CN105949861A - Self-repairing super-hydrophobic composite material, preparation method and application thereof - Google Patents

Abstract

The invention discloses a self-healing superhydrophobic composite material, its preparation method and application. The general structural formula of the composite material is: APA/M-PD/APA@HMS, wherein, APA is a composite material with C greater than or equal to 12 Alkyl primary amine with a long carbon chain, PD is polydopamine, HMS is hollow mesoporous SiO ₂ microspheres, APA@HMS refers to HMS loaded with APA, and the above M refers to an antifouling agent that can adhere to PD. The preparation method provided by the invention is easy to operate, has abundant sources of raw materials, and is suitable for large-scale production. The prepared APA/M‑PD/APA@HMS is used as a coating additive, which can make the coating have superhydrophobicity, antifouling properties, and self-repairing It is durable and durable, and can be used as a protective coating for marine materials.

Description

A self-healing superhydrophobic composite material, its preparation method and use

technical field

The invention relates to a superhydrophobic composite material, in particular to a self-repairing superhydrophobic composite material, its preparation method and application.

Background technique

The adhesion and corrosion of marine organisms to sea-related materials has become a global problem that seriously affects the service performance of marine facilities. As an anti-fouling concept that has emerged in recent years, super-hydrophobic biomimetic coatings are the most active type in the research field of new environment-friendly anti-fouling coatings. Antifouling coatings can greatly expand its application fields, and its development prospects are very broad. This type of coating is usually made by simulating the surface of animals and plants such as lotus leaves and shark skin, using hydrophobic materials to construct surface micro-nano rough structures or modifying low surface energy substances on the surface of rough porous materials to change the physical structure and chemical properties of the material surface , so that the material has super-hydrophobic properties to achieve the purpose of inhibiting fouling organisms from adhering.

Although superhydrophobic materials have shown excellent properties and great application prospects in the field of antifouling, they have been greatly restricted in practical applications. The main reason is that the conventional micro-nano hierarchical rough surface construction method (such as , chemical etching, plasma treatment, vapor deposition and electrochemical deposition, etc.), are too complicated and the process requirements are too high, which is not conducive to large-scale production; secondly, due to the rough structure of these modified superhydrophobic surfaces in practical applications , most of them have no self-healing function when they are worn or damaged. When the micro-nano hierarchical structure with rough surface is rubbed, its local sharp convex structure is easily damaged, resulting in the disappearance of the micro-nano hierarchical structure and it is difficult to maintain good mechanical stability. ; Furthermore, if in a relatively static marine environment, relying solely on the super-hydrophobic properties of the coating is not enough to achieve the purpose of completely inhibiting biological adhesion, other technologies need to be coordinated. Therefore, it is of great significance to study a superhydrophobic material with the characteristics of durability, self-healing and suitable for large-scale production.

Contents of the invention

The technical problem to be solved by the present invention is to provide a super-hydrophobic composite material, which can self-repair, has anti-fouling, super-hydrophobicity and durability, is suitable for large-scale production, and can be used in marine environments.

In order to achieve the above object, the present invention provides a self-repairing superhydrophobic composite material, its preparation method and use A self-repairing superhydrophobic composite material, the general structural formula of the composite material is: APA/M-PD /APA@HMS, wherein, APA is an alkyl primary amine with a long carbon chain with C greater than or equal to 12, PD is polydopamine, HMS is a hollow mesoporous _SiO2 microsphere, APA@HMS means that HMS is loaded with APA, The said M refers to the antifouling agent that can adhere to the PD.

The above-mentioned self-healing superhydrophobic composite material, wherein the composite material forms a polydopamine film on the HMS loaded with APA, then loads the antifouling agent M, and then mixes with APA to form a polymer film with an alkyl hydrophobic chain. have to.

The aforementioned self-healing superhydrophobic composite material, wherein the mass ratio of antifouling agent M and APA@HMS in the composite material is 0.4%~1%.

In the aforementioned self-healing superhydrophobic composite material, the APA is selected from any one of dodecylamine, tetradecylamine, hexadecylamine or octadecylamine or a mixture of any two or more.

In the above-mentioned self-healing superhydrophobic composite material, the SiO ₂ microspheres are nano-scale spherical particles with a particle size of 200 nm to 500 nm.

In the aforementioned self-healing superhydrophobic composite material, the SiO ₂ microspheres are micron-sized spherical particles with a particle size of 2 μm to 5 μm.

In the above-mentioned self-healing superhydrophobic composite material, the antifouling agent refers to any one or a mixture of any two or more of nano-silver particles, nano-cuprous oxide, nano-titanium dioxide, and graphene oxide.

The present invention also provides a kind of preparation method according to above-mentioned self-repairing superhydrophobic composite material, and this method comprises the following steps:

Step 1, load APA: mix HMS with APA and conventional organic solvents, and dry to obtain APA-loaded HMS microsphere powder APA@HMS;

Step 2, load antifouling agent, which comprises:

Step 2.1, mix APA@HMS and dopamine under alkaline conditions to form a polydopamine film on the surface of the microspheres to obtain PD/APA@HMS;

Step 2.2, add antifouling agent M to PD/APA@HMS, and stir to form APA@HMS microspheres M-PD/APA@HMS coated with M-loaded polydopamine film;

Step 3: Mix M-PD/APA@HMS with APA to form a polymer film with alkyl hydrophobic chains on its surface, and obtain self-healing superhydrophobic microspheres APA/ M-PD/APA@HMS;

Among them, APA is an alkyl primary amine with a long carbon chain with C greater than or equal to ₁₂ , PD is polydopamine, HMS is a hollow mesoporous SiO microsphere, APA@HMS means that HMS is loaded with APA, and the M refers to Antifouling agent that adheres to PD.

The preparation method of the above-mentioned self-healing superhydrophobic composite material, wherein, the HMS is a hollow mesoporous SiO microsphere, and the SiO microsphere is selected from nano _- scale spherical particles or micron _- scale spherical particles; APA selects any one of dodecylamine, tetradecylamine, hexadecylamine or octadecylamine or a mixture of any two or more; the M refers to nano-silver particles, nano-cuprous oxide, nano-titanium dioxide, and oxide Any one of graphene or a mixture of any two or more; the mass ratio of M to APA@HMS is 0.4%~1%.

The present invention also provides a kind of purposes of above-mentioned self-healing superhydrophobic composite material, wherein, this composite material APA/ M-PD/APA@HMS can be used as a self-healing superhydrophobic biomimetic coating.

The above-mentioned use, wherein, the preparation method of the self-healing superhydrophobic biomimetic coating is: mixing APA/M-PD/APA@HMS nano-scale microspheres with micron-scale microspheres in a mass of 1:1, and then mixing with Oil-based paints are mixed and painted to form a self-healing superhydrophobic biomimetic coating. The purpose of the above mixing is to form a multi-scale rough structure on the surface of the coating to achieve super-hydrophobic performance. The best mixing ratio is 1:1 in terms of mass ratio through experiments.

The superhydrophobic composite material prepared by the invention is used as a coating additive, which can make the coating have superhydrophobicity, antifouling property, self-repairing property, and has durability, and can be used for the protective coating of sea-related materials.

Description of drawings

Fig. 1 is the reaction schematic diagram of a kind of self-healing superhydrophobic composite material preparation method of the present invention.

detailed description

The present invention will be further described below through specific embodiments in conjunction with the accompanying drawings. These embodiments are only used to illustrate the present invention, and are not intended to limit the protection scope of the present invention.

The invention provides a self-repairing super-hydrophobic composite material, which is loaded with a nano antifouling agent and has a self-repairing super-hydrophobic surface. The general structural formula of the composite material is: APA/ M-PD/APA@HMS, where APA is a primary alkylamine with a long carbon chain with C greater than or equal to 12, PD is polydopamine, and HMS is hollow mesoporous SiO ₂ Microspheres, APA@HMS means that HMS is loaded with APA, and the above-mentioned M refers to an antifouling agent that can adhere to PD; the APA content in APA@HMS depends on the size of the hollow space inside HMS; M and APA@ The mass ratio of HMS is preferably 0.4%~1%. The composite APA/M-PD/APA@HMS is prepared by forming a polydopamine film on APA-loaded HMS, then loading antifouling agent M, and then mixing with APA to form a polymer film with alkyl hydrophobic chains.

As shown in Figure 1, it is the preparation principle of the superhydrophobic composite material of the present invention, and the preparation steps of the superhydrophobic composite material are as follows:

Step 1: Preparation of green environment-friendly nano antifouling agent. All green and environment-friendly inorganic nano-antifouling agents can be used as additives in this method, such as nano-silver particles, nano-cuprous oxide, nano-titanium dioxide, and graphene oxide, etc., which are used in this method. This case takes nano-silver as an example. The preparation process uses AgNO ₃ as a precursor and hydrolyzed casein as a reducing agent to prepare a batch of nano-silver particles with a particle size of 10-20nm under alkaline conditions.

Step 2, preparation of hollow mesoporous SiO ₂ microspheres (HMS). Spherical monodisperse solid SiO ₂ microspheres with a size of 200 nm to 500 nm and 2 μm to 5 μm were purchased as a template, and cetyltrimethylammonium bromide (CTAB) was used as a surfactant. Under alkaline conditions, Using TEOS (tetraethylorthosilicate) as the silicon source-shaped shell, calcining to remove the surfactant template, and finally adding sodium carbonate to selectively etch the solid SiO ₂ to form HMS with an air structure. The particle size is determined by adding The solid SiO ₂ decision.

Step 3, silver-loaded self-healing superhydrophobic microspheres can be prepared. First, take the above-mentioned synthesized HMS, load with alkyl primary amines (APA, such as octadecylamine, etc.) with long carbon chains, and obtain APA-loaded HMS microspheres (APA@HMS); Mix under alkaline conditions (pH = 8.5) to form a polydopamine film on the surface of the microspheres, and then add nano-scale silver particles under magnetic stirring conditions to form APA@HMS microspheres coated with silver-loaded polydopamine film , and finally mix it with APA again to make a polymer film with alkyl hydrophobic chains on its surface to realize silver-loaded self-healing superhydrophobic microspheres (APA/ Ag-PD/APA@HMS) nanoscale or microscale preparation.

Step 4: Mix the nanoscale silver-loaded self-healing superhydrophobic microspheres and micron-scale silver-loaded self-healing superhydrophobic microspheres obtained by the above synthesis method according to the mass 1:1, then add them to the oily paint, and finally pass By spraying, a silver-loaded self-healing superhydrophobic biomimetic coating can be obtained on the surface of the substrate.

The preparation method of the superhydrophobic composite material of the present invention will be described in detail below in conjunction with the examples.

Example 1

1. Preparation of Nanosilver

Combine 45 mg hydrolyzed casein and 10 mg Sodium hydroxide was dissolved in 45 mL of deionized water, and then 5 mL of silver nitrate (20 mM) solution was added dropwise. The above mixed solution was heated with magnetic stirring at 60 °C for 3 h, mixed with alcohol 1:4 and centrifuged at 20000 × g at high speed, and finally the precipitate was washed with deionized water and dried in vacuum to obtain silver nanoparticles (Ag NPs) particles.

2. Preparation of nanoscale hollow mesoporous silica (HMS)

First, in 1 L of deionized water, add 5 g of purchased nano-scale (200 nm~500 nm) spherical monodisperse solid _SiO2 microspheres, and ultrasonically disperse to form a white _SiO2 emulsion; then mix at a volume ratio of 5:1:1 CTAB, ethanol and deionized water, and adjust the pH value of the solution to 8.0~8.5 with ammonia water; mix the solution with the above SiO ₂ emulsion at a volume ratio of 10:1, stir evenly, quickly add a small amount of TEOS, and continue stirring for 5~6 After centrifugation for h, the obtained precipitate was washed with deionized water several times and then calcined in a muffle furnace at 500 °C for 6 h. Take the above-mentioned calcined powder, disperse every 1 g of it in 100 mL of deionized water, then add 2 g of sodium carbonate, and heat to 50 °C for 10 h. The precipitate was collected by centrifugation, washed with deionized water, and dried to obtain nanoscale HMS, which was stored for later use.

3. Preparation of APA-loaded HMS nanoscale microspheres (APA@HMS)

According to the mass ratio of 1:1:10, the HMS synthesized above and the alkyl primary amine with long carbon chain (APA, it is recommended that the C in the alkyl carbon chain is greater than 12, such as dodecylamine, tetradecylamine, hexadecylamine Amine or octadecylamine, etc.) and ethanol were mixed, ultrasonicated for 30 minutes and then dried to obtain APA-loaded HMS nano-scale microsphere powder (APA@HMS);

4. Preparation of self-healing superhydrophobic microspheres loaded with nanoscale silver (APA/Ag-PD/APA@HMS)

In 40 mL Tris (tris(hydroxymethyl)aminomethane)-HCl (pH=8.5) buffer solution, add 2.5 g of the above microsphere powder, after ultrasonic dispersion, add 75 mg dopamine hydrochloride, stirred at room temperature for 4-6 h, centrifuged and washed with ethanol to obtain polydopamine (PD)-wrapped APA@HMS microspheres (PD/ APA@HMS); the above microspheres were redispersed to 15 m L of ethanol, then add 0.01 g pre-prepared nano-silver, sonicate for 15 min and then magnetically stirred for 30 min, then added 100 mg APA, stirred at room temperature for 10-12 h, centrifuged and washed successively to obtain silver-loaded self-healing superhydrophobic microspheres (APA/ Ag-PD/APA@HMS).

5. Preparation of micron-sized silver-loaded self-healing superhydrophobic microspheres (APA/Ag-PD/APA@HMS)

The preparation of micron-sized silver-loaded self-healing superhydrophobic microspheres uses micron-sized (2 μm-5 μm) SiO ₂ as a template, and the method is the same as the above method.

The superhydrophobic composite material (APA/Ag-PD/APA@HMS) prepared by the present invention can be used as a self-healing superhydrophobic biomimetic coating. Repairing superhydrophobic microspheres and micron-sized silver-loaded self-repairing superhydrophobic microspheres are mixed according to the mass of 1:1, and then added to the oil-based paint, and finally sprayed to obtain silver-loaded self-repairing superhydrophobic bionics on the surface of the substrate coating. The hydrophobicity, self-healing and antifouling properties of the prepared coating can all meet the protection requirements of sea-related materials. The specific test results are as follows:

Hydrophobicity: Use epoxy resin as the base resin, dope silver-loaded self-healing superhydrophobic microspheres according to the above method, and spray it on the metal substrate. After the coating is dry, use JC2000D1 static contact angle measuring instrument to test its contact angle. The test results show that after doping self-healing superhydrophobic microspheres, the contact angle of the epoxy resin coating to deionized water increases from 66° to 157°, realizing superhydrophobicity. The reason why it can achieve super-hydrophobic performance lies in two points: one, because dopamine can generate polydopamine after oxidation, which can react with alkyl primary amines with long carbon chains to generate hydrophobic substances with low surface energy; Second, the doping of nano/micro-scale hydrophobic microspheres enables the surface of the coating to form a multi-scale micro-nano rough structure.

Self-healing: Use epoxy resin as the matrix resin, dope silver-loaded self-healing superhydrophobic microspheres according to the above method, and spray on the metal substrate. After the coating is dry, use PE-100 plasma etcher to coat The surface of the coating was etched, and then the contact angle was tracked and tested using the JC2000D1 static contact angle measuring instrument. The experimental results showed that after one etching, the contact angle of the coating surface recovered from 131° to 153° within 30 minutes; After 5 times of etching, the surface contact angle of the coating recovered from 106° to 147° within 30 minutes. It can be seen that the self-healing property of the superhydrophobic composite material prepared by the present invention is very good.

Anti-fouling: Use epoxy resin as the matrix resin, dope silver-loaded self-healing super-hydrophobic microspheres according to the above method, and spray on the metal substrate, and the coating will be used after drying. Diatoms were used as the target fouling organisms, enriched and cultured with seawater at 37°C for 2 days, then the above metal samples were immersed in the algae liquid, taken out after 1 day, rinsed with water, and observed with a NIKON/Ti-E inverted fluorescence microscope surface attachment. In the experiment, the epoxy resin without silver-loaded self-healing superhydrophobic microspheres was used as the control. The experimental results show that the coating doped with silver-loaded self-healing superhydrophobic microspheres has less diatom attachment, which is 7±3/mm ² , while the coating without silver-loaded self-healing superhydrophobic microspheres The number of diatoms attached to the layer is more, 1557±120/mm ² .

The superhydrophobic composite material prepared by the present invention is used for coating antifouling through two ways: one is that the superhydrophobic properties of the coating make it difficult for fouling organisms to attach to the surface of the coating; the other is that nano silver The role of antifouling agent, it can kill the fouling organisms that have attached to the surface of the coating. At the same time, since nano-silver and its carrier (that is, polydopamine on the surface of SiO ₂ microspheres) are combined by physical adhesion, other nano-antifouling agents (for example, CuO , TiO ₂ , graphene, etc.), more effectively achieve the purpose of anti-fouling organisms.

In summary, the superhydrophobic composite material prepared by the present invention is used as a coating additive, which can make the coating have superhydrophobicity, antifouling, self-healing, and has durability, and can be used as a protective coating for marine materials .

Although the content of the present invention has been described in detail through the above preferred embodiments, it should be understood that the above description should not be considered as limiting the present invention. Various modifications and alterations to the present invention will become apparent to those skilled in the art upon reading the above disclosure. Therefore, the protection scope of the present invention should be defined by 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.