regulation solution ph to 8.0 ~ 8.5；By this solution and above-mentioned SiO2Emulsion mixes according to 10:1 volume ratio, after uniform stirring, rapidly joins a small amount of TEOS, and centrifugal after continuing to stir 5 ~ 6 h, after the precipitate deionized water obtained repeatedly rinses, calcines 6 h in the Muffle furnace of 500 DEG C.Taking the powder after above-mentioned calcining, every 1 g is dispersed in 100m L deionized water, is subsequently adding 2 g sodium carbonate, is heated at 50 DEG C reacting 10 h.Centrifugal collecting precipitation, then with deionized water rinsing, it is dried to obtain nanoscale HMS, preserve stand-by.
3. prepared by the HMS nanoscale microsphere (APA@HMS) of load APA
According to mass ratio 1:1:10, by the HMS of above-mentioned synthesis and the kiber alkyl amine (APA with Long carbon chain, advise wherein in alkyl carbon chain C more than 12, such as lauryl amine, tetradecy lamine, cetylamine or 18-amine. etc.) and ethanol mixing, it is dried after ultrasonic 30min, obtains loading the HMS nanoscale microsphere powder (APA@HMS) of APA；
4. nanoscale load silver can be prepared by self-repairing super hydrophobic microsphere (APA/ Ag-PD/APA@HMS)
At 40 m L Tris(tri-(methylol) aminomethanes)-HCl(pH=8.5) in buffer solution, add the 2.5 above-mentioned microsphere powder of g, after ultrasonic disperse, add 75
Mg dopamine hydrochloride, stirs 4-6 h, obtains, with ethanol purge, the APA@HMS microsphere (PD/ APA@HMS) that poly-dopamine (PD) wraps up after being centrifuged under room temperature condition；Above-mentioned microsphere is re-dispersed into 15 m
In the ethanol of L, it is subsequently adding the 0.01 previously prepared nanometer silver of g, ultrasonic 15
Magnetic agitation 30 min after min, adds 100 the most again
Mg APA, is stirred at room temperature 10-12 h, successively centrifugal, cleaning, and obtaining carrying silver can self-repairing super hydrophobic microsphere (APA/
Ag-PD/APA@HMS).
5. micron order load silver can be prepared by self-repairing super hydrophobic microsphere (APA/ Ag-PD/APA@HMS)
Micron order carries silver the preparation of self-repairing super hydrophobic microsphere can then select micron order (2 μm-5 μm) SiO2For template, its method is same as mentioned above.
Super-hydrophobic composite (APA/ Ag-PD/APA@HMS) prepared by the present invention can be used as can self-repairing super hydrophobic bionic coating, its preparation method is: the nanoscale that obtained by above-mentioned synthetic method is carried silver can self-repairing super hydrophobic microsphere and micron order carry silver can self-repairing super hydrophobic microsphere, mix according to quality 1:1, it is then added in oil paint, finally by spraying, just can obtain carrying silver at matrix surface can self-repairing super hydrophobic bionic coating.The hydrophobicity of this coating prepared, self-repairability, soil resistance all can meet the protection requirements relating to sea material, and concrete testing result is as follows:
Hydrophobicity: with epoxy resin as matrix resin, according to the method described above doping carry silver can self-repairing super hydrophobic microsphere, and be sprayed on metallic matrix, dried use JC2000D1 Static Contact angle measuring instrument to be coated tests its contact angle, test result shows, doping can be after self-repairing super hydrophobic microsphere, and epoxy coating has brought up to 157 ° to the contact angle of deionized water from 66 °, it is achieved that super-hydrophobic.Its reason that can reach ultra-hydrophobicity is 2 points: one, is because dopamine and can generate poly-dopamine after peroxidating, and this material can react the hydrophobic substance generating low-surface-energy with the kiber alkyl amine with Long carbon chain；Its two, be the doping of the hydrophobic microsphere of Nano/micron level so that coating surface can form the micro-nano coarse structure of polynary yardstick.
Self-repairability: with epoxy resin as matrix resin, according to the method described above doping carry silver can self-repairing super hydrophobic microsphere, and be sprayed on metallic matrix, coating surface is etched by dried use PE-100 plasma etching instrument to be coated, and using JC2000D1 Static Contact its contact angle of angle measuring instrument tracking and testing subsequently, experimental result shows, after 1 time etches, contact angle on surface of coating, in 30 min, has been returned to 153 ° by 131 °；After 5 times etch, contact angle on surface of coating, in 30min, has been returned to 147 ° by 106 °.Visible, the self-repairability of super-hydrophobic composite prepared by the present invention is the best.
Soil resistance: with epoxy resin as matrix resin, according to the method described above doping carry silver can self-repairing super hydrophobic microsphere, and be sprayed on metallic matrix, coating is the most stand-by.With diatom for target fouling organism, using sea water enrichment culture 2 days at 37 DEG C, then immerse in algae solution by above-mentioned test button, take out after 1 day, current rinse, and use NIKON/Ti-E inverted fluorescence microscope to observe surface attachment situation.Test with undope carry silver can self-repairing super hydrophobic microsphere epoxy resin for comparison.Experimental result shows, doping carry silver can its diatom adhesion amount of coating of self-repairing super hydrophobic microsphere less, be 7 ± 3/mm2,
And do not adulterate carry silver can its diatom adhesion amount of coating of self-repairing super hydrophobic microsphere more, be 1557 ± 120/mm2。
Super-hydrophobic composite prepared by the present invention is realized by two kinds of approach for coating is antifouling: one is, the ultra-hydrophobicity of coating so that fouling organism is not easy to be attached to coating surface；Two are, the effect of nanometer silver anti-fouling agent, and it can kill the fouling organism being already attached to coating surface.Simultaneously as nanometer silver and its carrier (that is, SiO2The poly-dopamine on microsphere top layer) combined by physical adherence effect, it is possible to according to using environment or the difference in field, change or add other nano antifouling agent (such as, CuO, TiO2, Graphene etc.), more efficiently realize preventing and kill off the purpose of fouling organism.
In sum, super-hydrophobic composite prepared by the present invention is used as coating additive, coating can be made to have super-hydrophobicity, soil resistance, self-repairability, and have persistency, can be used for relating to the protective coating of sea material.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that the description above is not considered as limitation of the present invention.After those skilled in the art have read foregoing, multiple amendment and replacement for the present invention all will be apparent from.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. the super-hydrophobic composite of energy selfreparing, it is characterised in that the general structure of this composite is: APA/
M-PD/APA@HMS, wherein, APA is the kiber alkyl amine of the Long carbon chain being more than or equal to 12 with C, and PD is poly-dopamine, and HMS is the mesoporous SiO of hollow2Microsphere, APA@HMS refers to be loaded with the HMS of APA, described M and refers to stick to the anti-fouling agent on PD.
2. as claimed in claim 1 can the super-hydrophobic composite of selfreparing, it is characterised in that this composite is to form poly-dopamine film on the HMS of load APA, then loads anti-fouling agent M, then be mixed to form the polymeric film of band alkyl hydrophobic chain with APA and prepare.
3. the super-hydrophobic composite of energy selfreparing as claimed in claim 1, it is characterised in that in this composite, anti-fouling agent M and APA@HMS mass ratio are 0.4% ~ 1%.
4. the super-hydrophobic composite of energy selfreparing as claimed in claim 1, it is characterised in that described APA selects any one or any two or more mixing in lauryl amine, tetradecy lamine, cetylamine or 18-amine.；Described anti-fouling agent M refers to any one or any two or more mixture in nano-Ag particles, nano cuprous oxide, nano titanium oxide and graphene oxide.
5. the super-hydrophobic composite of energy selfreparing as claimed in claim 1, it is characterised in that described SiO2Nano-level sphere granule selected by microsphere, and its particle diameter is 200 nm ~ 500 nm.
6. the super-hydrophobic composite of energy selfreparing as claimed in claim 1, it is characterised in that described SiO2Micron-size spherical particles selected by microsphere, and its particle diameter is 2 μm ~ 5 μm.
7. the preparation method of the super-hydrophobic composite of an energy according to claim 1 selfreparing, it is characterised in that the method includes the steps of:
Step 1, loads APA: HMS with APA, conventional organic solvent are mixed, and is dried, and obtains loading the HMS microsphere powder APA@HMS of APA；
Step 2, loads anti-fouling agent, and it comprises:
Step 2.1, mixes with dopamine in the basic conditions by APA@HMS so that it is microsphere surface forms poly-dopamine thin film, obtains PD/APA@HMS；
Step 2.2, adds anti-fouling agent M in PD/APA@HMS, and stirring forms the APA@HMS microsphere M-PD/APA@HMS carrying M poly-dopamine film coated；
Step 3, mixes M-PD/APA@HMS with APA so that it is Surface Creation is with the polymeric film of alkyl hydrophobic chain, and obtain carrying anti-fouling agent can self-repairing super hydrophobic microsphere APA/ M-PD/APA@HMS；
Wherein, APA is the kiber alkyl amine of the Long carbon chain being more than or equal to 12 with C, and PD is poly-dopamine, and HMS is the mesoporous SiO of hollow2Microsphere, APA@HMS refers to that HMS is loaded with APA, described M and refers to stick to the anti-fouling agent on PD.
8. the preparation method of the super-hydrophobic composite of energy as claimed in claim 7 selfreparing, it is characterised in that described HMS is the mesoporous SiO of hollow2Microsphere, described SiO2Microsphere selects nano-level sphere granule or micron-size spherical particles；Described APA selects any one or any two or more mixing in lauryl amine, tetradecy lamine, cetylamine or 18-amine.；Described M refers to any one or any two or more mixture in nano-Ag particles, nano cuprous oxide, nano titanium oxide and graphene oxide；M Yu APA@HMS mass ratio is 0.4% ~ 1%.
9. the purposes of the super-hydrophobic composite of an energy according to claim 1 selfreparing, it is characterised in that this composite A PA/
M-PD/APA@HMS can serve as the super-hydrophobic bionic coating of selfreparing.
10. purposes as claimed in claim 9, it is characterized in that, the preparation method of the super-hydrophobic bionic coating of described selfreparing is: mixed with quality 1:1 with micron order microsphere by APA/ M-PD/APA@HMS nanoscale microsphere, mix with oil paint again, through covering with paint, lacquer, colour wash, etc. the super-hydrophobic bionic coating forming selfreparing.
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