CN100556944C - Nano silicon dioxide particles enhanced super-hydrophobic polystyrene film and preparation method thereof - Google Patents
Nano silicon dioxide particles enhanced super-hydrophobic polystyrene film and preparation method thereof Download PDFInfo
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- CN100556944C CN100556944C CNB2006101137774A CN200610113777A CN100556944C CN 100556944 C CN100556944 C CN 100556944C CN B2006101137774 A CNB2006101137774 A CN B2006101137774A CN 200610113777 A CN200610113777 A CN 200610113777A CN 100556944 C CN100556944 C CN 100556944C
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Abstract
The invention belongs to the applied technical field of inorganic nano material, particularly relate to the nano silicon dioxide particles that coupling agent treatment is crossed and be dispersed in the polystyrene solution, prepare silicon dioxide microparticle enhanced super-hydrophobic polystyrene film by electrospinning with porous microsphere and nanofiber composite structure.At first adopt organo silane coupling agent modified manometer silicon dioxide particulate, then with the silicon-dioxide after the modification with the blend of polystyrene organic solution, utilize electrospinning to prepare silicon-dioxide enhanced super-hydrophobic polystyrene film at last.This film can be applicable to aspects such as fluidic harmless transports, antifouling automatic cleaning coating, microfluid.
Description
Technical field
The invention belongs to the applied technical field of inorganic nano material, particularly relate to the nano silicon dioxide particles that coupling agent treatment is crossed and be dispersed in the polystyrene solution, prepare silicon dioxide microparticle enhanced super-hydrophobic polystyrene film by electrospinning with porous microsphere and nanofiber composite structure.
Background technology
In recent years, the preparation organic-inorganic nanocomposite is a focus of material science research, is an important channel exploring high performance composite.Organic-inorganic nanocomposite has and the remarkable different performance of conventional composite materials, can make matrix material obtain good rigidity, intensity and thermostability, and can improve fracture property, workability and the dielectric properties of polymeric matrix.Because with the toughness of polymkeric substance, good processing characteristics and the organic assembling such as intensity, modulus, thermotolerance and dimensional stability of packing material, polymer matrix composite has remarkable effect and advantage in the following areas:
1. good combination property,, height ratio mould strong, low density, good toughness and dimensional stability etc. as height ratio;
2. improve the temperature tolerance of polymeric matrix, widened the material use range;
3. give that material intercepts, function such as fire-retardant;
4. but design and cut-out, globality is strong.
Polystyrene (PS) is amorphous, nonpolar linear polymer, is tasteless, odorless, nontoxic white particle.Owing on the molecular chain benzene ring substitution group is arranged, the asymmetry of molecule increases, and internal rotation is restricted, and causes common PS to present rigidity and fragility, and PS is non-crystallizable to make it have very high transparency.The topmost advantage of PS is that the transparency is good, and transmittance can reach 88%～92%, and refractive index is 1.59～1.60, electrical insulating property is good, dimensional stability height, erosion resistance, flowability, easily machine-shaping is used for high gloss parts such as injection moulding telephone set, suction cleaner, video-tape shell.But PS wears no resistance, impact is bad, weathering resistance is poor, heat-resisting not high.Utilize nanoparticle to improve polymer properties and become the focus that everybody pays close attention to.When Nano particles of silicon dioxide is evenly distributed in the polystyrene, that polymkeric substance can be enhanced is toughness reinforcing, improve fragility.Once there was the report thermal silica to be usually used in as a kind of toughener in the specialty elastomer goods such as silicon rubber,, can improves processing characteristics and other physicalies though the enhancement in plastics is very little.In polyvinyl chloride film, can increase the roughness of film surface, prevent the interlayer adhesion.In polyvinyl chloride, add white carbon black and can improve tensile strength and hardness, improve thermotolerance, prevent the thickening material migration.White carbon black is added in polypropylene or the polyethylene can play nucleator, increases nucleus quantity, dwindles the geode structure, thereby improves the transparency.Number of patent application is that the patent application of CN200410067210.9 discloses the technical scheme that adopts nano-calcium carbonate enhancing polystyrene.Aerosil strengthens the super-hydrophobic polystyrene film with porous microsphere and nanofiber composite structure and yet there are no report.The mechanical property of matrix material depends primarily on the mechanical property of fortifying fibre.Therefore, the performance by nanoparticle raising fiber plays a part crucial to improving performance of composites.
Summary of the invention
The object of the present invention is to provide nano silicon dioxide particles enhanced super-hydrophobic polystyrene film.
A further object of the present invention provides the method for preparing nano silicon dioxide particles enhanced super-hydrophobic polystyrene film by electrospinning, thereby the performance inorganic nano-particle is filled and the effect of enhanced styroflex.
An also purpose of the present invention is to provide the purposes of nano silicon dioxide particles enhanced super-hydrophobic polystyrene film.
The nano silicon dioxide particles enhanced super-hydrophobic polystyrene film that the present invention utilizes electrospinning to prepare has the porous microsphere and the nanofiber composite structure of polystyrene/silica dioxide, and the component of its film and weight percent content are:
Polystyrene 50～98.9%
Nano silicon 1～40%
Organo silane coupling agent 0.1～10%.
The size of the porous microsphere of described polystyrene/silica dioxide is 500nm～10 μ m.
The diameter of the nanofiber of described polystyrene/silica dioxide is 50nm～500nm.
Described organo silane coupling agent is selected from one or more the mixture in γ-An Bingjisanjiayangjiguiwan, methyltrimethoxy silane, trimethylethoxysilane, the poly-dimethyl silyl siloxanes etc.
The weight-average molecular weight of described polystyrene is 200,000～350,000.
The preparation method of nano silicon dioxide particles enhanced super-hydrophobic polystyrene film of the present invention at first carries out surface modification to nanometer silicon dioxide particle, it is joined carry out electrospinning in the polystyrene solution again, and this method may further comprise the steps:
(1). the coupling modification of aerosil
The certain amount of nano silica dioxide granule is joined in the organo silane coupling agent solution (ratio of nanometer silicon dioxide particle and organo silane coupling agent is 1g/ml～5g/ml), under magnetic agitation, react 24h (± 10min), reaction finishes back seasoning to solvent and volatilizees substantially, in 80 ± 5 ℃ of baking ovens, dry by the fire 2h (± 5min), obtain the nanometer silicon dioxide particle of surperficial coupling modification;
(2). the preparation of enhanced super-hydrophobic polystyrene film
Nanometer silicon dioxide particle after step (1) modification is placed polystyrene organic solution (weight ratio of nanometer silicon dioxide particle and polystyrene is 1: 15～1: 30), after in ultrasonic pond, fully disperseing dozens of hour, carry out electrospinning by electrospinning silk equipment and obtain nano silicon dioxide particles enhanced super-hydrophobic polystyrene film.
The particle diameter of described nano silicon is 10～50 nanometers.
Described organo silane coupling agent is selected from one or more the mixture in γ-An Bingjisanjiayangjiguiwan, methyltrimethoxy silane, trimethylethoxysilane, the poly-dimethyl silyl siloxanes etc.
The organic solvent of described preparation organo silane coupling agent solution comprises C
5～C
16Alkane or ether, the sherwood oil in the preferred ether, wherein the weight ratio of organic solvent and organo silane coupling agent is 10～20: 1.
The organic solvent of described preparation polystyrene organic solution is N, dinethylformamide (DMF) or tetrahydrofuran (THF) etc., and wherein the weight ratio of organic solvent and polystyrene is 2～20: 1.
Nano silicon dioxide particles enhanced super-hydrophobic polystyrene film of the present invention is of many uses, particularly harmless transports at fluidic, aspects such as antifouling automatic cleaning coating, microfluid have broad application prospects.
Method of the present invention utilizes cheap polystyrene to be raw material, with the homodisperse in polymkeric substance of the silicon-dioxide powdery after the modification, adopt a kind of simple electrospinning, prepared a kind of based superhydrophobic thin films (can obtain the porous microsphere and the nanofiber composite structure of polystyrene/silica dioxide by the molecular weight of control polystyrene) with low roll angle (less than 5 °), novel structure.The present invention prepares nano silicon dioxide particles enhanced super-hydrophobic polystyrene film method and is easy to apply.
Description of drawings
Fig. 1. the porous microsphere of the polystyrene/silica dioxide of the embodiment of the invention 1 and nanofiber composite structure stereoscan photograph.
Fig. 2. the nano silicon dioxide particles enhanced styroflex transmission electron microscope photo of the embodiment of the invention 2.
Fig. 3. the water droplet of the embodiment of the invention 3 is at the porous microsphere and the photo on the nanofiber composite structure surface (contact angle is 153.3 °) of polystyrene/silica dioxide.
Embodiment
Embodiment 1
(1). the coupling modification of nano silicon
With the 3g particle diameter is that 10～50nm nanometer silicon dioxide particle joins in the mixing solutions of γ-An Bingjisanjiayangjiguiwan 3ml and sherwood oil 45ml, and reaction is 24 hours under magnetic agitation.Reaction finishes back seasoning to solvent volatilizees fully, and baking is 2 hours in 80 ℃ of baking ovens, obtains the nanometer silicon dioxide particle of surperficial coupling modification.
(2). the preparation of super-hydrophobic polystyrene film
With the SiO after the 0.025g modification
2Particle places 0.5g polystyrene (weight-average molecular weight is 200,000) and 9.5g N, in dinethylformamide (DMF) solution, in ultrasonic pond, fully disperse after tens of hours, carry out electrospinning by electrospinning silk equipment and obtain having the porous microsphere of polystyrene/silica dioxide and the nano silicon dioxide particles enhanced super-hydrophobic polystyrene film of nanofiber composite structure, wherein, the size of the porous microsphere of described polystyrene/silica dioxide is 500nm～10 μ m, and the diameter of the nanofiber of described polystyrene/silica dioxide is 50nm～500nm.
Embodiment 2
(1). the coupling modification of nano silicon
The 3g particle diameter is joined for the 20nm nanometer silicon dioxide particle in the mixing solutions of methyltrimethoxy silane 6ml and octane 60ml, and reaction is 24 hours under magnetic agitation.Reaction finishes back seasoning to solvent volatilizees fully, and baking is 2 hours in 80 ℃ of baking ovens, obtains the nanometer silicon dioxide particle of surperficial coupling modification.
(2). the preparation of super-hydrophobic polystyrene film
With the SiO after the 0.025g modification
2Particle places 0.375g polystyrene (weight-average molecular weight is 300,000) and 5.6g N, in dinethylformamide (DMF) solution, in ultrasonic pond, fully disperse after tens of hours, carry out electrospinning by electrospinning silk equipment and obtain having the porous microsphere of polystyrene/silica dioxide and the nano silicon dioxide particles enhanced super-hydrophobic polystyrene film of nanofiber composite structure, wherein, the size of the porous microsphere of described polystyrene/silica dioxide is 700nm～8 μ m, and the diameter of the nanofiber of described polystyrene/silica dioxide is 70nm～300nm.
Embodiment 3
(1). the coupling modification of nano silicon
The 3g particle diameter is joined for the 50nm nanometer silicon dioxide particle in the mixing solutions of γ-An Bingjisanjiayangjiguiwan 3ml, poly-dimethyl silyl siloxanes 6ml and sherwood oil 180ml, and reaction is 24 hours under magnetic agitation.Reaction finishes back seasoning to solvent volatilizees fully, and baking is 2 hours in 80 ℃ of baking ovens, obtains the nanometer silicon dioxide particle of surperficial coupling modification.
(2). the preparation of super-hydrophobic polystyrene film
With the SiO after the 0.025g modification
2Particle places 0.75g polystyrene (weight-average molecular weight is 350,000) and 7.5g tetrahydrofuran solution, in ultrasonic pond, fully disperse after tens of hours, carry out electrospinning by electrospinning silk equipment and obtain having the porous microsphere of polystyrene/silica dioxide and the nano silicon dioxide particles enhanced super-hydrophobic polystyrene film of nanofiber composite structure, wherein, the size of the porous microsphere of described polystyrene/silica dioxide is 800nm～10 μ m, and the diameter of the nanofiber of described polystyrene/silica dioxide is 120nm～500nm.
Claims (5)
1. nano silicon dioxide particles enhanced super-hydrophobic polystyrene film, it is characterized in that: this film has the porous microsphere and the nanofiber composite structure of polystyrene/silica dioxide, and the component of its film and weight percent content are:
Polystyrene 50～98.9%
Nano silicon 1～40%
Organo silane coupling agent 0.1～10%
The size of the porous microsphere of described polystyrene/silica dioxide is 500nm～10 μ m;
The diameter of the nanofiber of described polystyrene/silica dioxide is 50nm～500nm;
Described organo silane coupling agent is selected from one or more the mixture in γ-An Bingjisanjiayangjiguiwan, methyltrimethoxy silane, trimethylethoxysilane, the poly-dimethyl silyl siloxanes.
2. film according to claim 1 is characterized in that: the weight-average molecular weight of described polystyrene is 200,000～350,000.
3. the preparation method according to each described film of claim 1～2 at first carries out surface modification to nanometer silicon dioxide particle, it is joined carry out electrospinning in the polystyrene organic solution again, it is characterized in that this method may further comprise the steps:
(1). the coupling modification of aerosil
Nanometer silicon dioxide particle is joined in the organo silane coupling agent solution, wherein: the ratio of nanometer silicon dioxide particle and organo silane coupling agent is 1g/ml～5g/ml, under magnetic agitation, react, reaction finishes the back seasoning to solvent evaporates, in baking oven, dry, obtain the nanometer silicon dioxide particle of surperficial coupling modification;
(2). the preparation of enhanced super-hydrophobic polystyrene film
Nanometer silicon dioxide particle after step (1) modification is placed polystyrene organic solution, wherein: the weight ratio of nanometer silicon dioxide particle and polystyrene is 1: 15～1: 30, after in ultrasonic pond, fully disperseing, carry out electrospinning by electrospinning silk equipment and obtain nano silicon dioxide particles enhanced super-hydrophobic polystyrene film;
The organic solvent of described preparation organo silane coupling agent solution is C
5～C
16Alkane or ether, wherein the weight ratio of organic solvent and organo silane coupling agent is 10～20: 1;
The organic solvent of described preparation polystyrene solution is N, dinethylformamide or tetrahydrofuran (THF), and wherein the weight ratio of organic solvent and polystyrene is 2～20: 1.
4. method according to claim 3 is characterized in that: the particle diameter of described nano silicon is 10～50 nanometers.
5. method according to claim 3 is characterized in that: described temperature of drying in baking oven is 80 ± 5 ℃.
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