CN104877089A - Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion - Google Patents
Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion Download PDFInfo
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- CN104877089A CN104877089A CN201510230914.1A CN201510230914A CN104877089A CN 104877089 A CN104877089 A CN 104877089A CN 201510230914 A CN201510230914 A CN 201510230914A CN 104877089 A CN104877089 A CN 104877089A
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Abstract
The invention discloses a preparation method of a modified fluorine-containing acrylic superhydrophobic resin emulsion, which comprises the following steps: preparing an organic hydrophobic modified SiO2 sol by a sol-gel process, and carrying out free-radical polymerization reaction under emulsifying conditions to graft SiO2 onto the fluorine-containing acrylic copolymer resin, thereby obtaining the SiO2 in-situ modified fluorine-containing acrylic superhydrophobic resin emulsion. While free radical emulsion polymerization is utilized to prepare the organic fluorine modified polyacrylate resin, the SiO2 nanoparticles are grafted by the copolymerization reaction, thereby successfully preparing the SiO2 nanoparticle in-situ modified fluorine-containing acrylic resin emulsion, and avoiding the key technical problem of very low modification ratio in the mechanical blending process. After the emulsion is completely dried, the composite coating can have excellent superhydrophobicity, and thus, the emulsion can be abundantly applied to many industrial fields. The reaction technique has the advantages of higher success rate and lower cost, and is simple to operate.
Description
[technical field]
The present invention relates to the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid, particularly relate to one and utilize SiO
2nanoparticle carries out the preparation method of the super-hydrophobic resin emulsion of fluorine-containing of situ-formed graft modification by copolymerization.
[background technology]
Polyacrylate type resin has excellent photostabilization, ageing resistance, alkali resistance etc., and has good film forming properties and sticking power, is thus widely used in the industries such as coating, ink, tackiness agent, automobile, plastics, fiber.But, the chemical stability of polyacrylate type resin, weathering resistance, erosion resistance and the aspect such as anti-oxidant are short of to some extent, and therefore the way of current main-stream utilizes organic fluorine to carry out chemical modification (i.e. fluorinated acrylate copolymer resins) to polyacrylate type resin.
The modification theory of fluorinated acrylate copolymer resins utilizes the C-F key bond energy in organofluorine compound large and stable, F atom can at the outer close-packed arrays of carbochain simultaneously, effectively prevent carbochain from exposing, and keep the features such as high stability, carbon fluorine chain is introduced in the main carbochain of polyacrylic ester as side chain, carbon fluorine side chain can the structure of coated main chain, thus the main carbochain of polyacrylic ester is played well " shielding protection ", thus fluorinated acrylic ester copolymer resins is not easily gone bad because of environmental factors effect, namely excellent hydrophobicity is shown, erosion resistance, stain resistant, the performance such as anti-oxidant, thus at coating, fabric, optical fiber, the fields such as microelectronics are widely used.
In order to improve the hydrophobic performance of fluorinated acrylate copolymer resins further, also need SiO
2, TiO
2, CaCO
3be incorporated in the coating of fluorinated acrylate copolymer resins Deng the nanoparticle containing oxygen inorganics, by the surface microstructure of structure coating, manufacture certain roughness, thus realize the ultra-hydrophobicity of coating.Due to comparatively strong containing oxygen inorganics nanoparticle wetting ability, be difficult to direct introducing, although direct mixing method technique is simple, be often difficult to reach expection to hydrophobic contribution function.Therefore, the good method of modifying of effect is situ aggregation method, i.e. functional group in the surface modification of nanoparticle, then adds monomer and is polymerized in nanoparticle surface.But due to wetting ability difference in essence, the current success ratio of situ aggregation method is also less, be difficult to meet the growing demand to the super-hydrophobic resin of high-performance fluorine-containing vinylformic acid.
[summary of the invention]
The present invention seeks to overcome the deficiencies in the prior art, there is provided a kind of technique simple, cost is low, the preparation method of the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid that percentage of grafting is good, the super-hydrophobic resin emulsion hydrophobic performance of modified fluoride-containing vinylformic acid prepared by the method is good, and erosion resistance, stain resistant, antioxidant property are excellent.
The present invention for achieving the above object, by the following technical solutions:
A preparation method for the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, is characterized in that comprising the following steps:
A, tetraethoxy and hydrophobic silane to be thrown in spirituous solution jointly, be warming up to 70 ~ 90 DEG C, and stirring reaction 4 ~ 6h, add emulsifying agent and polyvinyl alcohol again, continue to stir until material dissolves completely, stop heating and in left at room temperature ageing 10 ~ 20h, obtain hydrophobically modified SiO
2sol solution;
B, following weight parts monomers mixed obtain mix monomer:
C, by hydrophobically modified SiO
2colloidal sol is warming up to 75 ~ 85 DEG C, drip the initiator solution of mix monomer and 1/4 ~ 1/2 more respectively simultaneously, control time for adding is 3 ~ 5h, then disposable add 1/4 ~ 1/3 initiator solution, continue insulation reaction 0.5 ~ 1h, property adds remaining initiator solution again, and by solution warms to 85 ~ 90 DEG C, stopped reaction after continuation insulation reaction 1 ~ 3h, is cooled to room temperature.
First the present invention prepares organic hydrophobic modified SiO by sol-gel method
2colloidal sol, then by Raolical polymerizable under the condition of emulsification, by SiO
2in grafting on fluorine-containing copolymer resins, prepare SiO
2the super-hydrophobic resin emulsion of in-situ modified fluorine-containing.Fluorinated acrylate/the SiO obtained by complete drying by this emulsion
2compound coating not only presents ultra-hydrophobicity, and reaction process is simple, and success ratio is high, and cost is comparatively cheap.
Hydrophobic silane in the present invention is one or more in Union carbide A-162, dimethyldiethoxysilane and trimethylchlorosilane.
The ratio of the tetraethoxy in the present invention and the mole number of hydrophobic silane is 0.1 ~ 0.9.
First the present invention is inorganic hydrolysis presoma with tetraethoxy (TEOS) and hydrophobic silane, prepares the SiO containing hydrophobic grouping under certain condition
2homogeneous sol.When the mole number of tetraethoxy and hydrophobic silane ratio 0.1 ~ 0.9 scope, inorganic SiO
2gel particle surface can connect the vinyl group of sufficient amount; When hydrophobic silane amount is too much, sol system is layering very easily, and there will be a large amount of extragranular microcrystalline phase of reuniting.
Then the present invention adds emulsifying agent and protecting glue polyvinyl alcohol in sol system, and heating, until protecting glue dissolves completely, obtains emulsion reaction medium.Again the monomer mixed and part initiator solution are added drop-wise in emulsion reaction medium simultaneously, after reacting for some time at a certain temperature; Then add a small amount of initiator solution, continue insulation reaction, repeat again once afterwards; Last stopped reaction, is cooled to room temperature discharging and namely obtains resin emulsion.This stage the most important thing is that the kind of soft or hard monomer, reaction process condition parameter, fluorine monomer, content and addition manner are on the impact of resin emulsion properties.
The excellent property such as film-forming properties, water tolerance, photostabilization, ageing resistance of polyacrylate resin, but the aspects such as its pollution resistance, weathering resistance, contamination resistance are unsatisfactory.Introduce organic fluorine group by chemical reaction, modified fluorine-containing copolymer resins not only maintains polyacrylate resin primary characteristic, and effectively improves the weathering resistance, pollution resistance, hydrophobic performance etc. of resin, therefore applies quite extensive.
Research shows, the effect of the composite use of anion surfactant and nonionogenic tenside is better.The preferred emulsifying agent of the present invention is one or more in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, Span-20, Span-40, Span-60, Tween-20, Tween-40, Tween-60, AES, AEO-7 and AEO-9.
Hard monomer in the present invention is one or more in vinylbenzene, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate and vinyl acetate.
Soft monomer in the present invention is one or more in ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer.
Functional fluoropolymer monomer in the present invention is one or more in Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate and Perfluoroalkylethyl methacrylate.
Initiator in the present invention is one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
Carboxylic monomer in the present invention is one or more in 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester and trifluoroethyl methacrylate.
In organic fluorine monomer, the diameter of F atom is little, and C-F bond energy is high, and simultaneously compared with H atom, F atom at the outer close-packed arrays of C-C main chain, can effectively can wrap up protection C-C main chain.The present invention by organic fluorine monomer and acrylic ester copolymer, prepares the hydrophobicity fluorinated acrylate random copolymers of low surface energy by free-radical emulsion polymerization.
In order to obtain and SiO
2gel be copolymerized into power, the present invention adds hydroxyl or carboxylic functional monomer and participates in copolyreaction.
The chemical constitution of coating and geometry microtexture all directly affect the wettability of coatingsurface.Theoretical according to Wenzel, if coatingsurface exists roughness to a certain degree, then hydrophilic coating surface can be more hydrophilic, and hydrophobic coating surface can be more hydrophobic.Low surface energy fluorine-containing copolymer resins prepared by the present invention is first the hydrophobic prerequisite of coatingsurface, then introduces SiO by situ aggregation method
2nanoparticle, can significantly improve coatingsurface hydrophobic performance, makes compound coating present excellent water tolerance.
SiO prepared by the present invention
2nanogel biocatalytic particle surface connects the hydrophobic group with C=C, participates in the copolyreaction of hard monomer, soft monomer, organic fluorine monomer and functional monomer in emulsion reaction medium, thus by SiO
2nanoparticle has passed through in chemical bond grafting in the structure of fluorinated acrylate copolymer resins, in the roughness that resin coating structure is enough large, thus obtained super-hydrophobic organic-inorganic hybrid nanocomposite coating.Experiment proves, modified component is introduced by situ aggregation method, in compound coating, organic being separated and combination on nanoscale with inorganic component, can produce the nano and micro relief structure of the uniqueness not available for mechanical blending method, make compound coating possess excellent superhydrophobic characteristic.
The present invention compared with the prior art, has following advantage:
The present invention passes through free-radical emulsion polymerization method while the polyacrylate resin of preparation organic fluorine modification, by SiO in copolyreaction grafting
2nanoparticle, successfully prepares SiO
2the in-situ modified fluoroacrylic resin emulsion of nanoparticle, has stopped the gordian technique difficult problem that the degree of modification of mechanical blending method is very low.After this emulsion complete drying, compound coating can present excellent super-hydrophobicity, can be applied in large quantities in a lot of industrial circle.The success ratio of this reaction process is higher, and simple to operate, relative inexpensiveness.
[embodiment]
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
Prepare the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, step is as follows:
A, tetraethoxy and Union carbide A-162 to be thrown in spirituous solution jointly according to the ratio of the mole number of 0.1, be warming up to 70 DEG C, and stirring reaction 4h, then add emulsifier op-10 and polyvinyl alcohol, continue stir until material dissolves completely, stop heating and in left at room temperature ageing 10h;
B, following weight parts monomers mixed obtain mix monomer:
C, the solution warms to 75 DEG C that a step is obtained, drip the initiator potassium persulfate solution of mix monomer and 1/4 more respectively simultaneously, control time for adding is 3h, then disposable add 1/4 initiator solution, continue insulation reaction 0.5h, property adds remaining initiator solution again, and by solution warms to 85 DEG C, stopped reaction after continuation insulation reaction 1h, is cooled to room temperature, is called I emulsion.
Embodiment 2:
Prepare the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, step is as follows:
A, tetraethoxy and dimethyldiethoxysilane to be thrown in spirituous solution jointly according to the ratio of the mole number of 0.9, be warming up to 90 DEG C, and stirring reaction 6h, add emulsifier op-10, sodium lauryl sulphate and polyvinyl alcohol again, continue stir until material dissolves completely, stop heating and in left at room temperature ageing 20h;
B, following weight parts monomers mixed obtain mix monomer:
C, the solution warms to 85 DEG C that a step is obtained, drip the initiator potassium persulfate solution of mix monomer and 1/2 more respectively simultaneously, control time for adding is 5h, then disposable add 1/3 initiator solution, continue insulation reaction 1h, property adds remaining initiator solution again, and by solution warms to 90 DEG C, stopped reaction after continuation insulation reaction 3h, is cooled to room temperature, is called II emulsion.
Embodiment 3:
Prepare the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, step is as follows:
A, tetraethoxy, Union carbide A-162, dimethyldiethoxysilane and the trimethylchlorosilane ratio according to the mole number of 0.5:0.5:0.25:0.25 to be thrown in spirituous solution jointly, be warming up to 80 DEG C, and stirring reaction 5h, add emulsifier op-10, AES, sodium lauryl sulphate and polyvinyl alcohol again, continue stir until material dissolves completely, stop heating and in left at room temperature ageing 15h;
B, following weight parts monomers mixed obtain mix monomer:
C, the solution warms to 80 DEG C that a step is obtained, drip the mixed initiator solution (in initiator solution, Sodium Persulfate and ammonium persulphate mass ratio are 1:2) of mix monomer and 1/3 more respectively simultaneously, control time for adding is 4h, then disposable add 30% initiator solution, continue insulation reaction 40min, property adds remaining initiator solution again, and by solution warms to 85 DEG C, stopped reaction after continuation insulation reaction 2h, is cooled to room temperature, is called III emulsion.
Embodiment 4:
Prepare the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, step is as follows:
A, tetraethoxy, Union carbide A-162, dimethyldiethoxysilane and the trimethylchlorosilane ratio according to the mole number of 0.6:0.25:0.45:0.3 to be thrown in the spirituous solution of pH≤10 jointly, be warming up to 85 DEG C, and stirring reaction 5h, add emulsifier op-10, AES, Tween-60, sodium lauryl sulphate and polyvinyl alcohol again, continue stir until material dissolves completely, stop heating and in left at room temperature ageing 10 ~ 20h;
B, following weight parts monomers mixed obtain mix monomer:
C, the solution warms to 80 DEG C that a step is obtained, drip the mixed initiator solution (in initiator solution, the mass ratio of potassium sulfate, Sodium Persulfate and ammonium persulphate is 1:1:2) of mix monomer and 40% more respectively simultaneously, control time for adding is 4h, then disposable add 30% initiator solution, continue insulation reaction 45min, property adds remaining initiator solution again, and by solution warms to 85 DEG C, stopped reaction after continuation insulation reaction 2h, be cooled to room temperature, be called IV emulsion.
The resin supernatant liquid prepared by embodiment 1-4 is coated on tinplate respectively, and controlling wet-film thickness is 10 μm, and then at 80 DEG C, dry 2 ~ 3h, until coating complete drying, then carries out various performance test, and result is as shown in table 1:
Table 1: the test performance data of coating
| Coating is numbered | I | Ⅱ | Ⅲ | Ⅳ | Remarks |
| Water contact angle/° | 150 | 151 | 156 | 152 | —— |
| Sticking power | 0 grade | 0 grade | 0 grade | 0 grade | GB/T9286-1998, cross cut test |
| Pencil hardness | 2H | 2H | 3H | 2H | Standard GB/T/T6739 |
As shown in Table 1, the present invention passes through SiO
2the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid that nanoparticle is in-situ modified produced, after complete drying, not only to excellent propertys such as the sticking power of tinplate isopolarity ground and coating hardness, and coating presents excellent super-hydrophobic, is all greater than 150 ° to the static contact angle of water.Reaction process of the present invention is simple, with low cost, cost performance is high, introduces SiO especially by in-situ chemical modification
2nanoparticle, degree of modification is higher, and super-hydrophobicity and other application performance of coating are all very excellent, and therefore prospects for commercial application is very bright, is worth Devoting Major Efforts To Developing to be promoted.
The above-mentioned object with reference to embodiment is to be described in detail the technology of the present invention, is illustrative instead of determinate.For a person skilled in the art; under the prerequisite not deviating from scope of the present invention and general plotting; it is apparent for making different modifications and variations according to the method for the technology of the present invention, should belong to the technology of the present invention and be sought within protection domain by official channel in the future.
Claims (9)
1. a preparation method for the super-hydrophobic resin emulsion of modified fluoride-containing vinylformic acid, is characterized in that comprising the following steps:
A, tetraethoxy and hydrophobic silane to be thrown in spirituous solution jointly, be warming up to 70 ~ 90 DEG C, and stirring reaction 4 ~ 6h, add emulsifying agent and polyvinyl alcohol again, continue to stir until material dissolves completely, stop heating and in left at room temperature ageing 10 ~ 20h, obtain hydrophobically modified SiO
2sol solution;
B, following weight parts monomers mixed obtain mix monomer:
C, by hydrophobically modified SiO
2sol solution is warming up to 75 ~ 85 DEG C, drip the initiator solution of mix monomer and 1/4 ~ 1/2 more respectively simultaneously, control time for adding is 3 ~ 5h, then disposable add 1/4 ~ 1/3 initiator solution, continue insulation reaction 0.5 ~ 1h, property adds remaining initiator solution again, and by solution warms to 85 ~ 90 DEG C, stopped reaction after continuation insulation reaction 1 ~ 3h, is cooled to room temperature.
2. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described hydrophobic silane is one or more in Union carbide A-162, dimethyldiethoxysilane and trimethylchlorosilane.
3. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that the ratio of the mole number of described tetraethoxy and hydrophobic silane is 0.1 ~ 0.9.
4. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described emulsifying agent is one or more in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10, Span-20, Span-40, Span-60, Tween-20, Tween-40, Tween-60, AES, AEO-7 and AEO-9.
5. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described hard monomer is one or more in vinylbenzene, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate and vinyl acetate.
6. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described soft monomer is one or more in ethyl propenoate, butyl acrylate and Isooctyl acrylate monomer.
7. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described functional fluoropolymer monomer is one or more in Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate and Perfluoroalkylethyl methacrylate.
8. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described initiator is one or more in ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
9. the preparation method of the super-hydrophobic resin emulsion of a kind of modified fluoride-containing vinylformic acid according to claim 1, is characterized in that described carboxylic monomer is one or more in 2-Hydroxy ethyl acrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester and trifluoroethyl methacrylate.
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