CN102140179A - Method for preparing styrene grafted silicon dioxide superhydrophobic thin film - Google Patents
Method for preparing styrene grafted silicon dioxide superhydrophobic thin film Download PDFInfo
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Abstract
The invention discloses a method for preparing a styrene grafted silicon dioxide superhydrophobic thin film, which comprises: firstly, adding tetraethoxysilane into mixed solution of a catalyst and an alcohol solvent to obtain nano silicon dioxide spheres by reaction; secondly, adding the nano silicon oxide spheres into the alcohol solvent, and adding a silane coupling agent and the catalyst to obtain vinyl modified nano silicon oxide spheres; and finally, adding the vinyl modified nano silicon oxide spheres into a benzene or ketone organic solvent, adding an initiator and a styrene monomer in turn to obtain the styrene grafted silicon dioxide spheres, dispersing the styrene grafted silicon dioxide under ultrasonic waves, and preparing the styrene grafted silicon dioxide by using an organic or inorganic material as a substrate and by a coating method. The preparation process is simple and high in repeatability, the cost is low, and the promotion is more convenient.
Description
Technical field
The present invention relates to the applied technical field of organic/inorganic composite material, relate in particular to a kind of preparation method of organic-inorganic nano matrix material based superhydrophobic thin films.
Background technology
Organic is since coming out, caused that with its particular structure and performance people more and more pay attention to, organic/inorganic composite material combines the characteristics (good toughness of organic materials, shock-resistant, light weight, easily processing etc.) and advantage (high strength, the hardness of inorganic materials, thermostability, anticorrosive and excellent optical property).The organic-inorganic nano matrix material in fields such as automobile, building materials, space flight, aviation, the energy, environmental protection, biomedicines, demonstrates important researching value and application prospect as very noticeable material of 21 century.
Wetting property is one of critical nature of solid surface, mainly is made up of with micro-geometry surface chemistry to determine jointly.So-called super hydrophobic surface is meant that generally contact angle with water is greater than 150 °, roll angle is less than 10 ° surface, in general super hydrophobic surface can prepare by two kinds of methods: a kind of is to make up coarse structure on the hydrophobic material surface, and another kind is a material of modifying low surface energy on uneven surface.Originally, people are to the understanding of super hydrophobic surface, mainly from " automatically cleaning " phenomenon of leaf-lotus leaf surface.Such as, the globule can roll on the surface of lotus leaf, even water some sewage in the above, also can not stay stains on leaf.This characteristic of emerging unstained from the filth of lotus leaf is known as " automatically cleaning " effect.In recent years, the research of relevant super hydrophobic surface has caused investigator's extensive concern, relates to multi-door subjects such as phytology, chemistry, polymer science, engineering mechanics.At present, the method for preparing super-hydrophobic uneven surface mainly contains template, etching method, chemical Vapor deposition process, electrochemical method, electrospinning etc.Chinese patent (CN1379128A) adopts chemical Vapor deposition process to make super two thin film.Chinese patent (CN1397668A) is prepared the polymer nanofiber with ultra-hydrophobicity by the template extrusion process.But aforesaid method has very big limitation, and employed equipment complexity, cost costliness, preparation condition harshness can't working special-shaped surface or wide area surface, and the foraminous die plate required as template is difficult for preparation: the inapplicable field operation of electrospinning method; Employed low surface energy material (as the perfluor siloxanes) price is very expensive, and production cost is higher.Above-mentioned reason has limited practical ranges.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of cost of manufacture is low, and making processes is simple, and well organic materials and inorganic materials is combined, and has possessed the preparation method of the styrene-grafted silicon-dioxide based superhydrophobic thin films of two aspect characteristics simultaneously.
For solving the problems of the technologies described above, technical scheme of the present invention is: the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films comprises step:
Preparation nano silicon ball
Tetraethoxy is joined in the mixed solution of catalyzer and alcoholic solvent, under 25～35 ℃, reacted 8～12 hours, grind afterwards and make the nano silicon ball;
The nano silicon ball of preparation modified by vinyl
Described nano silicon ball is added in the alcoholic solvent, add silane coupling agent and catalyzer afterwards, under 25～35 ℃, reacted 8～12 hours, drying and grinding becomes powder, obtains the nano silicon ball of modified by vinyl;
Prepare styrene-grafted nano silicon ball
The nano silicon ball of described modified by vinyl is joined in benzene class or the organic solvent of ketone, add initiator afterwards successively, styrene monomer carried out graft reaction 3～7 hours between 75～95 ℃, through washing, drying, obtain styrene-grafted nano silicon ball again;
Preparation styrene-grafted silicon-dioxide based superhydrophobic thin films
Behind described styrene-grafted nano silicon ball ultra-sonic dispersion, be substrate with inorganic or organic material, make described styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method.
As optimized technical scheme, in the process of described system nano silicon ball, described catalyzer is an ammoniacal liquor, and described alcoholic solvent is methyl alcohol, ethanol or butanols, and consumption is 10～15 times of tetraethoxy, preferred 8～12 hours of reaction times, the mass ratio of described tetraethoxy and described ammoniacal liquor is 1: 1～2, and after reaction finished, alcohol was washed centrifugal three times, last 110 ℃ of dryings were pulverized after 2 hours.
As optimized technical scheme, in the process of the nano silicon ball of described system modified by vinyl, described alcoholic solvent is an ethanol, described silane coupling agent is vinyltriethoxysilane or 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, catalyzer is an ammoniacal liquor, in preferred 8～12 hours of reaction times, the mass ratio of described nano silicon ball, described ethanol, described silane coupling agent and described ammoniacal liquor is 1: 80: 9～12: 8; After reaction finished, alcohol was washed centrifugal three times, and last 110 ℃ of dryings were pulverized after 2 hours.
As optimized technical scheme, in the process of described preparation of styrene grafted nano silicon ball, described benzene class or organic solvent of ketone are toluene, dimethylbenzene or pimelinketone, described initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate, reacted preferred 3～7 hours, the nano silicon ball of modified by vinyl, initiator and styrene monomer mass ratio are 1: 0.2～0.3: 8～15; Benzene class or organic solvent of ketone consumption are 2～3 times of styrene monomer quality.
As optimized technical scheme, described inorganic or organic materials is silicon-dioxide, pottery, glass, semi-conductor, timber, macromolecular material, Mierocrystalline cellulose or ceramic tile.
Owing to adopted technique scheme, the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films, comprise step: preparation nano silicon ball, tetraethoxy is joined in the mixed solution of catalyzer and alcoholic solvent, under 25～35 ℃, reacted 8～12 hours, and ground afterwards and make the nano silicon ball; The nano silicon ball of preparation modified by vinyl adds described nano silicon ball in the alcoholic solvent, adds silane coupling agent and catalyzer afterwards, under 25～35 ℃, reacted 8～12 hours, drying and grinding becomes powder, obtains the nano silicon ball of modified by vinyl; Prepare styrene-grafted nano silicon ball, the nano silicon ball of described modified by vinyl is joined in benzene class or the organic solvent of ketone, add initiator, styrene monomer afterwards successively, between 75～95 ℃, carried out graft reaction 3～7 hours, through washing, drying, obtain styrene-grafted nano silicon ball again; Preparation styrene-grafted silicon-dioxide based superhydrophobic thin films behind described styrene-grafted nano silicon ball ultra-sonic dispersion, is substrate with inorganic or organic materials, makes described styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method; By the grafted mode, between organic phase and inorganic phase, strengthen chemical bonding, improve interface bond strength, this has not only opened up a new field for polymer modification, while also provides new approach for the preparation of super hydrophobic material, preparation process is simple, good reproducibility, need not complex chemical treatment and also do not need expensive equipment, be easy to industrialization, be convenient to promote the use of, the product surface that makes has good super-hydrophobic and self-cleaning property, and this film is tasteless nontoxic, carries in the liquid free of losses, automatically cleaning, field such as the waterproof and dampproof prospect that is widely used.
Description of drawings
Fig. 1 is the sem photograph of the based superhydrophobic thin films of the embodiment of the invention one acquisition.
Fig. 2 is the based superhydrophobic thin films of the embodiment of the invention one acquisition and the contact angle test pattern of water.
Fig. 3 is that the water droplet that obtains of the embodiment of the invention one exists form on this based superhydrophobic thin films.
Embodiment
Below in conjunction with drawings and Examples, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one:
The preparation of silicon ball:
15g ammoniacal liquor joins in the 150g dehydrated alcohol, stirs it to be mixed in 20 minutes.Use the constant voltage separating funnel, slowly drip tetraethoxy 10g, under 30 ℃, magnetic agitation reaction 10 hours, alcohol is washed centrifugal three times, and last 110 ℃ of dryings two hours are pulverized, and make the nano silicon ball.
The preparation of the silica nanosphere of modified by vinyl:
Take by weighing the above-mentioned silica nanosphere 1g that makes and place the 80g ethanol solution, disperse to stir after 10 minutes, add the 9g vinyltriethoxysilane rapidly, 8g ammoniacal liquor under 30 ℃, reacted 10 hours, alcohol is washed centrifugal three times, last 110 ℃ of dryings two hours are pulverized, and make the silica nanosphere of modified by vinyl.
Styrene-grafted nano silicon ball:
The silica nanosphere 1g of the above-mentioned modified by vinyl that makes is placed the 20g toluene organic solvent, add initiator dibenzoyl peroxide 0.3g, monomer styrene 10g, under 95 ℃, reacted 4 hours, and through washing, drying, obtained styrene-grafted nano silicon ball again.Disperseing in ultrasonic after 1 hour, is substrate with the sheet glass, prepares styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method.
As shown in Figure 1, by the electron scanning micrograph of super hydrophobic surface as seen, the coarse surface topography of this super hydrophobic surface.
As shown in Figure 2, obtained by the test of contact angle tester, the contact angle of this film surface and water is 156 °, and roll angle is 2 °.
As shown in Figure 3, there is form in the water droplet of being taken by digital camera on prepared based superhydrophobic thin films.
Embodiment two:
The preparation of silicon ball:
10g ammoniacal liquor joins in the 100g methyl alcohol, stirs it is mixed.Use the constant voltage separating funnel, slowly drip tetraethoxy 10g, under 25 ℃, magnetic agitation reaction 8 hours, alcohol is washed centrifugal three times, and last 110 ℃ of dryings two hours are pulverized.
The preparation of the silica nanosphere of modified by vinyl:
Take by weighing the above-mentioned silica nanosphere 1g that makes and place the 80g ethanol solution, disperse to stir after 10 minutes, add 12g3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane rapidly, 8g ammoniacal liquor, 25 ℃ were reacted 8 hours down, and alcohol is washed centrifugal three times, last 110 ℃ of dryings two hours are pulverized.
Styrene-grafted nano silicon ball:
The silica nanosphere 1g of the above-mentioned modified by vinyl that makes is placed 30g dimethylbenzene organic solvent, add initiator dibenzoyl peroxide 0.3g, monomer styrene 15g, under 80 ℃, reacted 3 hours, and through washing, drying, obtained styrene-grafted nano silicon ball again.Disperseing in ultrasonic after 1 hour, is substrate with the titanium dioxide silicon chip, prepares styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method.
Embodiment three:
The preparation of silicon ball:
20g ammoniacal liquor joins in the 130g dehydrated alcohol, stirs it is mixed.Use the constant voltage separating funnel, slowly drip tetraethoxy 10g, under 35 ℃, magnetic agitation reaction 12 hours, alcohol is washed centrifugal three times, and last 110 ℃ of dryings two hours are pulverized.
The preparation of the silica nanosphere of modified by vinyl:
Take by weighing the above-mentioned silica nanosphere 1g that makes and place the 80g ethanol solution, disperse to stir after 10 minutes, add the 10g vinyltriethoxysilane rapidly, 8g ammoniacal liquor, 35 ℃ were reacted 12 hours down, and alcohol is washed centrifugal three times, last 110 ℃ of dryings two hours are pulverized.
Styrene-grafted nano silicon ball:
The silica nanosphere 1g of the above-mentioned modified by vinyl that makes is placed 20g pimelinketone organic solvent, add initiator Diisopropyl azodicarboxylate 0.2g, monomer styrene 12g, under 75 ℃, reacted 7 hours, and through washing, drying, obtained styrene-grafted nano silicon ball again.Disperseing in ultrasonic after 1 hour, is substrate with the ceramic tile, prepares styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
All from the present invention is to devise, the structural transformation of having done without creative work all drops within protection scope of the present invention.
Claims (5)
1. the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films is characterized in that, comprises step:
Preparation nano silicon ball
Tetraethoxy is joined in the mixed solution of catalyzer and alcoholic solvent, under 25～35 ℃, reacted 8～12 hours, grind afterwards and make the nano silicon ball;
The nano silicon ball of preparation modified by vinyl
Described nano silicon ball is added in the alcoholic solvent, add silane coupling agent and catalyzer afterwards, under 25～35 ℃, reacted 8～12 hours, drying and grinding becomes powder, obtains the nano silicon ball of modified by vinyl;
Prepare styrene-grafted nano silicon ball
The nano silicon ball of described modified by vinyl is joined in benzene class or the organic solvent of ketone, add initiator afterwards successively, styrene monomer carried out graft reaction 3～7 hours between 75～95 ℃, through washing, drying, obtain styrene-grafted nano silicon ball again;
Preparation styrene-grafted silicon-dioxide based superhydrophobic thin films
Behind described styrene-grafted nano silicon ball ultra-sonic dispersion, be substrate with inorganic or organic materials, make described styrene-grafted silicon-dioxide based superhydrophobic thin films by coating method.
2. the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films as claimed in claim 1, it is characterized in that: in the process of described system nano silicon ball, described catalyzer is an ammoniacal liquor, described alcoholic solvent is methyl alcohol, ethanol or butanols, consumption is 10～15 times of tetraethoxy quality, in preferred 8～12 hours of reaction times, the mass ratio of described tetraethoxy and described ammoniacal liquor is 1: 1～2.
3. the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films as claimed in claim 1, it is characterized in that: in the process of the nano silicon ball of described system modified by vinyl, described alcoholic solvent is an ethanol, described silane coupling agent is vinyltriethoxysilane or 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, catalyzer is an ammoniacal liquor, in preferred 8～12 hours of reaction times, the mass ratio of described nano silicon ball, described ethanol, described silane coupling agent and described ammoniacal liquor is 1: 80: 9～12: 8.
4. the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films as claimed in claim 1; it is characterized in that: in the process of described preparation of styrene grafted nano silicon ball; described benzene class or naphthenic organic solvent are toluene, benzene or tetrahydrofuran (THF); consumption is 2～3 times of vinylbenzene quality; described initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate; reacted preferred 3～7 hours, the nano silicon ball of modified by vinyl, initiator and styrene monomer mass ratio are 1: 0.2～0.3: 8～15.
5. the preparation method of styrene-grafted silicon-dioxide based superhydrophobic thin films as claimed in claim 1 is characterized in that: described inorganic or organic materials is silicon-dioxide, pottery, glass, semi-conductor, timber, macromolecular material, Mierocrystalline cellulose or ceramic tile.
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