CN102050955A - Preparation method of polystyrene-based mesoporous silica film - Google Patents
Preparation method of polystyrene-based mesoporous silica film Download PDFInfo
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Abstract
The invention relates to a preparation method of a polystyrene-based mesoporous silica film. The preparation method comprises the following steps: carrying out surface sulfonation modification on a polystyrene slice; mixing and stirring water (H2O), ammonia water (NH3) and tetraethoxysilane (TEOS) in a mole proportion of 1:0.008:0.012 to prepare a sol solution, wherein the ammonia water serves as a catalyst, and the tetraethoxysilane serves as a silicon source; putting two electrode pads in the sole solution, deviating a polystyrene matrix to an anode plate, applying an electric field at two ends of the electrode pads, and applying an electric field at the two ends of the electrode pads for 4 hours-7 hours by using a voltage of 2.8V-4.0V; and obtaining a polystyrene-based mesoporous silica deposition film, drying and then obtaining the polystyrene-based mesoporous silica film. The film is even in thickness, the surface is smooth and has no crack, and vermicule-like mesoporous pore canals are formed and have a certain order. The preparation method in the invention is low in cost, simple to operate and easy to control, the required equipment is simple, and the large-scale production can be achieved.
Description
Technical field:
The present invention relates to a kind of preparation method of mesoporous silica film, particularly a kind of method that on the high molecular polymer matrix, prepares mesoporous silica film with sol-gel method.
Background technology:
Mesoporous silica film has various excellent physical properties: as have ultralow specific refractory power and low-k etc., excellent mechanical property, and make it have potential to use in fields such as transmitter, electronics, anti-reflection film, dura mater, multilayer film and optical materials.The preparation method of present mesoporous silica film, mostly be that silica membrane is deposited on the inorganic matrix, as: at document Thin Solid Films, 2003, among the 437:211, people such as Ford are at 400 ℃, the 6Pa oxygen pressure, the 550mJ/pulse laser energy obtains silica membrane with the silica deposit that generates under the laser repetition rate 25Hz condition on Si (001) matrix, this method preparation cost height, the equipment complexity.At document Nature, 1996, among the 379:703, people such as Yang obtain directed silica membrane in conjunction with sol-gel technique on mica substrate.The body material price that this method is used is high and frangible.At document J.Mater.Chem., 1997,7 (7): in 1285, people such as Yang utilize sol-gel technique to prepare the inorganic silicon mesopore film on regular graphite substrate.Above-mentioned bibliographical information all is to prepare silicon dioxide film on the inorganics matrix, prepares silicon dioxide film with polymkeric substance as matrix and does not appear in the newspapers.
Summary of the invention:
The invention provides a kind of method of using sol-gel method to prepare mesoporous silica film on the polystyrene matrix, the mesoporous silica film toughness height of preparing does not ftracture, and can reduce cost.
The present invention is achieved by the following technical solutions: thin polystyrene sheet is at room temperature soaked with sulfuric acid carry out the sulfonating surface modification, with the thin polystyrene sheet deionized water rinsing after the modification, oven dry obtains the polystyrene matrix; With ammoniacal liquor is catalyzer, and tetraethoxy is as the silicon source, with water, ammoniacal liquor and tetraethoxy n (H in molar ratio
2O): n (NH
3): n (TEOS)=join in reactor mixing stirring at 1: 0.008: 0.012, finally become half settled solution until two-phase system, solution to be filtered, clear filtrate at room temperature ageing obtains sol solution; Two electrode pads are put in the sol solution, the centre is left at interval, simultaneously polystyrene matrix deflection positive plate place is placed, and apply electric field, voltage 2.8V-4.0V at the pole plate two ends, under effect of electric field, silica sol particles deposits on the polystyrene matrix, applies electric field after 4 hours-7 hours, obtains polystyrene-based silica deposit film, film is dry under room temperature, obtain polystyrene-based mesoporous silica film.
P-poly-phenyl ethene of the present invention soaks with sulfuric acid and carries out the sulfonating surface modification, purpose is mol ratio and the water contact angle that changes the sulphur/carbon (S/C) of polystyrene surface, so that silicon-dioxide is deposited at the polystyrene matrix surface, has interface combination preferably, soak and generally be no less than 72 hours, the mol ratio that employing Britain Thermo VG Scientific Sigma probe x-ray photoelectron spectroscopy is measured its surperficial sulphur/carbon (S/C) after the modification adopts quiet contact angle of JC2000A/interfacial tension survey meter (Shanghai Zhongchen digital technology equipment Co., Ltd) to measure water contact angle less than 15.0 ° greater than 0.035.
Stirring of the present invention is under 20 ℃ of-30 ℃ of temperature of normal temperature, churning time 2 hours-3 hours.
The present invention adopts under electric field action, make silica sol particles be deposited on the polystyrene matrix, principle is: the silicon dioxide gel iso-electric point is about pH=2, and sol particle is electronegative under alkaline condition, sol particle is under the extra electric field effect, and anode is moved.In deposition process, apply electric field acceleration silica sol particles and on polystyrene surface, deposit, apply voltage and improve, the travelling speed of charged colloidal particles is fast more, and sedimentary film is thick more in the unit time, but travelling speed is too fast, can make thin film deposition inhomogeneous, influence material property.In addition, prolong depositing time thickness is increased, rete is blocked up, and is can stress uneven and cause cracking.So the voltage of electric field that applies, time will be regulated in right amount, the preferred 3.2V-4.0V of voltage; Apply preferred 5 hours-7 hours time of electric field.
Two electrode pads of the present invention are put in the sol solution, and the centre is left at interval and decided preferred interval 20mm-30mm according to treatment capacity and plant bulk.
The present invention places polystyrene matrix deflection positive plate place, accumulates near a large amount of sol particles of anode after helping moving and deposits in shorter time.The polystyrene matrix preferably is placed near positive plate 1mm-2mm place.
The sulfuric acid concentration that modified polystyrene of the present invention is used is the above vitriol oil of 95-98%.
Effect of the present invention: the present invention is by p-poly-phenyl vinyl surface sulfonation modifying, improve the mol ratio of polymer surfaces sulphur/carbon (S/C), reduce water contact angle, polystyrene surface becomes wetting ability by hydrophobic nature, make silicon-dioxide in polystyrene matrix surface deposition, have interface combination preferably; By regulating the suitable voltage of electric field of control, depositing time etc. make sol particle under the extra electric field effect, the anode migration.Thereby synthesize polystyrene-based mesoporous silica film, the silica membrane thickness of preparation is even, the smooth surface flawless, formation is worm meso-porous duct, has certain order, preparation method's cost of the present invention is low, and this preparation method easy and simple to handle, be easy to control, required equipment is simple, can scale operation.
Embodiment:
Below in conjunction with embodiment the present invention is done further specific descriptions, but be not limited to these embodiment.
Embodiment 1: preparation process is carried out according to the following steps
(1) modified polystyrene: with thin polystyrene sheet (15 * 15 * 2mm), be that 98% the vitriol oil soaks and carried out sulfonation modifying in 72 hours at room temperature with concentration, with the thin polystyrene sheet deionized water rinsing after the modification, dry and obtain the polystyrene matrix;
(2) preparation of sol-gel precursor liquid: with ammoniacal liquor is catalyzer, and tetraethoxy is as the silicon source, with water, ammoniacal liquor and tetraethoxy n (H in molar ratio
2O): n (NH
3): n (TEOS)=1: 0.008: 0.012 joins in the reactor and stirred 2-3 hour, finally becomes half settled solution until two-phase system, and solution is filtered, and clear filtrate ageing at room temperature 20 hours obtains sol solution;
(3) preparation of mesopore film: two electrode pads are put in the sol solution, interval 20mm, simultaneously the polystyrene matrix is placed near anode 1mm place, and applies electric field, strength of electric field 2.8V at the pole plate two ends, under effect of electric field, silica sol particles will deposit on the polystyrene matrix, apply electric field after 6 hours, obtain polystyrene-based silica deposit film, film is dry under room temperature, and making thickness is the polystyrene-based mesoporous silica film of 0.34 μ m.
Embodiment 2: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with the routine in molar ratio n (H of ammoniacal liquor, water and tetraethoxy
2O): n (NH
3): n (TEOS)=join in flask at 1: 0.008: 0.012 vigorous stirring 2-3 hour, finally becomes half settled solution until two-phase system.Solution is filtered, clear filtrate ageing at room temperature 20 hours, standby; Two electrode pads are put in the sol solution, and 20mm is placed on the polystyrene matrix simultaneously near anode 1mm place at interval, and adds external electric field voltage 3.2V at the pole plate two ends.After 6 hours, obtain polystyrene-based silica deposit film, with film dry polystyrene base mesoporous silica film under room temperature, thickness is 0.42 μ m, and film is more smooth.
Embodiment 3: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with the routine in molar ratio n (H of ammoniacal liquor, water and tetraethoxy
2O): n (NH
3): n (TEOS)=join in flask at 1: 0.008: 0.012, stirred 2-3 hour, finally become half settled solution until two-phase system.Solution is filtered, clear filtrate ageing at room temperature 20 hours, standby; Two electrode pads are put in the sol solution, and 20mm is placed on the polystyrene matrix simultaneously near anode 1mm place at interval, and adds external electric field 3.6V at the pole plate two ends.After 6 hours, obtain polystyrene-based silica deposit film, film drying under room temperature is obtained polystyrene-based mesoporous silica film, film is smooth smooth, and surperficial zero defect, thickness are 0.75 μ m, and the duct is vermiform.
Embodiment 4: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with the routine in molar ratio n (H of ammoniacal liquor, water and tetraethoxy
2O): n (NH
3): n (TEOS)=mix stirring 2-3 hour at 1: 0.008: 0.012 finally becomes half settled solution until two-phase system.Solution is filtered, clear filtrate ageing at room temperature 20 hours, standby; Two electrode pads are put in the sol solution, and 20mm is placed on the polystyrene matrix simultaneously near anode 1mm place at interval, and adds external electric field 4.0V at the pole plate two ends.After 6 hours, obtain polystyrene-based silica deposit film, film is dry under room temperature.Make polystyrene-based mesoporous silica film, thickness is 1.20 μ m.
Embodiment 5: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with the routine in molar ratio n (H of ammoniacal liquor, water and tetraethoxy
2O): n (NH
3): n (TEOS)=mixing in 1: 0.008: 0.012 was stirred 2-3 hour, become half settled solution until two-phase system, solution is filtered, clear filtrate ageing at room temperature 20 hours, two electrode pads are put in the sol solution, 20mm is placed on the polystyrene matrix near anode 1mm place at interval, and adds external electric field 3.6V at the pole plate two ends.Obtain polystyrene-based silica deposit film after 4 hours, drying makes polystyrene-based mesoporous silica film, and thickness is 0.17 μ m.
Embodiment 6: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with the routine in molar ratio n (H of ammoniacal liquor, water and tetraethoxy
2O): n (NH
3): n (TEOS)=join in flask at 1: 0.008: 0.012, stirred 2-3 hour, finally become half settled solution until two-phase system.Solution is filtered, clear filtrate ageing at room temperature 20 hours, standby; Two electrode pads are put in the sol solution, and 20mm is placed on the polystyrene matrix simultaneously near anode 1mm place at interval, and adds external electric field 3.6V at the pole plate two ends.After 5 hours, obtain polystyrene-based silica deposit film, film is dry under room temperature, make polystyrene-based mesoporous silica film, thickness is 0.40 μ m, film is more smooth smooth, does not have cracking.
Embodiment 7: the polystyrene matrix that makes with embodiment 1 step (1), at room temperature, with ammoniacal liquor, water and tetraethoxy n (H in molar ratio
2O): n (NH
3): n (TEOS)=mix stirring 2-3 hour at 1: 0.008: 0.012 finally becomes half settled solution until two-phase system.Solution is filtered, clear filtrate ageing at room temperature 20 hours, standby; Two electrode pads are put in the sol solution, and 20mm is placed on the polystyrene matrix simultaneously near anode 1mm place at interval, and adds external electric field 3.6V at the pole plate two ends.After 7 hours, obtain polystyrene-based mesoporous silicon oxide deposited film, drying.Make polystyrene-based silica membrane, thickness is 0.83 μ m, and film is smooth smooth, surperficial zero defect.
Claims (5)
1. the preparation method of a polystyrene-based mesoporous silica film, it is characterized in that, thin polystyrene sheet is at room temperature carried out the sulfonating surface modification with the sulfuric acid immersion, and with the thin polystyrene sheet deionized water rinsing after the modification, oven dry obtains the polystyrene matrix; With ammoniacal liquor is catalyzer, and tetraethoxy is as the silicon source, with water, ammoniacal liquor and tetraethoxy n (H in molar ratio
2O): n (NH
3): n (TEOS)=mix stirring at 1: 0.008: 0.012, become half settled solution until system, solution to be filtered, clear filtrate at room temperature ageing obtains sol solution; Two electrode pads are put in the sol solution, the centre is left at interval, simultaneously polystyrene matrix deflection positive plate place is placed, and apply electric field, voltage 2.8V-4.0V at the pole plate two ends, under effect of electric field, silica sol particles deposits on the polystyrene matrix, applies electric field after 4 hours-7 hours, obtains polystyrene-based silica deposit film, film is dry under room temperature, obtain polystyrene-based mesoporous silica film.
2. according to the preparation method of claim 1, it is characterized in that described stirring is under 20 ℃ of-30 ℃ of temperature of normal temperature, churning time 2 hours-3 hours.
3. according to the preparation method of claim 1, it is characterized in that the described voltage of electric field that applies is 3.2V-4.0V; The time that applies electric field is 5 hours-7 hours.
4. according to the preparation method of claim 1, it is characterized in that, leave in the middle of described two electrode pads and be spaced apart 20mm-30mm.
5. according to the preparation method of claim 1, it is characterized in that, described with polystyrene matrix deflection positive plate 1mm-2mm place's placement.
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| CN106278371A (en) * | 2016-09-30 | 2017-01-04 | 温州生物材料与工程研究所 | A kind of functional hierarchical three-dimensional porous silica-base film preparation method and biologic applications thereof |
| CN106693715A (en) * | 2016-11-22 | 2017-05-24 | 扬州大学 | Electric field coating process of ultrafiltration membrane |
| CN112616853A (en) * | 2020-04-03 | 2021-04-09 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN115091828A (en) * | 2022-06-30 | 2022-09-23 | 江苏耀鸿电子有限公司 | High-corrosion-resistance and high-toughness PPO resin-based copper-clad plate and preparation method thereof |
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| CN103194774A (en) * | 2012-03-03 | 2013-07-10 | 曲阜师范大学 | Preparation method and use of Pd nano-rod array/sol-gel membrane-modified electrode |
| CN103194774B (en) * | 2012-03-03 | 2016-03-30 | 曲阜师范大学 | The preparation method and application of Pd nanometer stick array/sol-gel film modified electrode |
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| CN106278371B (en) * | 2016-09-30 | 2019-05-14 | 温州生物材料与工程研究所 | A kind of three-dimensional porous silica-base film preparation method of functionality hierarchical and its biologic applications |
| CN106693715A (en) * | 2016-11-22 | 2017-05-24 | 扬州大学 | Electric field coating process of ultrafiltration membrane |
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| CN112616853A (en) * | 2020-04-03 | 2021-04-09 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN115091828A (en) * | 2022-06-30 | 2022-09-23 | 江苏耀鸿电子有限公司 | High-corrosion-resistance and high-toughness PPO resin-based copper-clad plate and preparation method thereof |
| CN115193421A (en) * | 2022-09-16 | 2022-10-18 | 临沂市冠宇工业科技有限公司 | Preparation method of sewage treatment adsorbent |
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