CN103131275A

CN103131275A - Nano silicon dioxide (SiO2) improved fluorocarbon coating and preparation thereof

Info

Publication number: CN103131275A
Application number: CN2012105171125A
Authority: CN
Inventors: 宋仁国; 李鑫伟; 王超; 姜冬
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2012-12-06
Filing date: 2012-12-06
Publication date: 2013-06-05

Abstract

The invention relates to a preparation method of SiO ₂ nanocomposite fluorocarbon coating, which is characterized in that: the components of the fluorocarbon coating are calculated by mass percentage: nano-SiO ₂ , 1-5%; acrylic resin with 40% solid content , 25-28%; polyvinylidene fluoride resin, 24-27%; fumed silica, 0.4%; aluminum silver paste, 6%; cellulose acetate, 4%; dispersant, 2-5%; mixed solvent, margin. The invention adds nanometer _SiO2 to the fluorocarbon paint, thereby improving the stain resistance, ultraviolet aging resistance, corrosion resistance, etc. of the fluorocarbon paint, and belongs to the technical field of paint processing.

Description

Fluorocarbon coating of a kind of nanometer SiO2 modification and preparation method thereof

Technical field

The present invention relates to a kind of SiO ₂The preparation method of Nanocomposite Fluorocarbon Coatings is mainly with nanometer SiO ₂Add in fluorocarbon coating, thereby improve stain resistant performance, anti-ultraviolet ageing performance, corrosion resistance nature of fluorocarbon coating etc., belong to the coating processing technique field.

Background technology

Fluorocarbon coating has very high chemical resistance, thermotolerance, weathering resistance and weather resistance, and many soda acids, solvent are had inertness, thus in each department, each field all is widely used; Nanometer SiO ₂It is unformed white powder, it is a kind of tasteless, nontoxic, free of contamination ceramic, it has very high activity, can produce many especially in character such as optics shieldings, its application in modified rubber, pottery, engineering plastics, biomedicine, building materials, optics, polymer matrix composites modification had had many reports; Add nanometer SiO in fluorocarbon coating ₂After, can improve stain resistant, anti-ultraviolet ageing and the corrosion resistance nature of fluorocarbon coating.

Find through the literature search to prior art, the Lu Xiang of Nanjing Aero-Space University etc. are at " nanometer SiO ₂The research of modification aviation fluorocarbon coating " in mention, with nanometer SiO ₂After scattered in mixed solvent, add also high speed dispersion 2h again of fluorocarbon resin, ultra-sonic dispersion 1h, and it is all right only need to stir after in this patent, fluorocarbon resin etc. being added, the time of the coating that greatly shortens, be considerable this time of drying of saving in production application; Lu Xiang is by adding nanometer SiO ₂Improve the ageing resistance of fluorocarbon coating, Ma Lizhi etc. in " applied research of fluorocarbon coating in sealing and protecting irony cultural relics " by adding silicon-dioxide to improve the thermostability of coating, but so far seldom relevant for SiO ₂The research report of Nanocomposite Fluorocarbon Coatings corrosion resistance nature, and the roundup of stain resistant, anti-ultraviolet ageing, the performance such as corrosion-resistant, the aerosil that adds in present technique (trade mark A200) can effectively improve the stability of filler, improve the dispersiveness of filler, anti-settling, sag prevention, and raising paint film adhesion, its add-on is also the comparatively appropriate vol through the overtesting gained, and the adding the surface drying that can promote coating, interiorly do of cellulose acetate, outer doing make paint film not easy to crack.

Summary of the invention

The object of the present invention is to provide a kind of nanometer SiO ₂The preparation method of fluorocarbon modified coating improves stain resistant performance, anti-ultraviolet ageing performance and the corrosion resistance nature of fluorocarbon coating.

For reaching goal of the invention the technical solution used in the present invention be: a kind of nanometer SiO ₂The fluorocarbon coating of modification is characterized in that being achieved through the following technical solutions:

Nanometer SiO involved in the present invention ₂Fluorocarbon modified coating, the component that comprises and mass percent are:

Nanometer SiO ₂1-5%;

The acrylic resin of 40% solid content (trade mark B-44) 25-28%;

Polyvinylidene fluoride resin (PVDF) 24-27%;

Aerosil (trade mark A200) 0.4%;

Aluminium-silver slurry 6%;

Cellulose acetate (trade mark CAB551) 4%;

Dispersion agent (trade mark TAZ-ND1, sky, Nanjing capable novel material company limited produces) 2-5%;

The mixed solvent surplus.

Described nanometer SiO ₂The nanometer SiO through surface modification ₂Particle, nano particle diameter scope between 10-80nm, the nanometer SiO of surface modification ₂Particle is through the silane resin acceptor kh-550 modification; Modifying process is as follows: silane resin acceptor kh-550 is joined in deionized water, and sonic oscillation prehydrolysis 20min, KH-550 consumption are 1% of deionized water quality, then the silane coupling agent aqueous solution is joined in dehydrated alcohol, then add nanometer SiO ₂The KH-550 consumption is 2% of nano silicon quality, the nano silicon consumption is 3% of dehydrated alcohol quality, 80 ℃ of lower magnetic forces stir 4h, first with product separation, and washing, dry, 30 ℃ of freeze-day with constant temperature 24h in vacuum drier again, the gained white powder is the SiO that silane resin acceptor kh-550 is modified ₂Nanoparticle.

Described mixed solvent contains diethylene glycol ether acetic ester (DCAC) 15%, isophorone 15%, 1-Methoxy-2-propyl acetate (PMA) 20%, butanone 20%, hexone (MIBK) 10%, propylene glycol phenylate (PPH) 10%, propyl carbinol 10%(mass percent), it is used for dissolving resin, forms dispersed system, makes system reach stable.

A kind of nanometer SiO ₂The preparation method of the fluorocarbon coating of modification is characterized in that step is as follows:

A, the dispersion agent of 2-5% is dissolved in mixed solvent, then adds the nanometer SiO of the process surface modification of 1-5% ₂, 2000-4000r/min disperses 0.5-2h in dispersion machine (the prosperous 400W type dispersion machine that reaches chemical's production in Laizhou);

B, with acrylic resin (40% solid content) 25-28%, PVDF 24-27%, A200 0.4%, aluminium-silver slurry 6% and CAB551 4% successively joins in solution scattered in A, mixes and namely gets SiO ₂Nanocomposite Fluorocarbon Coatings.

Coating of the present invention is sprayed at steel surface under the Air drying environment, film front that the steel surface processing is clean, is coated with in advance priming, adopts aerial spraying, and coating thickness is 35 ± 5 μ m.

SiO of the present invention ₂The beneficial effect of Nanocomposite Fluorocarbon Coatings is mainly reflected in: (1) described SiO ₂Nanocomposite Fluorocarbon Coatings, its stain resistant performance, anti-ultraviolet ageing performance and corrosion resistance nature improve; (2) raw material is inexpensive, and technique is simple, and cost is low, is beneficial to suitability for industrialized production.

Description of drawings

Fig. 1 is SiO ₂The ultraviolet-visible absorption curves comparison diagram that Nanocomposite Fluorocarbon Coatings is filmed (b) and unmodified fluorocarbon coating is filmed (a);

Fig. 2 is SiO ₂The surface topography map of Nanocomposite Fluorocarbon Coatings paint film;

Fig. 3 is film (a) and SiO of unmodified fluorocarbon coating ₂The film contact angle contrast schematic diagram of (b) of Nanocomposite Fluorocarbon Coatings;

Fig. 4 is film (b) and SiO of unmodified fluorocarbon coating ₂The film electro-chemical test contrast schematic diagram of (a) of Nanocomposite Fluorocarbon Coatings.

Embodiment

The present invention is described further below in conjunction with concrete mode:

Embodiment 1:

Formulation for coating material:

Nanometer SiO ₂1%;

The acrylic resin of 40% solid content (trade mark B-44) 27%;

Polyvinylidene fluoride resin (PVDF) 26.7%;

Aerosil (trade mark A200) 0.4%;

Aluminium-silver slurry 6%;

Cellulose acetate (trade mark CAB551) 4%;

Dispersion agent (trade mark TAZ-ND1) 2%;

The mixed solvent surplus.

A, the dispersion agent with 2% are dissolved in mixed solvent, then add the nanometer SiO of 1% process surface modification ₂, 2000r/min disperses 1h in dispersion machine;

B, with acrylic resin (40% solid content) 27%, PVDF 26.7%, A200 0.4%, aluminium-silver slurry 6% and CAB551 4% successively joins in solution scattered in A, mixes and namely gets SiO ₂Nanocomposite Fluorocarbon Coatings.

The present embodiment gained coating is sprayed under the environment of Air drying through pretreated steel surface, and coating thickness is 35 ± 5 μ m.

Embodiment 2:

Formulation for coating material:

Nanometer SiO ₂2%;

The acrylic resin of 40% solid content (trade mark B-44) 26.5%;

Polyvinylidene fluoride resin (PVDF) 26%;

Aerosil (trade mark A200) 0.4%;

Aluminium-silver slurry 6%;

Cellulose acetate (trade mark CAB551) 4%;

Dispersion agent (trade mark TAZ-ND1) 3%;

The mixed solvent surplus.

A, the dispersion agent with 3% are dissolved in mixed solvent, then add the nanometer SiO of 2% process surface modification ₂, 2500r/min disperses 1h in dispersion machine;

B, with acrylic resin (40% solid content) 26.5%, PVDF 26%, A200 0.4%, aluminium-silver slurry 6% and CAB551 4% successively joins in solution scattered in A, mixes and namely gets SiO ₂Nanocomposite Fluorocarbon Coatings.

Embodiment 3:

Formulation for coating material:

Nanometer SiO ₂3%;

The acrylic resin of 40% solid content (trade mark B-44) 26.2%;

Polyvinylidene fluoride resin (PVDF) 25.6%;

Aerosil (trade mark A200) 0.4%;

Aluminium-silver slurry 6%;

Cellulose acetate (trade mark CAB551) 4%;

Dispersion agent (trade mark TAZ-ND1) 4%;

The mixed solvent surplus.

A, the dispersion agent with 4% are dissolved in mixed solvent, then add the nanometer SiO of 3% process surface modification ₂, 3000r/min disperses 1h in dispersion machine;

B, with acrylic resin (40% solid content) 26.2%, PVDF 25.6%, A200 0.4%, aluminium-silver slurry 6% and CAB551 4% successively joins in solution scattered in A, mixes and namely gets SiO ₂Nanocomposite Fluorocarbon Coatings.

Embodiment 4:

Formulation for coating material:

Nanometer SiO

₂4%;

The acrylic resin of 40% solid content (trade mark B-44) 25.6%;

Polyvinylidene fluoride resin (PVDF) 25.1%;

Aerosil (trade mark A200) 0.4%;

Aluminium-silver slurry 6%;

Cellulose acetate (trade mark CAB551) 4%;

Dispersion agent (trade mark TAZ-ND1) 5%;

The mixed solvent surplus.

A, the dispersion agent with 5% are dissolved in mixed solvent, then add the nanometer SiO of 4% process surface modification ₂, 3500r/min disperses 1h in dispersion machine;

B, with acrylic resin (40% solid content) 25.6%, PVDF 25.1%, A200 0.4%, aluminium-silver slurry 6% and CAB551 4% successively joins in solution scattered in A, mixes and namely gets SiO ₂Nanocomposite Fluorocarbon Coatings.

Prepared SiO ₂The Nanocomposite Fluorocarbon Coatings paint film is observed transmittance and the surface topography of ultraviolet-visible light through ultraviolet-visible pectrophotometer, scanning electronic microscope (SEM).

(1) ultraviolet-visible pectrophotometer analysis

Fig. 1 is SiO ₂Nanocomposite Fluorocarbon Coatings the film ultraviolet-visible absorption curves of (b) of (a) and unmodified fluorocarbon coating of filming (a) shows SiO with (b) contrast ₂The Nanocomposite Fluorocarbon Coatings uv absorption rate of filming at Same Wavelength than unmodified fluorocarbon coating of filming obviously increases, and the declaratives UV-light is by nanometer SiO ₂Absorb; Coating aging is mainly that the irradiation by UV-light causes, organic compound absorbs ultraviolet energy and the fracture of generating keys, cause aging, as nanometer SiO ₂When existing, due to it can absorption portion ultraviolet ray, can play a kind of ultraviolet shielded effect, thereby stop the aging of coating.

(2) SEM observes

Use sem observation SiO ₂The surface topography of Nanocomposite Fluorocarbon Coatings paint film, as seen from Figure 2, nanoparticle disperses more even.

(3) contact angle determination

In Fig. 3, (a) films for unmodified fluorocarbon coating, and its contact angle is 70.710 °, is (b) SiO ₂Nanocomposite Fluorocarbon Coatings is filmed, and its contact angle is 81.469 °, shows to add nanometer SiO ₂After, the hydrophobic performance of filming obviously increases, SiO ₂Nanocomposite Fluorocarbon Coatings is filmed and is also had ultralow surface energy, makes dust be difficult for adhering to, and cleaning for a long time can keep filming.

(4) electro-chemical test

In figure below (a) and (b) be respectively SiO ₂The Tafel polarization curve of Nanocomposite Fluorocarbon Coatings and unmodified fluorocarbon coating, correlation parameter is listed in table, corrosion potential (E) more just, (I) is less for corrosion current, the corrosion resistance nature of the less illustrative material of erosion rate is better; By data in table 1 as can be known, SiO ₂The corrosion resistance nature of Nanocomposite Fluorocarbon Coatings is far above unmodified fluorocarbon coating.

Claims

1. a nanometer SiO The fluorocarbon coating _modified , is characterized in that: the component of described fluorocarbon coating is calculated according to mass percent:

Nano SiO ₂ 1-5%;

40% solid content of acrylic resin 25-28%;

Polyvinylidene fluoride resin 24-27%;

Fumed silica 0.4%;

Aluminum silver paste 6%;

Cellulose acetate 4%;

Dispersant 2-5%;

Mixed solvents Balance.

2. A kind of nano-SiO as claimed in claim ₁ Modified fluorocarbon coating, it is characterized in that: described nano-SiO is through the nano _- SiO of silane coupling agent KH-550 _surface modification Particle, nano-particle The particle size range is between 10-80nm.

3. A kind of nano- _SiO2 modified fluorocarbon coating as claimed in claim 2, characterized in that: the modification process is as follows: silane coupling agent KH-550 is added to deionized water, pre-hydrolyzed by ultrasonic vibration 20min, the amount of KH-550 is 1% of the mass of deionized water, then add the aqueous solution of silane coupling agent to absolute ethanol, and then add nano-SiO ₂ , the amount of KH-550 is 2% of the mass of nano-silica, nano The amount of silicon dioxide is 3% of the mass of absolute ethanol, stirred magnetically at 80°C for 4h, the product is separated, washed, air-dried, and then dried at a constant temperature of 30°C in a vacuum dryer for 24h, the obtained white powder is silane Linking agent KH-550 modified SiO ₂ nanoparticles.

4. a kind of nano-SiO as claimed in claim 1 _Modified fluorocarbon coating, it is characterized in that: the component of described mixed solvent is calculated as: diethylene glycol ethyl ether acetate 15%, isofor 15% ketone, 20% propylene glycol methyl ether acetate, 20% methyl ethyl ketone, 10% methyl isobutyl ketone, 10% propylene glycol phenyl ether, and 10% n-butanol are used to dissolve the resin and form a dispersion system so that the system reaches Stablize.

5. a kind of nano-SiO as claimed in claim ₁ The preparation method of the modified fluorocarbon coating is characterized in that the steps are as follows:

A. Dissolve 2-5% dispersant in the mixed solvent, then add 1-5% surface-modified nano-SiO ₂ , and disperse in the disperser at 2000-4000r/min for 0.5-2h;

B. Add 25-28% of acrylic resin with 40% solid content, 24-27% of polyvinylidene fluoride resin, 0.4% of fumed silica, 6% of aluminum silver paste and 4% of cellulose acetate into A to disperse well solution, and mix evenly to obtain nano- _SiO2 modified fluorocarbon coating.